BIOLOGICALLY IIMPORTANT COf4POUNDS I14 SYNFUELS PROCESSES*. 8. R. C l a r k , C.-h. Ho, W. H.

G r i e s t , and 14. R. G u e r i n . A n a l y t i c a l C h e m i s t r y D i v i s i o n , Oak Ridge N a t i o n a l Labora-

t o r y , P . 0. Box X, Oak Ridge, Tennessee 37830.

Crude products, b y - p r o d u c t s and wastes f r o m s y n f u e l processes c o n t a i n a broad spec-

t r u m o f chemical compounds--many o f w h i c h a r e a c t i v e i n b i o l o g i c a l systems. D i s c e r n i n g
which compound c l a s s e s a r e most i m p o r t a n t i s necessary i n o r d e r t o e s t a b l i s h e f f e c t i v e
c o n t r o l o v e r r e l e a s e o r exposure. P o l y c y c l i c a r o m a t i c hydrocarbons (PAH), mu1 t i - a 1 k y l -
a t e d PAH, p r i m a r y a r o m a t i c amines and N - h e t e r o c y c l i c PAH a r e s i g n i f i c a n t c o n t r i b u t o r s t o
t h e o v e r a l l mutagenic a c t i v i t i e s o f a l a r g e number o f m a t e r i a l s examined. Ames t e s t d a t a
show t h a t t h e b a s i c , p r i m a r y a r o m a t i c amine f r a c t i o n i s t h e most a c t i v e . PAHs, m u l t i -
a l k y l a t e d PAHs and N - h e t e r o c y c l i c PAHs a r e a l l components o f t h e n e u t r a l f r a c t i o n . In
n e a r l y a l l cases, t h e n e u t r a l f r a c t i o n s c o n t r i b u t e t h e l a r g e s t p o r t i o n o f t h e mutagenic
a c t i v i t y , w h i l e t h e b a s i c p r i m a r y a r o m a t i c amine f r a c t i o n s have t h e h i g h e s t s p e c i f i c
a c t i v i t y . N e u t r a l f r a c t i o n s a r e u s u a l l y t h e l a r g e s t ( w t x ) whereas t h e t o t a l b a s i c f r a c -
t i o n s a r e m a l ? by comparison; t h u s , t h e o v e r a l l g r e a t e r c o n t r i b u t i o n o f t h e n e u t r a l
f r a c t i o n t o t h e mutagenic a c t i v i t y o f most samples. B i o l o g i c a l l y a c t i v e c o n s t i t u e n t s a r e
i s o l a t e d i n p r e p a r a t i v e s c a l e amounts f r o m complex m i x t u r e s u t i l i z i n g c o m b i n a t i o n s o f
l i q u i d - l i q u i d e x t r a c t i o n and v a r i o u s 1 i q u i d chromatographic c o l u m n - e l u e n t c o m b i n a t i o n s .
F r a c t i o n s a r e c h a r a c t e r i z e d u s i n g a c o m b i n a t i o n o f s p e c t r o s c o p i c t e c h n i q u e s and gas
chromatography/mass s p e c t r o r r e t r y . (*Research sponsored by t h e O f f i c e o f H e a l t h and
Environmental Research, Cepartment o f Energy, under c o n t r a c t 1.1-7405-eng-26 w i t h t h e
Union Carbide C o r p o r a t i o n . )

1
 THE ELEMENTAL COMPOSITION OF SHALE OILS. J. P. Fox. Energy and Environment Divisiob
Lawrence Berkeley L a b o r a t o r y , U n i v e r s i t y of C a l i f o r n i a , Berkeley, CA 94720.

The abundance of 47 e l e m e n t s were measured i n 1 2 s h a l e o i l s from LETC's c o n t r o l l e d -

s t a t e retort, 7 s h a l e o i l s from LLL'S 125-kg s i m u l a t e d i n - s i t u r e t o r t and i n o i l s from
t h e G e o k i n e t i c s , O c c i d e n t a l , E q u i t y and Paraho p r o c e s s e s u s i n g n e u t r o n a c t i v a t i o n
a n a l y s i s , x-ray f l u o r e s c e n c e s p e c t r o m e t r y and Zeeman atomic a b s o r p t i o n s p e c t r o s c o p y .
The elements s t u d i e d i n c l u d e C , H, N , A s , Se, Co, N i , Fe, Mn, Zn, U, C 1 , N a and o t h e r s .
The r e s u l t i n g d a t a were analyzed t o d e t a r m i n e t h e e f f e c t of r e t o r t o p e r a t i n g c o n d i t i o n s
on measured e l e m e n t a l abundances.

T h i s paper compares t h e e l e m e n t a l abundances i n o i l s from s i m u l a t e d , s u r f a c e and i n

s i t u p r o c e s s e s i n t h e framework o f r e t o r t o p e r a t i n g c o n d i t i o n s and d i s c u s s e s t h e poten-
t i a l environmental i m p l i c a t i o n s o f observed t r a c e element p a t t e r n s . T h i s i n v e s t i g a t i o n
i n d i c a t e s t h a t t h e major elements i n s h a l e o i l s ( > l o ppm) a r e C , H , N , S , Fe, A s , C 1 and
Na. The elements A l , B a , Co, C r , Cu, Hg, Mg, Mn, Mo, N i , Se, V and Zn O C C U K a t concen-
t r a t i o n s of from 0 . 1 ppm t o less t h a n 10 ppm. A l l o t h e r elements s t u d i e d occured a t less
t h a n 0 . 1 ppm i n most o i l s . S t r i k i n g d i f f e r e n c e s were observed between t h e e l e m e n t a l
abundances o f Antrim, Moroccan and Green R i v e r s h a l e o i l s .

2
 ANALYSIS OF ENERGY WASTE EFFLUENTS FOR ORGANIC CHEMICALS U S I N G THE MASTER ANALYTICAL
SCHEXE. Linda Sheldon, S h i r l e y Yung, Roger Wiseman, Larry Michael, and Edo P e l l i Z Z a r i
A n a l y t i c a l S c i e n c e s D i v i s i o n , Chemistry and L i f e S c i e n c e s Group, Research T r i a n g l e
I n s t i t u t e , P. 0. Box 12194, Research T r i a n g l e Park, NC 27709.

A v a r i e t y of a n a l y t i c a l methods were t e s t e d d u r i n g t h e development of a comprehen-

s i v e scheme t o i d e n t i f y and q u a n t i t a t e v o l a t i l e o r g a n i c chemicals i n aqueous samples
u s i n g high r e s o l u t i o n g a s chromatographylmass spectrometrylcomputer (GCI?fS/CO?P) a s t h e
major a n a l y t i c a l t o o l . V o l a t i l e o r g a n i c s a r e d e f i n e d a s t h o s e compounds which w i l l ei-
t h e r e l u t e from a GC column a t 3OO9C i n one hour o r less o r which may be d e r i v a t i z e d t o
meet t h e s e c r i t e r i a .
Highly v o l a t i l e (bp <175'C), hydrophobic compounds were analyzed u s i n g a modified
purge and t r a p procedure. S o l v e n t e x t r a c t i o n w i t h pH a d j u s t m e n t served t o c o n c e n t r a t e
t h e less v o l a t i l e (bp ,175'C) hydrophobic compounds. I o n i c o r g a n i c s were c o n c e n t r a t e d
by i o n exchange, then chemically d e r i v a t i z e d p r i o r t o g a s chromatography. L a s t l y ,
v o l a t i l e p o l a r o r g a n i c s were c o n c e n t r a t e d by f r a c t i o n a l d i s t i l l a t i o n . A s an a l t e r n a t i v e
t o d i r e c t aqueous i n j e c t i o n , t h e d i s t i l l a t e was i n j e c t e d o n t o a Tenax GC precolumn
through a h e a t e d i n j e c t i o n p o r t , t h e w a t e r v e n t e d , and t h e o r g a n i c s were t h e r m a l l y
desorbed i n t o a g a s chromatograph. For energy waste e f f l u e n t s , methods which gave a
minimum d e t e c t i o n l i m i t o f 1 0 ppb w i t h 40% recovery were considered a c c e p t a b l e .
Developed methods were t e s t e d on a v a r i e t y of s p i k e d and unspiked sample w a t e r s
i n c l u d i n g energy waste e f f l u e n t s . S p e c i f i c problems w i t h t h i s sample m a t r i x and t e s t
r e s u l t s w i l l be p r e s e n t e d . T h i s r e s e a r c h w a s supported by EPA C o n t r a c t No. 68-03-2704.

3
 TRACE ELEMENT BEHAVIOR I N THE SOLVENT REFINED COAL PROCESSES. R. H. F i l b S. R.
K h a l i l , * and M. L. Hunt. Nuclear R a d i a t i o n Center, Washington d k i t y ,
Pullman, Washington 991 64.

High s u l f u r c o a l s c o n t a i n s i g n i f i c a n t q u a n t i t i e s o f t r a c e metals which may have un-

d e s i r a b l e e f f e c t s on l i q u e f a c t i o n processes, on upgrading o f d e r i v e d syncrudes, o r on
t h e environment. A s t u d y o f t h e f a t e of up t o 35 t r a c e elements i n t h e SRC I and SRC I 1
processes b y n e u t r o n a c t i v a t i o n a n a l y s i s (NAA) and atomic a b s o r p t i o n spectroscopy (AAS)
shows t h a t s i g n i f i c a n t emissions o f t o x i c elements from t h e F o r t Lewis, Washington 50
t o n p e r day p i l o t p l d n t ( o p e r a t e d by P i t t s b u r g & Midway Coal M i n i n g Co.) occur and t h a t ,
except f o r Hg i n t h e SRC I1 process s a t i s f a c t o r y m a t e r i a l balances can be o b t a i n e d f o r
SRC I and SRC I1 processes. I n t h e case o f Hg i n t h e SRC I 1 process, and t o a l e s s e r
e x t e n t As, Se and Sb, t r a n s p o r t v i a gaseous streams has been demonstrated and can be
r e l a t e d t o t h e v o l a t i l i t y and r e a c t i o n s o f HgO, HgS, H2Se, A s O , e t c . The NAA and AAS
techniques and t h e i r a p p l i c a t i o n t o t h e complex m a t r i c e s e n c o h t e r e d i n coal l i q u e f a c -
t i o n processes a r e discussed.

P r e s e n t l y a t U n i v e r s i t y o f Kentucky

4
 CHARACTERIZATION AND MUTAGENICITY OF SHALE OIL FRACTIONS, Deborah S. Sklarew,
Donald M. Schoengold, R i c h a r d A. P e l r o y t , S y l v i a P. Downey, Barbara A . Vieux,
James T. Crestot, P h y s i c a l Sciences Dept. and B i o l o g y Oept.t, P a c i f i c Northwest
L a b o r a t o r y , o p e r a t e d f o r t h e Department o f Energy by B a t t e l l e Memorial I n s t i t u t e

Product o i l s from s e v e r a l s h a l e o i l o p e r a t i o n s have been analyzed f o r o r g a n i c compounds

w h i c h a r e p o t e n t i a l biological/environmental hazards. Two f r a c t i o n a t i o n schemes have
been compared b o t h from an a n a l y t i c a l and a b i o l o g i c a l p o i n t o f view. The f i r s t method
i n v o l v e s a c i d - b a s e f r a c t i o n a t i o n ; t h e second uses p a r t i t i o n chromatography o n Sephadex
LH-20. F r a c t i o n s have been t e s t e d f o r m u t a g e n i c i t y i n t h e Ames assay and those which
gave p o s i t i v e r e s u l t s were f u r t h e r s u b d i v i d e d and analyzed by gas chromatography-mass
s p e c t r o m e t r y . I n t h e case o f t h e Sephadex LH-20 method, m u t a g e n i c i t y i s c o n c e n t r a t e d
i n t h e methanol f r a c t i o n s ; i n t h e acid-base s e p a r a t i o n , m u t a g e n i c i t y i s f o u n d i n t h e
b a s i c and t a r f r a c t i o n s .

5
 COMPARISON AND CONTRAST OF TRACE ELOIENTS IN CRUDE SHALE OILS AND PETROLEUM
C . L . Wilkerson, D . 5 . Sklarew, J . C . Evans and J . S. Fruchter,Pacific Flortliwest
Laboratory, Richland, WA 99352

The abundances and chemical forms of a large group of elements including t h e t r a c e metals
A s , Co, Fe, Elo, Ni, Se, V and Zn were determined i n three whole and fractionated shale
o i l s obtained from Colorado and Utah o i l shale reserves. The crude shale o i l s were rep-
resentative product o i l s from a n above-ground, a modified i n - s i t u , and a t r u e i n - s i t u
r e t o r t i n g process and were produced by p i l o t plant or larger sized f a c i l i t i e s . Elemen-
t a l abundances were determined by several modern analytical techniques including instru-
mental neutron a c t i v a t i o n a n a l y s i s , energy dispersive X-ray fluorescence a n a l y s i s ,
prompt y-ray a c t i v a t i o n a n a l y s i s , and plasma emission spectrometry. The analyses were
compared to identify major differences between elemental partitioning y i e l d s of the
various retorting technologies and were f u r t h e r compared and contrasted with reported
elemental concentrations i n petroleum. The elements As and Fe were found t o be the
most prominent t r a c e metals i n t h e shale o i l m a t r i x and As and Se l e v e l s were observed
t o be 1 to 2 orders of magnitude g r e a t e r than those reported f o r petroleum.

6
 ENVIRONMENTAL ORGANIC CHEMISTRY: THE ISOLATION AND IDENTIFICATION OF ORGANIC AXD
ORGANOMETALLIC COMPOUNDS FROM OIL SHALE RETORT WATERS.* Richard H. Fish and Mathilde
J. Kland. Energy and Environment Division, Lawrence Berkeley Laboratory, University
of California, Berkeley, CA 94720.

The complex nature of the inorganic, organic and organometallic contaminants found i n
oil shale retort waters is important to elucidate in order to evaluate the potential
problems connected with the release of these compounds to the environment.

Our efforts have focused on more clearly defining the organic and the organometallic
species, either synth.xized o r released during the retorting process, that eventually
end up in the retort waters. Retort waters from LLL and LETC simulated in situ retorts
and from Occidental's Logan Wash experiments were extracted with methylene chloride and
the components separated and analyzed by a combination of dry column, thin layer and high
performance liquid chromatography as well as capillary gas chromatography-mass spectro-
metry and nuclear magnetic resonance spectroscopy.

A discussion of the classes of organic and organometallic species identifed, together

with some of their toxicological and environmental implications, will be presented.

C + . . r l l - ~SuDDorted through the Department of Energy under contract no. W-7405-ENG-48.

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 INTERLABORATORY COMPARISON OF ENVIRONMENTAL ANALYSES ASSOCIATED W I T H SYNFUEL
PRODUCTION, W. E . Play, J. M. Brown, S . N . C h e s l e r , F. R . Guenther, H . S . H e r t z ,
L. R. H i l p e r t , R. Pi. P a r r i s , K . L . R i t c h i e , and S . A. Wise, Center f o r A n a l y t i c a l Chemis-
t r y , National Bureau of S t a n d a r d s , Washington, DC 20234
I n o r d e r t o b e g i n e v a l u a t i n g t h e s t a t e - o f - t h e - a r t of t h e d e t e r m i n a t i o n of p o l l u t a n t s
a s s o c i a t e d w i t h t h e p r o d u c t i o n of a l t e r n a t e f u e l s , seven c o l l a b o r a t i v e s t u d i e s have
been conducted by NBS. The aim of t h e f i v e i n i t i a l s t u d i e s w a s t o a s c e r t a i n how w e l l
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 could p e r f o m t h e f i n a l q u a n t i t a t i o n s t e p i n a t r a c e
o r g a n i c a n a l y t i c a l scheme. The m a t e r i a l s examined in t h e s e i n i t i a l s t u d i e s were two
polynuclear a r o m a t i c hydrocarbon in hexane samples, a phenols i n water sample, a
phenols i n hexane sample and a N-heterocyclic compounds ( a z a a r e n e s ) i n hexane sample.
Each of t h e s e samples c o n t a i n e d between f i v e and e i g h t pure compounds, w i t h each
compound being p r e s e n t a t t h e 1-100 pg/mL (ppm) l e v e l .
The l a s t two c o l l a b o r a t i v e s t u d i e s involved q u a n t i a t i a v e a n a l y s e s of s e l e c t e d
phenols, polynuclear a r o m a t i c hydrocarbons and N - h e t e r o c y c l i c s i n a s h a l e o i l and a
s o l v e n t r e f i n e d c o a l (SRC) material. Such a n a l y s e s u s u a l l y r e q u i r e d a minimum o f
t h r e e steps: (1) I s o l a t i o n of t h e a n a l y t e from t h e sample m a t r i x ; (2) S e p a r a t i o n of
t h e a n a l y t e from n o n - a n a l y t e i n t e r f e r e n c e ; ( 3 ) measurement o f d e t e c t o r r e s p o n s e f o r
t h e a n a l y t e and r e l a t i n g t h a t t o t h e c o n c e n t r a t i o n of the a n a l y t e i n t h e o r i g i n a l
sample. The r e s u l t s of t h e s e c o l l a b o r a t i v e s t u d i e s w i l l be r e p o r t e d and d i s c u s s e d
a l o n g w i t h methodologies developed a t NBS f o r c e r t i f y i n g t h e c o n c e n t r a t i o n of s e l e c t e d
phenols, PAH and N-heterocylces i n a l t e r n a t e f u e l s .
 ANALYSIS OF SULFUR HETEROCYCLES IN COAL-DERIVED PRODUCTS AND SHALE OILS? C. W i l l e l
M. Iwao, T. A . Broadbent, R. N. Castle, and M. L . Lee, Department o f Chemistry,
Brigham Young U n i v e r s i t y , Provo, Utah 84602.

The c a r c i n o g e n i c a c t i v i t y demonstrated by complex m i x t u r e s o f p o l y c y c l i c a r o m a t i c

compounds (PAC) has s t i m u l a t e d much e f f o r t by researchers t o i d e n t i f y i n d i v i d u a l mixturc
components. Found i n l o w c o n c e n t r a t i o n s among t h e m i x t u r e components o f most PAC
f r a c t i o n s from c o a l - d e r i v e d products and s h a l e o i l s a r e t h e s u l f u r h e t e r o c y c l e s . Due
t o t h e i r low c o n c e n t r a t i o n s , an enrichment o f t h e h e t e r o c y c l i c s u l f u r compounds i s
necessary f o r i d e n t i f i c a t i o n . A r e c e n t l y developed method t o i s o l a t e t h e s u l f u r
h e t e r o c y c l e f r a c t i o n from a composite aromatic f r a c t i o n has g r e a t l y a i d e d e f f o r t s t o
separate and i d e n t i f y i n d i v i d u a l h e t e r o c y c l i c s u l f u r compounds by g l a s s c a p i l l a r y gas
chromatographic mass s p e c t r o m e t r y .
I n t h i s study, t h e developed methodology f o r t h e enrichment and subsequent s e p a r a t i o n
and i d e n t i f i c a t i o n o f s u l f u r h e t e r o c y c l e f r a c t i o n s has been a p p l i e d t o s e l e c t e d c o a l
g a s i f i c a t i o n t a r s , c o a l l i q u i d s , and s h a l e o i l s . I d e n t i f i c a t i o n was accomplished
through comparison o f mass s p e c t r a l and chromatographic r e t e n t i o n d a t a o f m i x t u r e
components H i t h standard r e f e r e n c e compounds.
Since few standard r e f e r e n c e compounds o f s u l f u r h e t e r o c y c l e s a r e commercially
a v a i l a b l e , compounds p r e d i c t e d by mass spectrometry t o be p r e s e n t i n e n r i c h e d s u l f u r
h e t e r o c y c l e f r a c t i o n s were synthesized. These compounds were used t o o b t a i n chromato-
g r a p h i c r e t e n t i o n d a t a and f o r b i o l o g i c a l t e s t i n g .
*This s t u d y was supported by the U . S . Department o f Energy, D i v i s i o n o f Biomedical
and Environmental Research, C o n t r a c t No. DE-ACOZ-79EV10237.

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THE IIQR(Tp CF "NO A C I M " . J. G. Seay, -titUte Of G3S T&lxlOkX~y, 3436 S. S t a t e
St. Chicago IL 60616.

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,
15
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 TRANSPORTATION FUEIS F R O M SYNTHESIS GAS. R. H . F i s c h e r a n d R . E . H i l d e b r a n d . U.S.
Department o f Energy O f f i c e o f F o s s i l ElleKgy r o g r a m s , D i v i s i o n o f F o s s i l F u e l
P r o c e s s i n g , M a i l s t o p E - j 3 8 / G e n ~ n t o w n , Washington: 20545.
ABSTRACT
The Department of Energy (WE) h a s f o r m u l a t e d a program t o d e v e l o p improved p r o c e s s e s
t o c o n v e r t s y n t h e s i s g a s f r o m c o a l t o q u a l i t y t r a n s p o r t a t i o n f u e l s . T h e program i n v o l v e s
f o u r elements.
Improved i n t e g r a t i o n o f g a s i f i c a t i o n w i t h l i q u e f a c t i o n . T h i s i n v o l v e s t h e use of low
r a t i o H2 t o CO s y n t h e s i s g a s i n t h e h y d r o c a r b o n f o r m a t i o n s t e p . Low r a t i o H2 t o CO
c a n be c o n v e r t e d t o h y d r o c a r b o n by means o f t h e K o l b e l - E n g e l h a r d t r e a c t i o n . The n e t
r e s u l t i s considerable energy savings i n steam.
Improved s e l e c t i v i t y b u s e of s h a p e s e l e c t i v e c a t a l y s t . Normal F i s c h e r - T r o p s c h re-
a c t i o n c h e m i s t r y is s u g j e c t t o i n h e r e n t l i m i t a t i o n s due t o t h e c h a i n growthmechanisms.
Use o f s h a p e s e l e c t i v e c a t a l y s t s c a n r e s u l t i n c i r c u m v e n t i o n of t h i s l i m i t a t i o n by t h e
u s e o f a n i n t e r m e d i a t e t h a t c a n be formed i n h i g h s e l e c t i v i t y ( m e i h a n o l ) or b y i n h i b i -
tioi

The i n i t i a l c o n t r a c t s i n t h i s program a r e a b o u t t o be s i g n e d and o t h e r s are b e g i n n i n g

n e g o t i a t i o n . The g o a l s o f t h e program a n d t h i s up coming work w i l l be d i s c u s s e d .

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EVIDENCE FOR ADSORBED HYDROCARBON INTERMEDIATES DURING THE INITIAL STAGES OF CO
HYDROGENATION ON IRON

H.P. Bonze1 and H.J. Krebs

Institut fur Grenzfllchenforschung und Vakuumphysik, Kernforschungsanlage Julich,

D-5170 Jiilich, Germany

1. Introduction
Surface science techniques have been applied to the study of the surface
properties of the transition metals Fe, Co, Ni and Ru /1-12/ and it is natural
to extend the same approach to the study of Fischer-Tropsch synthesis (FTS) re-
actions on the same metal surfaces. However, reaction products in the adsorbed
or gaseous phase apparently cannot be detected under vacuum conditions. There-
fore, in order to utilize surface analytical techniques for the study of FTS, a
combination of a surface analysis ultra-high vacuum system and an atmospheric
reaction chamber has to be used, such as pioneered by Somorjai and coworkers /13,
141.
In this paper we report on the use of such a combination apparatus of novel
design with Auger electron (AES) and X-ray photoelectron spectroscopy (XPS) as
analytical capabilities and a differential microreactor. The analysis of the re-
action products is performed by gas chromatography (GC). Using this system we
studied the hydrogenation of CO on polycrystalline iron foils and a Fe(ll0)
single crystal at a total pressure of 100 kPa (= 1 bar 1 atm) / 1 5 / .

2. Experimental
The experimental system, sketched in Fig. 1, consisted of a stainless steel
ultra-high-vacuum (UHV) chamber pumped by an ion pump, and an attached sample
transfer system containing a small micro-reactor. The UHV chamber shown on the
left hand side of Fig. 1 operates at a base pressure of 1 x lo-' Pa. This system
(Leybold-Heraeus) features an ion sputter gun for surface cleaning, an electron
gun, X-ray sour.ce and high resolution electron spectrometer for Auger electron
(AES) and photoelectron (XPS) spectroscopies, and a quadrupole mass spectrometer
for residual gas analysis. The sample is either a polycrystalline iron foil about
0.1 nun thick, or a Fe(ll0) single crystal, with an active area of 0.35 cm2. It is
situated at a cutout portion of a stainless steel rod of 2 cm diameter. This rod
serves as a transfer mechanism between UHV chamber, micro-reactor and atmosphere.
The Fe sample can be heated resistively up to 1400 K in vacuum and about 900 K in
100 kPa of a H,/CO mixture. The temperature of the sample is measured by a
sheathed Chromel-Alumel thermocouple attached to the underside of the sample.
The micro-reactor of about 4 cm' total volume is a small section of the
sample transfer system, Fig. 1. A mixture of CO and H, was passed continuously
through this reactor at a rate of 50 cm3/min. The partial pressure ratio of CO
to H, was fixed by adjusting the individual flow rates of these two gases before
entering the mixing stage. Partial pressure ratios of CO to H, from 1:lOO to 1 : 4
could be easily chosen.
The transfer of the Fe-foil from the UHV system into the micro-reactor was
accomplished by pulling the sample rod until the sample was located inside the
reactor. The sample could be moved to the atmospheric loading position i n a si-
milar way, and also back into the UHV chamber. The transfer time from the reactor
into the UHV position including pump-down to Pa was 45 seconds. The sample
rod itself is water cooled such that during heating of the Fe sample inside the
micro-reactor no parts other than the sample and the tip of the thermocouple get
hot. During the catalytic rate measurements the hydrocarbon products were ana-
lyzed by gas chromatography. A 0.5 cm3 sample (loop volume) of the gas mixture
was taken by the GC sample valve and passed over a 8 ft. Porapak Q column. The
separated products were analyzed by a flame ionization detector.
The Fischer-Tropsch measurements were carried out in the following way: The
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c l e a n e d F e sample w a s t r a n s f e r e d from UHV i n t o t h e m i c r o - r e a c t o r where a s t e a d y
s t a t e gas f l o w was a l r e a d y e s t a b l i s h e d . As soon a s t h e sample came t o a h a l t , t h e
t e m p e r a t u r e was r a i s e d t o t h e d e s i r e d v a l u e a s measured by t h e thermocouple. From
t h i s p o i n t on t h e t i m e was measured and GC samples were t a k e n p e r i o d i c a l l y . A t a
l a t e r time t h e r e a c t i o n was s t o p p e d by t u r n i n g o f f t h e h e a t i n g c u r r e n t . About 4
s e c l a t e r t h e sample was t r a n s f e r e d back t o UHV f o r s u r f a c e a n a l y s i s by AES o r
XPS .
3 . R e s u l t s and D i s c u s s i o n
The measurements of FTS from CO and H, on Fe were c a r r i e d o u t a t a t o t a l
p r e s s u r e of 100 kPa (=1 a t m ) and CO/H, r a t i o s o f 1:100, 1:20 and 1:4. The tempe-
r a t u r e r a n g e i n v e s t i g a t e d w a s 460-750 K. I n a l l c a s e s methane was t h e dominant
p r o d u c t and i t s r a t e of f o r m a t i o n t i m e d e p e n d e n t . In o r d e r t o check t h i s time d e -
pendence, a s e r i e s of GC r e a c t i v i t y measurements w i t h a c y c l e of a p p r o x i m a t e l y
100 s e c was c a r r i e d o u t at t h e same t e m p e r a t u r e . Three examples of such c u r v e s
a r e shown i n F i g . 2 f o r a CO/H, r a t i o of 1:20 and d i f f e r e n t t e m p e r a t u r e s where
t h e l o g a r i t h m of t h e t u r n o v e r number f o r methane i s p l o t t e d as a f u n c t i o n of t i m e .
These curves e x h i b i t s e v e r a l i n t e r e s t i n g f e a t u r e s : F i r s t , t h e r e i s a s t r o n g r i s e
i n t h e methane r a t e of f o r m a t i o n w i t h i n t h e f i r s t 40-60 s e c a f t e r r e a c h i n g t h e
r e a c t i o n t e m p e r a t u r e . T h i s r i s e s i g n a l s t h e s t a r t of t h e r e a c t i o n , and t h e appa-
r e n t d e l a y o f a b o u t 30 s e c p r i o r t o t h e r i s e (which i s more o b v i o u s i n a l i n e a r
p l o t of r a t e v e r s u s t i m e ) r e p r e s e n t s t h e t i m e i t t a k e s f o r t h e g a s t o f l o w from
t h e r e a c t o r t o t h e GC s a m p l i n g v a l v e . Second, t h e r e i s a maximum i n t h e r a t e o f
methane f o r m a t i o n f o l l o w e d b y a s t e a d y d e c l i n e ; b o t h t h e p o s i t i o n of t h e maximum
a n d t h e s l o p e of t h e d e c l i n e depend on t h e t e m p e r a t u r e of t h e F e - f o i l and t h e
CO/H, r a t i o .
The o c c u r e n c e of t h e maximum i n t h e s e c u r v e s of F i g . 2 i s c o n n e c t e d w i t h t h e
known pehnomenon of c a r b o n a c c u m u l a t i o n on t h e Fe s u r f a c e a s a f u n c t i o n o f t i m e
/ 1 4 , 1 5 / . The r a t e o f c a r b o n a c c u m u l a t i o n i s f a s t e r , t h e h i g h e r t h e t e m p e r a t u r e o r
t h e h i g h e r ‘ t h e r a t i o of CO/H,. However, t h e i n f l u e n c e of t h e r a t e of c a r b o n accu-
m u l a t i o n o n t h e r a t e of CO h y d r o g e n a t i o n i s c o m p l i c a t e d due t o d i f f e r e n t k i n d s of
c h e m i c a l l y bound c a r b o n . We h a v e measured t h e r e l a t i v e c a r b o n c o n c e n t r a t i o n by
XPS and p r e s e n t as a n example t h e d a t a i n F i g . 3. T h i s f i g u r e shows t h e c a r b o n
( I s ) s i g n a l a t d i f f e r e n t r e a c t i o n times f o r s i m i l a r e x p e r i m e n t a l c o n d i t i o n s a s
t h o s e of F i g . 2 . In t h e s e e x p e r i m e n t s t h e Fe sample w a s moved i n t o t h e micro-
r e a c t o r for r e a c t i o n f o r a s h o r t t i m e , t h e n i n t o t h e UHV chamber f o r s u r f a c e (AES
o r XPS) a n a l y s i s , a n d b a c k i n t o t h e r e a c t o r f o r a c o n t i n u a t i o n of t h e r e a c t i o n .
The d a t a i n F i g . 3 i l l u s t r a t e t h e r a p i d i n c r e a s e i n s u r f a c e c a r b o n concen-
t r a t i o n a s a f u n c t i o n of t h e r e a c t i o n t i m e and a l s o a s h i f t i n t h e b i n d i n g e n e r g y
EB of t h e C l s l e v e l from a b o u t 283.9 eV t o 284.6 e V . F i g u r e 4 a shows t h e s h i f t i n
EB(CIS) v e r s u s t i m e f o r a p a r t i c u l a r r u n a t 530 K and CO/H, = 1:20. F i g u r e 4b
Shows t h e c o r r e s p o n d i n g i n t e g r a t e d C I S peak a r e a v e r s u s time. Note i n F i g s . 4a
and 4b t h a t t h e i n i t i a l c h a n g e i n t h e p l o t t e d q u a n t i t i e s , i . e . d u r i n g t h e f i r s t
50 sec, is v e r y r a p i d f o l l o w e d by a s l o w e r i n c r e a s e . It i s t e m p t i n g t o a s s o c i a t e
t h i s b e h a v i o u r w i t h t h e p r e s e n c e of d i f f e r e n t c h e m i c a l c a r b o n a c e o u s s p e c i e s on
the iron surface and w i t h t h e r a t e of CHr f o r m a t i o n .
T h e r e f o r e we performed a number of e x p e r i m e n t s which were aimed a t i d e n t i f y -
i n g t h e chemical n a t u r e o f t h e c a r b o n a c e o u s s u r f a c e p h a s e s a f t e r t h e CO/H, reac-
t i o n . The p r o c e d u r e c o n s i s t s e s s e n t i a l l y i n comparing t h e c a r b o n Auger peak ‘ I
s h a p e s and C l s b i n d i n g e n e r g i e s o f carbonaceous s u r f a c e l a y e r s of known chemical
o r i g i n ( c o m p o s i t i o n ) w i t h t h o s e of t h e s u r f a c e p h a s e s g e n e r a t e d by t h e hydrogena-
t i o n of CO.
A t o t a l of t h r e e s i g n i f i c a n t l y d i f f e r e n t c a r b o n a c e o u s l a y e r s were o b s e r v e d
a f t e r t h e h y d r o g e n a t i o n r e a c t i o n . F i g u r e 5 shows t h e c a r b o n Auger s p e c t r a of t h e s e
t h r e e l a y e r s which we c a l l t h e s u r f a c e p h a s e s I , I1 and 111, r e s p e c t i v e l y . These
s p e c t r a were o b t a i n e d f o r CO/H, = 1:20. In comparing t h e Auger s p e c t r a of F i g . 5
o n e should i n p a r t i c u l a r pay a t t e n t i o n t o t h e r e l a t i v e h e i g h t s of t h e peaks l a -
b e l l e d A, B and c. O t h e r d i f f e r e n c e s c a n b e n o t e d i n t h e n e g a t i v e peak e x c u r s i o n
a t 2 7 0 - 285 e V . T h e s e , however, w i l l n o t b e r e f e r r e d t o i n t h i s p a p e r .

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 The c a r b o n 1s s p e c t r a c o r r e s p o n d i n g t o t h e AES s p e c t r a i n F i g . 5 showed d i f -
f e r e n t b i n d i n g e n e r g i e s s i m i l a r t o t h o s e o f F i g . 3 . T h e s e measured C l s b i n d i n g
e n e r g i e s are l i s t e d i n T a b l e I t o g e t h e r w i t h t h e d a t a f o r a d s o r b e d a c e t y l e n e , se-
g r e g a t e d c a r b i d i c and g r a p h i t i c c a r b o n .

Table I
Cls Binding Energies

I Species I B i n d i n g Energy (eV) I

i n UHV

graphitic C 285.0

Phase I-CHx 283.9

after
Phase I1 284.2
r e a c t ion
Phase 111 284.7

Surface phase I
The C l s b i n d i n g e n e r g i e s of t h i s s u r f a c e p h a s e and chemisorbed m o l e c u l a r
a c e t y l e n e a r e i d e n t i c a l w i t h i n experimental e r r o r . T h i s f a c t s u g g e s t s t h a t s u r -
f a c e p h a s e I i s a h e a v i l y h y d r o g e n a t e d c a r b o n l a y e r . A comparison o f Auger d a t a ,
F i g . 6 , shows, however, a s u b s t a n t i a l d i f f e r e n c e f o r s u r f a c e p h a s e I and a c e t y -
l e n e . On t h e o t h e r h a n d , a v e r y good s i m u l a t i o n of t h e s u r f a c e p h a s e I Auger
s p e c t r u m i s o b t a i n e d when a c a r b i d i c s u r f a c e c a r b o n produced i n UHV by h e a t i n g
t h e sample t o 7 2 0 K f o r a b o u t 2 min i s exposed t o C,H, a t 400 K f o r 5 min ( 2 X
lo-’ P a ) . It is l i k e l y t h a t under t h e s e c o n d i t i o n s some d e c o m p o s i t i o n of C,H, i n -
t o CH s p e c i e s w i l l o c c u r / 1 6 , 1 7 / . We p r o p o s e t h e r e f o r e t h a t t h e s u r f a c e phase I
c o n s i s t s mainly of c a r b i d i c c a r b o n and CH s p e c i e s .

S u r f a c e p h a s e I1
A t f i r s t s i g h t t h e Auger s p e c t r u m o f s u r f a c e p h a s e 11, F i g . 5, a p p e a r s t o
be i d e n t i c a l t o t h e s p e c t r u m of c a r b i d i c c a r b o n s e g r e g a t e d u n d e r UHV c o n d i t i o n s .
However, t h i s i s n o t t h e case. F i g u r e 7 shows b o t h s p e c t r a f o r a d i r e c t compari-
son, and i t c a n b e n o t e d t h a t t h e peaks B and C of t h e s e two s p e c t r a a r e s h i f t e d
a g a i n s t e a c h o t h e r by a b o u t 2 e V . The r e a s o n f o r t h i s s h i f t i s presumably bonded
hydrogen i n t h e c a s e o f t h e s u r f a c e p h a s e 11, a s e x p e c t e d from t h e s h i f t of 0 . 9
e V f o r t h e C l s s p e c t r a of UHV c a r b i d i c c a r b o n and s u r f a c e p h a s e I1 c a r b o n ( s e e
T a b l e I ) . The f a c t t h a t some hydrogen is n e c e s s a r y i n o r d e r t o g e n e r a t e t h e Auger
peak of s u r f a c e p h a s e I1 i s i l l u s t r a t e d by t h e f o l l o w i n g e x p e r i m e n t : F e ( l l 0 ) w i t h
s e g r e g a t e d c a r b i d i c c a r b o n was exposed t o C,H, a t 475 ( 2 x P a , 5 m i n ) . The
Auger s p e c t r u m t a k e n s u b s e q u e n t l y i s shown a s t r a c e ( c ) i n F i g . 7 a n d i t h a s f e a -
t u r e s i d e n t i c a l t o t h o s e o f t h e s u r f a c e p h a s e I1 s p e c t r u m .
The amount of bonded hydrogen i n t h e s u r f a c e p h a s e I1 i s presumably l e s s
t h a n i n t h e CHx l a y e r , m a i n l y f o r two r e a s o n s : (1) There i s no shape change i n
t h e Auger peak r e l a t i v e t o c a r b i d i c c a r b o n , o n l y a n e n e r g e t i c s h i f t ; ( 2 ) t h e pro-
c e d u r e o f s i m u l a t i n g p h a s e I1 i n v o l v e s a n C,H, e x p o s u r e a t h i g h e r t e m p e r a t u r e s
( 4 7 5 K compared t o 400 K f o r CHx s i m u l a t i o n ) f a c i l i t a t i n g t h e d e h y d r o g e n a t i o n of
C,H,. The s u r f a c e p h a s e I1 c a n t h u s b e c h a r a c t e r i z e d a s a c a r b i d i c c a r b o n l a y e r
w i t h bonded hydrogen.

S u r f a c e p h a s e 111
The c a r b o n Auger
- -peak of t h e s u r f a c e p h a s e 111 h a s a -
great similarity with
t h a t of g r a p h i t i c c a r b o n / 1 8 , 1 9 / . F i g u r e 8 shows an Auger ’ t r a c e o f g r a p h i t i c
21
c a r b o n on F e ( l l 0 ) which was s e g r e g a t e d t o t h e s u r f a c e by h e a t t r e a t i n g t h e crys-
t a l i n ,WV ( 6 2 5 K , 2 5 m i n ) . Looking a t t h e r e l a t i v e peak h e i g h t s A , B and C one
c a n n o t i c e t h e same s e q u e n c e a s i n t h e s p e c t r u m o f p h a s e 111. I n a p r o c e d u r e e q u i -
v a l e n t to t h o s e d i s c u s s e d i n t h e p r e v i o u s s e c t i o n s we c a n a l s o p r o d u c e a phase
111 t y p e c a r b o n a c e o u s l a y e r by e x p o s i n g t h e Fe c r y s t a l w i t h c a r b i d i c c a r b o n t o
C,H, a t a b o u t 580 K ( 2 X P a , 20 m i d . The Auger peak o f t h i s l a y e r i s shown
a s t r a c e ( b ) i n F i g . 8. For comparison t h e p h a s e I11 peak i s i n c l u d e d a s t r a c e
( c ) . A l l t h r e e t r a c e s ( a ) - ( c ) h a v e v e r y s i m i l a r s h a p e s b u t from a c l o s e r i n -
s p e c t i o n o f t h e e n e r g e t i c p o s i t i o n s of t h e peaks it is a p p a r e n t t h a t peak B f o r
t h e t r a c e s ( b ) and ( c ) i s s h i f t e d t o lower k i n e t i c e n e r g i e s r e l a t i v e t o t h a t of
trace ( a ) . S i n c e b o t h l a y e r s c h a r a c t e r i z e d by ( b ) and ( c ) a r e o r i g i n a t i n g from
g a s phase r e a c t i o n s i n v o l v i n g hydrogen, i t i s r e a s o n a b l e t o assume t h a t t h i s
peak s h i f t i s i n d i c a t i v e of bonded hydrogen.

Hydrogenation b e h a v i o r
An i n t e r e s t i n g o b s e r v a t i o n was made when t h e v a r i o u s c a r b o n a c e o u s l a y e r s
were s u b j e c t e d t o hydrogen a t m o s p h e r e a t e l e v a t e d t e m p e r a t u r e . I t was s e e n t h a t
t h e CH, l a y e r and t h e hydrogen c o n t a i n i n g c a r b i d i c c a r b o n l a y e r ( p h a s e s I and 11,
r e s p e c t i v e l y ) c o u l d be r e a d i l y removed by h y d r o g e n a t i o n b u t t h a t t h e g r a p h i t i c
l a y e r was q u i t e i n e r t t o w a r d s H,. An example of a h y d r o g e n a t i o n o f a mixed phase
I I / p h a s e I11 l a y e r i s p r e s e n t e d i n F i g . 9. The t o t a l amount of c a r b o n i s s e e n t o
d e c r e a s e b u t t h e b i n d i n g e n e r g y s h i f t from 284.4 e V t o 284.9 eV i n d i c a t e s t h a t
c a r b i d i c c a r b o n ( p h a s e 1 1 ) i s removed a n d g r a p h i t i c c a r b o n l e f t b e h i n d on t h e
s u r f ace.
The f a s t h y d r o g e n a t i o n of s u r f a c e p h a s e s I and I1 r e l a t i v e t o the much slow-
e r removal of s m a l l amounts of g r a p h i t i c c a r b o n c r e a t e s a p o s s i b i l i t y t o s e p a r a t e
t h e d i f f e r e n t p h a s e s i n a mixed l a y e r . Experiments of t h i s k i n d showed t h a t t h e
t o t a l amount of c a r b o n p l o t t e d f o r example i n F i g . 4b c o u l d b e b r o k e n up i n t o a
p o r t i o n r e p r e s e n t i n g CH, a n d c a r b i d i c c a r b o n and a p o r t i o n r e p r e s e n t i n g g r a p h i t i c
c a r b o n . The f i r s t p o r t i o n p l o t t e d v e r s u s t i m e y i e l d s a maximum a t a b o u t 3 0 - 5 0
s e c similar t o t h e maximum i n F i g . 2 . The second p o r t i o n , g r a p h i t i c c a r b o n , in-
c r e a s e s s t e a d i l y w i t h t i m e . We c o n c l u d e t h a t t h e maximum i n r e a c t i v i t y i s l i n k e d
t o t h e maximum i n CHx a n d c a r b i d i c c a r b o n on t h e s u r f a c e whereas t h e g r a p h i t i c
c a r b o n a c t s as a n i n h i b i t o r on t h e m e t h a n a t i o n a s w e l l a s t h e F i s c h e r - T r o p s c h re-
a c t ion.

4 . Conclusions
1 . L a y e r s of (UHV s e g r e g a t e d ) c a r b i d i c and g r a p h i t i c c a r b o n , m o l e c u l a r l y ad-
s o r b e d CO and C,H, c a n b e f a i r l y w e l l c h a r a c t e r i z e d by t h e i r r e s p e c t i v e c a r b o n
Auger peak f i n e s t r u c t u r e and C ( l s ) b i n d i n g e n e r g i e s .
2 . Carbonaceous l a y e r s d e p o s i t e d by t h e CO h y d r o g e n a t i o n r e a c t i o n a t 1 b a r
were a n a l y z e d by AES a n d XPS and c o u l d be c l a s s i f i e d by a comparison of c a r b o n
Auger l i n e s h a p e s a n d C ( t s ) b i n d i n g e n e r g i e s w i t h t h o s e of l a y e r s of known che-
mical composition.
3 . A c a r b o n a c e o u s l a y e r of p a r t i c u l a r i n t e r e s t formed i n t h e i n i t i a l phase
of CO h y d r o g e n a t i o n on F e ( l l 0 ) w a s found t o c o r r e s p o n d t o h e a v i l y hydrogenated
c a r b i d i c c a r b o n , most l i k e l y a CHx p h a s e . T h i s p h a s e i s s u g g e s t e d t o c o n s i s t
m o s t l y of CH r a d i c a l s .
4 . The CHx p h a s e a n d c a r b i d i c c a r b o n c a n b e e a s i l y removed from t h e s u r f a c e
by h y d r o g e n a t i o n ; g r a p h i t i c c a r b o n i s q u i t e s t a b l e towards hydrogen a t 1 b a r and
elevated temperatures.
5. The maximum i n t h e t i m e dependent m e t h a n a t i o n r a t e c o r r e l a t e s w i t h t h e
maximum i n CHx and c a r b i d i c c a r b o n ; t h e s e l a t t e r s p e c i e s a r e i m p o r t a n t i n t e r m e -
d i a t e s f o r t h e f o r m a t i o n of methane a n d p r o b a b l y h i g h e r m o l e c u l a r w e i g h t pro-
ducts.
22
References

I l l K. K i s h i and M.W. R o b e r t s , J. Chem. SOC. F a r a d a y T r a n s . 1 2 ( 1 9 7 5 ) 17 5

/2/ R.W. Joyner and M.W. R o b e r t s , J . Chem. SOC. F a r a d a y Trans. I lo ( 1 9 7 4 ) 1819
/3/ K.Y. Yu, W.E. S p i c e r , I . L i n d a u , P. P i a n e t t a a n d S.F. L i n , S u r f a c e S c i - 57
(.1 9 7 6 .) 157
..
141 C.R. Brundle, I B M J. R e s . Develop 11 ( 1 9 7 8 ) 235
151 G . BrodLn, G. Gafner and H.P. Bonzel, Appl. P h y s . 13 ( 1 9 7 7 ) 333
161 T.N. Rhodin and C.F. B r u c k e r , S o l i d S t a t e Corn. 2 3 7 1 9 7 7 ) 275
I71 W. E r l e y and H. Wagner, S u r f a c e S c i . 7 4 ( 1 9 7 8 ) 3m.
181 G. Wedler, K.G. Colb, G. McElhiney a n d W . H e i n r i c h , Appl. S u r f a c e S c i . 2
(1978) 30
I91 K.A. P r i o r , K. Schwaha and R.M. Lambert, S u r f a c e S c i . 7 7 ( 1 9 7 8 ) 193
I101 R. Ku, N.A. G j o s t e i n and H.P. B o n z e l , S u r f a c e S c i . s f i 9 7 7 ) 465
I111 H.P. Bonzel and T.E. F i s c h e r , S u r f a c e S c i . 51 ( 1 9 7 5 ) 213
1121 K . J . Singh and H. Grenga, J. C a t a l . 5 ( 1 9 7 7 328
1131 B.A. S e x t o n and G.A. S o m o r j a i , J . Catal. 46 ( 1 9 7 7 ) 167
I141 D . J . D y e r and G.A. S o m o r j a i , J. C a t a l . 52 56
( 1 9 7 8 ) 291 and J. C a t a l .
( 1 9 7 9 ) 249
I151 H . J . Krebs, H.P. Bonzel and G. G a f n e r , S u r f a c e S c i . ( t o b e p u b l i s h e d )
I161 C.F. Brucker and T.N. Rhodin, J . C a t a l . 47 ( 1 9 7 7 ) 214
1171 T.N. Rhodin, C.F. B r u c k e r and A.B. Anderson, J . C a t a l y s i s ( t o a p p e a r )
I181 J . P . Coad and J . C . R i v i s r e , S u r f a c e S c i . -25 ( 1 9 7 1 ) 609
I191 C.C. Chang, S u r f a c e S c i . ( 1 9 7 1 ) 53

23
 ELECTRON
SPECTROMETER

GAS
MIXTURE
11-6 BAR1

1
ION PUMP
I- l o a m i 1 PUMPING
Figure 1 : Schematic of UHV apparatus with attached sample transfer system and
micro-reactor for catalytic rate measurements. The sample, located at the sur-
face analysis position "C" in the center of the UHV chamber, can be moved by
pulling the stainless steel rod, to the position "B" (reactor for chemical re-
action) or position "A", the atmospheric loading position.

290 288 286 28L 282

i / E,leVl
id ,
Figure 3: Carbon,ls XPS data after reac-
yx) 200 303 4w 5M) 600
t (sed tion, CO/H, = 1:20, T = 530 K, reaction
times a) 3 sec, b) 23 sec, c) 83 sec and
'Figure 2 : Semilog-plot of methane d) 600 sec. Note shift in maxirrum.
turnover number versus time for a
CO/H, ratio of 1:20.
24
 -2 1L
200 LOO 600

-
5 12

ea
c
L

10
a
dE
-o 8
?
a 6
3
a
% L

O A " '
200 . ' LOO ' . 600
tlsec!
F i g u r e 4 : Same r e a c t i o n d a t a as i n F i g .
3 . ( a ) C l s b i n d i n g e n e r g y as a f u n c t i o n
of r e a c t i o n time. (b) I n t e g r a t e d C l s 230 250 270 290
peak a r e a ( a s a measure of s u r f a c e c a r - EAA4
bon c o n c e n t r a t i o n ) v e r s u s r e a c t i o n t i m e .
F i g u r e 5: Carbon Auger s p e c t r a of t h e
t h r e e carbonaceous s u r f a c e p h a s e s formed
a f t e r t h e CO/H, r e a c t i o n a t 1 b a r and
CO/H, = 1:20. R e a c t i o n c o n d i t i o n s : Sur-
f a c e p h a s e I - T = 565 K , t = 15 s e c ;
s u r f a c e p h a s e I1 - T = 615 K , t = 15 s e c ;
s u r f a c e p h a s e 111 - T = 615 K , t = 90
min .

F i g u r e 6: Carbon Auger s p e c t r a . ( a ) Af-

t e r h e a t i n g t h e F e ( l 1 O ) c r y s t a l i n UHV
a t 720 K f o r a b o u t 3 min; (b) a f t e r ex-
p o s u r e of t h e c a r b i d i c c a r b o n on Fe
(110) t o 2~ Pa C,H, f o r 5 min a t
400 K ; ( c ) a f t e r r e a c t i o n a t 1 b a r ;
(d) a f t e r exposing t h e c l e a n F e ( l l 0 )
c r y s t a l t o C,H, a t room t e m p e r a t u r e
(2 x 1 0 - ~ Pa, 5 m i n ) .

25
 I " ' X B C " "

, ,idt , , I
F i g u r e 7: Carbon Auger s p e c t r a . ( a ) F e ( l l 0 )
230 250 no 290
c r y s t a l was h e a t e d i n UHV t o 720 K f o r
a b o u t 3 min; ( b ) a f t e r CO/H, r e a c t i o n a t
1 b a r ; ( c ) a f t e r e x p o s i n g t h e s u r f a c e pro-
duced under ( a ) t o C,H, a t 475 K ( 2 X
Pa, 5 min) . p o s u r e of t h e Fe s u r f a c e t o C,H, a t
580 K ( 2 X Pa, 2 0 m i d ; a f t e r
1 1 1 1 1 1 I I I CO/H, r e a c t i o n a t 1 b a r .

Mixed Carbtdic
ond Graphitic

NIE

F i g u r e 9: Cls s p e c t r a . ( a ) A f t e r CO/H,
r e a c t i o n a t 1 b a r and 630 K (CO/H, =
1:20, 10 min r e a c t i o n t i m e ) ; ( b ) a f t e r
hydrogenation of t h e s u r f a c e under ( a )
a t 1 b a r , 630 K f o r 6 0 min.

--
la)

(b)
290 286 202 270
Eeldl

26
 CO HYDROGENATION OVER RHODIUM FOIL AND SINGLE CRYSTAL CATALYSTS:

CORREUTIONS OF CATALYST ACTIVITY, SELECTIVITY, AND SURFACE COMPOSITION

D. G. Castner,* R. L. Blackadar, and G. A. Somorjai

Materials and Molecular Research Division, Lawrence Berkeley Laboratory

and Department of Chemistry, University of California,
Berkeley, California 94720

*Present address: Chevron Research Company, P.O. Box 1627, Richmond,

California,94802

ABSTRACT

CO hydrogenation at 6 atm over polycrystalline Rh foil and single crys-

tal Rh (111) catalysts was investigated in a system where the surface struc-

ture and composition of the catalysts could be characterized both before and

after the reaction. The reaction conditions ( H 2 :CO ratio, reaction tempera-

ture, and surface pretreatment) were systematically varied to determine the

optimum conditions for formation of oxygenated hydrocarbons. Initially clean

Rh catalysts showed no structure sensitivity, primarily produced methane

(90 wt%) at an initial rate of 0.15 molecules site-lsec-’ at 3OO0C, and did

not produce detectable amounts of oxygenated hydrocarbons. Preoxidation of

the Rh catalysts (800 Torr 0 2 , 6OO0C, 30 min.) resulted in dramatically in-

creased initial rates, a larger fraction of higher molecular weight hydrocar-

bons, some structure sensitivity, and formation of methanol, ethanol, and

acetaldehyde. The different Arrhenius parameters over the clean and preoxi-

dized foils indicate that the methanation mechanism is different on these two

surfaces. Decreasing the reaction temperature or H2:C0 ratio increased the

C H to C H ratio and shifted the product distribution towards higher mole-

2 4 26
cular weight hydrocarbons.

27
 INTRODUCTION

Reaction of H -CO mixtures over t h e Group

2
VI11 metals u s u a l l y y i e l d s a

wide range of p r o d u c t s , i n c l u d i n g a l k a n e s , a l k e n e s , and oxygenated hydrocar-

bons. I n recent s t u d i e s , Rh supported on S i 0 2 showed a unique s e l e c -

t i v i t y f o r production of t h e two-carbon oxygenated s p e c i e s acetaldehyde,

a c e t i c a c i d , and e t h a n o l . S i m i l a r s e l e c t i v i t y was shown a t 1 a t m on c a t a -

l y s t s prepared by d e p o s i t i n g Rh c l u s t e r s on b a s i c metal This

c o n t r a s t s with r e s u l t s f o r Rh and Rh supported on A 1 0j , ( 6 ) over

which no oxygenated hydrocarbons were formed a t 1 atm. A need t h e r e f o r e

e x i s t s f o r s t u d y i n g CO hydrocarbons over w e l l - c h a r a c t e r i z e d Rh a t e l e v a t e d

p r e s s u r e s , under a v a r i e t y of r e a c t i o n c o n d i t i o n s and s u r f a c e p r e t r e a t m e n t s ,

t o determine t h e c o n d i t i o n s necessary f o r oxygenated product s e l e c t i v i t y .

We have measured r e a c t i o n r a t e s and product d i s t r i b u t i o n s over c l e a n and pre-

oxidized Rh f o i l and R h ( l l 1 ) c r y s t a l s u r f a c e s a t 6 atm and 250-4OO0C, with

H :CO r a t i o s of 3:l t o 1:3. S u r f a c e s t r u c t u r e and chemical composition were
2
c h a r a c t e r i z e d u s i n g low-energy e l e c t r o n d i f f r a c t i o n (LEED) and Auger e l e c t r o n

spectroscopy (AFS). The r e s u l t s w i l l be compared t o previous r e s u l t s on

Rh c a t a l y s t s .

EXPERIMENTAL

The a p p a r a t u s and technique employed i n t h e s e experiments a r e described

c\
elsewhere.(j' " B r i e f l y , t h e r e a c t i o n c e l l is l o c a t e d i n s i d e a n u l t r a - h i g h

vacuum (UHV) chamber t o a l l o w i o n s p u t t e r c l e a n i n g and s u r f a c e c h a r a c t e r i z a -

t i o n by LEED and AES immediately before and a f t e r r e a c t i o n . After closing

the cell, f i r s t the H2 (99.9995% p u r i t y ) and then t h e CO (99.99% p u r i t y ,

28
Fe and Ni carbonyls removed in a dry ice trap) were admitted and circulated

in the closed loop. Allowing a few minutes for mixing at room temperature,

the reaction was then started by heating the Rh sample resistively. The

buildup of products was monitored by a gas chromatograph using a Chromasorb

102 column and flame ionization detector. The reaction was stopped after

times ranging up to 3 hr, by cooling to room temperature and pumping down to

UHV, to measure changes in surface composition.

For preoxidized samples, the surface was heated to 6OO0C in 1 atm 0

2
for 30 minutes inside the reaction cell. During this treatment, an epitaxial

oxide was formed, and oxygen also dissolved into the bulk. The oxide layer

was amorphous and had an 0510/F&jo2 AES peak intensity ratio of 0.5 to 0.6,

although ratios up to 2.6 were obtained by oxidizing carbon-covered surfaces.

The initial turnover numbers ( T N ) were determined from a least squares

fit to the initial slope of the product concentration vs. time curves. In

the calculation, the atom density of the %(Ill) surface (1.6 x IOl5 atoms

was used as the active site density. The same figure was also used for pre-

oxidized samples, thus ignoring possible increases in surface area as well as

a reduced Rh surface density on the oxide.

RESULTS

Fig. 1 shows the-buildup of products during a typical run on clean Rh at

300°C and 3H2:1C0. Results on the clean Rh foil and %(Ill) were identical.

Under the above conditions, CH4 was the main product (90 wt%) with initial

TN 0.15 molecules site-'set- 1 . C2 and C

3
hydrocarbons were formed, but no

oxygenated hydrocarbons were detected. All rates of product formation, ex-

29
c e p t C2H6, d e c l i n e d o v e r t h e c o u r s e of t h r e e hours. The AES s p e c t r a before

and a f t e r r e a c t i o n , i n F i g . 2, show t h a t small amounts o f S and C1 and a mono-

l a y e r of C b u i l t up on t h e s u r f a c e during CO hydrogenation. AFS peak i n t e n -

s i t i e s f o r t h e s e i m p u r i t i e s remained n e a r l y c o n s t a n t a f t e r t h e f i r s t 30 minute

minutes, a l t h o u g h t h e r e a c t i o n r a t e s continued t o d e c l i n e . The proximity of

t h e Rh and Rh302 p e a k s prevented AES l i n e s h a p e a n a l y s i s t o determine whe-

256
t h e r t h e carbon s t a t e w a s changing d u r i n g t h i s time.

P r e o x i d a t i o n of t h e Rh(ll1) c r y s t a l ( s e e Figs. 3 and 4) g r e a t l y increased

t h e i n i t i a l T N ' s , s h i f t e d product d i s t r i b u t i o n s l i g h t l y t o h i g h e r molecular

weight, and r e s u l t e d i n t h e appearance of t h e oxygenated products methanol,

e t h a n o l , and acetaldehyde. The marked d e c r e a s e i n TN's d u r i n g t h e f i r s t 30

minutes coincided with r a p i d l o s s of t h e e p i t a x i a l oxide. After t h i s period,

t h e near-surface oxygen c o n c e n t r a t i o n reached a low s t e a d y - s t a t e v a l u e , as

shown i n Fig. 5. Methane w a s s t i l l formed a t a h i g h e r r a t e on t h e steady-

s t a t e s u r f a c e w i t h oxygen than on t h e c l e a n s u r f a c e . Oxygenated p r o d u c t s

were formed during t h e e n t i r e t h r e e hours. Decreasing t h e temperature l e d

t o a f u r t h e r s h i f t toward h i g h e r molecular weight and an i n c r e a s e i n t h e C H

2 4
t o C2H6 r a t i o , as shown i n F i g s . 6 and 7. During t h e CO-rich r e a c t i o n s a c e t -

aldehyde was t h e only oxygenated hydrocarbon produced. Also, two t o f o u r

monolayers of carbon were d e p o s i t e d on t h e p r e o x i d i z e d Rh d u r i n g CO-rich runs

a t 3OO0C, probably a c c o u n t i n g f o r t h e i n c r e a s e d poisoning r a t e (Fig. 6 ) .

Resuits f o r preoxidized Rh f o i l were s i m i l a r t o those f o r preoxidized

Rh(lll) except for a s m a l l s t r u c t u r e s e n s i t i v i t y shown i n a lower CH4 TN and

l a r g e r C2H4 t o C2H6 r a t i o . Also, e t h a n o l formed a smaller f r a c t i o n of t h e

oxygenated products. I n CO-rich r u n s , more carbon w a s d e p o s i t e d on t h e pre-

o x i d i z e d f o i l than on p r e o x i d i z e d Rh(lll), g i v i n g a faster p o i s o n i n g r a t e .

30
The activation energy for methanation was found to be 12 kcal/mole on preoxi-
dized foil, half the value (24 kcal/mole) found on clean Rh foil. (5)

DISCUSSION

Preoxidation of the Rh surfaces markedly changes their activity and selec-

tivity, indicating that the chemical environment of the Rh atoms is important

in determining their catalytic properties. This is consistent with the varia-

bility of supported Rh catalysts depending on their The

CH4 formation rate depends directly on the oxygen concentration in the near-

surface region, as shown in Table I. The lowest initial CH4 production rate

is obtained during CO hydrogenation over clean catalysts and the highest over

the catalyststwith an epitaxial oxide. An intermediate value is given by per-

oxidized surface which are flashed in vacuum prior to CO hydrogenation,( 5 )

resulting in a low near-surface oxygen concentration.(lo) The fact that C02

hydrogenation gives a higher CH4 TN than CO hydrogenation under the same reac-

tion conditions suggests that C 0 2 oxidizes the catalysts during hydrogenation.

C02 has been shown to dissociatively adsorb on Rh surfaces,(839,ll)and an

oxygen AES signal was detected in the early stages of C02 hydrogenation over

Fe .(12)
The changes in Arrhenius parameters, shown in Table 11, strongly indicate

that a change in mechanism is the cause of the increased CH4 TN on preoxidized

surfaces. In particular, a simple effect of surface area or active site den-

sity can be ruled out. The activation energy on the oxygen-treated surface

is 12kcal/mole, half that on the clean surface, 24 k~al/mole,(~)and within

experimental error of the value for C02 hydrogenation on clean Rh. This again

31
s u g g e s t s o x i d a t i o n by t h e C02. Preexponential f a c t o r s show a similar trend.

The e f f e c t of i n c r e a s i n g p r e s s u r e from 1 a t m ( 5 ) t o 6 atm ( t h i s s t u d y )

was minor. The C H t o C H r a t i o was s m a l l e r , presumably t h e r e s u l t of the

2 4 2 6
higher H p a r t i a l p r e s s k r e i n c r e a s i n g o l e f i n hydrogenation. Also, t h e poison-
2
i n g observed i n t h i s s t u d y at 6 atm w a s n o t observed at 1 atm. P o s s i b l y the

e f f e c t of S and C 1 i m p u r i t i e s , or d e a c t i v a t i o n of C o v e r l a y e r s , i s enhanced a t

high p r e s s u r e . Behavior a t 6 atm is i n o t h e r r e s p e c t s similar t o t h a t a t

1 a t n ~ ' ~and
) a g r e e s w e l l w i t h f i n d i n g s f o r supported Rh c a t a l y s t s which produce

hydrocarbons. ( 1 ' 2 ' 6 ) This i n d i c a t e s t h a t m e t a l l i c Rh o r a complex of Rh and C

is a c t i v e i n hydrocarbon formation, b u t t h a t t h e s e s u r f a c e s do not p r o v i d e t h e

c o n d i t i o n s necessary f o r oxygenated hydrocarbon formation, suggesting t h a t a

h i g h e r Rh oxidation s t a t e may be c r u c i a l t o t h i s process. Production of oxy-

genated hydrocarbons a f t e r t h e near-surface oxygen c o n c e n t r a t i o n reaches steady-

s t a t e i n d i c a t e s t h a t CO i s t h e source of oxygen i n t h e s e p r o d u c t s , b u t bulk

oxygen d i f f u s i n g i n t o the near-surface reagion i s a n o t h e r p o s s i b l e source. We

are undertaking i s o t o p i c l a b e l i n g s t u d i e s t o r e s o l v e t h i s question.

Varying t h e temperature and H2:C0 r a t i o produces r e s u l t s t h a t f o l l o w the

trends p r e d i c t e d f o r a mixture of p r o d u c t s i n equilibrium,(13) t h a t is, higher

molecular weight and more u n s a t u r a t e d or oxygenated products a r e favored at

low temperature, and t h e hydrogen-poor s p e c i e s C2H4 and CH CHO a r e favored

3
a t low H2:C0 r a t i o . Thus thermodynamicsseemsto have relevance even though

t h e o v e r a l l CO-H conversion t o any of t h e p r o d u c t s is f a r from equilibrium

2
i n o u r experiments. A p o s s i b l e e x p l a n a t i o n is t h a t an i n i t i a l slow s t e p i n

t h e mechanism is followed by r a p i d combination and p a r t i a l e q u i l i b r a t i o n of

hydrocarbon fragments.

32
 REFERENCES

1. M. Ichikawa, Bull. Chem. SOC. Japan 2, 2268 (1978).

2. M. Ichikawa, Bull. Chem. SOC. Japan 2, 2273 (1978).
3. M. M. Bhasin, W. J. B a r t l e y , P. C. E l l g e n , and T. P. Wilson,

J. Catal. 2,120 (1978).

4. P. C. E l l g e n , W. J. B a r t l e y , M. M. Bhasin, and T. P. Wilson, 175th ACS

Meeting, Los Angeles, C a l i f . , Div. P e t r o l . Chem. P r e p r i n t s 3,616 (1978).

5. B. A. Sexton and G. A. Somorjai, J. Catal. 5,167 (1977).

6. M. A. Vannice, J. C a t a l . 7 ,449 (1975).
7. D. W. B l a k e l y , E. I. Kozak, B. A. Sexton, and G. A. Somorjai, J. Vac. S c i .

Technol. 2, 1091 (1976).

8. D. G. C a s t n e r , B. A. Sexton, and G. A. Somorjai, S u r f a c e S c i . Tl,
519 (1978).
9. D. G. Castner and G. A. Somorjai, S u r f a c e S c i . B, 60 (1979).
IO. D. G. Castner and G. A. Somorjai, LBL-9288.

11. L. H. Dubois and G. A. Somorjai, LBL-8976 and LBL-9280.

12. D. J. Dwyer and G. A. Somorjai, J. Catal. 2,291 (1978).

13. D. J. Dwyer, K. Yoshida, and G. A. Somorjai, 175th ACS Meeting, Los

Angeles, C a l i f . , Div. P e t r o l . Chem. P r e p r i n t s 3,521 (1978).

33
Table I. Comparison of initial methanation TN for CO and C02 hydrogenation

in a batch reactor at 300OC over Rh and Fe catalysts. Methane TN is

-1 -1
in molecules site sec.

Reaction Surface Initial CH4

Catalyst Ref.
Conditions Pretreatment TN at 30OoC

0.92 atm clean 0.13 (5)

Rh foil
3 ~1co
~ : preoxidized(a) 0.33 (5)

0.92 atm clean 0.33 (5)

Rh foil preoxidized(a)
3H2: 1C02 1.7 (5)

6 atm clean 0.15 this

Rh foil
3H2:1CO preoxidized(b) 1.7 study

6 atm clean 0.15 this

Rh(ll1)
3H2: IC0 preoxidized(b) 4.6 study

Fe foil
6 atm clean 1.9 (12)
3H2: IC0 preoxidized (C) 18.7 (12)

Fe foil 6 atm clean 10.9 (12)

3H2: IC0
2

(a) 15 min at 3OO0C in 700 T o r r 02,then heated to 1000°C in vacuum.

(b) 30 min at 600Oc in 800 Torr 02.

(c) 20 min at 300°C in 4 atm 02.

34
Table 11. Comparison of the Arrhenius methanation parameters (TN = A

for CO and CO hydrogenation over polycrystalline Rh foils. Units for

2
1
TN and A are molecules site- sec
-1
. Ea is in kcal/mole.

Reaction Surface CH4 TN

A Ref.
Conditions Pretreatment at 3OO0C Ea

0.92 atm
3H2:1C0 clean 0.13 i 0.03 10 (a) 24 i 3 (5)

0.92 atm
3H2:1C02 clean

6 atm
3~~:1c02 preoxidized(b)

(a) determined from data in Ref. (5).

(b) 30 min. at 6OO0C in 800 Torr 02.

35
 1401 1 I I I I I I I I 1 I 1

3 H2: I CO, 6 atm

0 30 60 90 I20 150
Time (minutes)
X BL794- 6130

Fig. 1. Buildup of t h e GI to C hydrocarbon p r o d u c t s d u r i n g GO hydrogena-

3
t i o n over i n i t i a l l y c l e a n Rh f o i l o r & ( I l l ) c a t a l y s t s a t 6 atrn,

300°C, and 3H2:1C0.

36
 Rh

(a)
Clean rhodium

NIE:

(b)
4fter 3 hr at 3OO0C
3 H:, I CO, 6 a t m

Fig. 2.
-
3 0 200 300 400 500 60(
Energy (eV)
XBL 797- 66 55

A B s p e c t r a o f t h e i n i t i a l l y c l e a n Rh c a t a l y s t s (a) b e f o r e and

(b) a f t e r 3 hr of CO hydrogenation a t 6 atrn, 3OO0C, and 3H2:1C0.

37
 I120 I 1 I I I I I I I I I I'
- Preoxidized Rh (111)
R
/,O
-h,,, 0.6
960 - 3 H:, ICO, 6 atm
- 300 "C CH ~ (x 1/10)

800-

-
.-
2640-
v,
\

-
v)
al -
3
0
;w--
I
-
320-

I I I I 1 I I 1
0 30 60 90 120 I50 18
Time (minutes)
XBL794-6136

Fig. 3 . Buildup of t h e C1 t o C hydrocarbon p r o d u c t s d u r i n g CO hydrogena-

3
t i o n o v e r a p r e o x i d i z e d % ( I l l ) c a t a l y s t a t 6 atm, 3OO0C, and 3H2:1C0.

38
 Q
a,
N
.-
.-
Q
X
0
Q)
L
(L

-0
a,
.-N
-0
.-
x
0
a,
rt

I I I I I I
0 0 0 0
0
- O
CD c o e ( \ I o

39
 eoxidi zed
Rh (111)

3 H2: I CO, 6 otm

N'(E
#X l C - - . X 2

(C)
fter 3hr at 300°C
I H2: 3 CO, 6otm

a
100 200 .
Energy ( e V )
XBL797-6654

F i g . 5. AES s p e c t r a of t h e preoxidized Rh(ll1) c a t a l y s t ( a ) b e f o r e and

(b) a f t e r 3 h r of CO hydrogenation a t 6 atm, 3OO0C, 3H2:1C0, o r

(c) a f t e r 3 hr of C O hydrogenation a t 6 atm, 3OO0C, 1H2:3C0.

 Rh 011) Rh(lll)
3 ti2: I CO, Gatm I Hi 3 CO, 6 atm
300°C 300°C

40

20

Preoxidized Rh (111)
0510/Rh302=0.6
r
r 00- 3l+lCO,6atm I H2 3 CO, 6 atm
3OO0C 300 *c
C
.-
5 60-
n
.-
I-

E 40-
0
c

s
U
20-
0
L

O-

100- Preoxidized Rh(lll) Preoxidized Rh (111)

05K)/Rh302 =0.5 % ~ 1 0 / ~ ~ 3 0=0.5
2
80 - 3 ti2: I CO, Gatm I Hi3CO.60tm
25OoC 250’C
60-

40 -

20 -

0-

XB L 7 9 7 4 6 53

~ i 6. Buildup of C1 to C 4 hydrocarbon products during CO hydrogenation

~ .
Over a preoxidized Rh(ll1) catalyst at 6 atm, 25OoC, and 1H2:3C0.

41
 I I I I I I I I I I I I

560- Preoxidized Rh (Ill)

0510/Rh302 = 0.5
-
I H 2 : 3 CO, 6atm.
480- 250°C

400 -
a
c
.- -
v)
\
m
-2
3
320-
0
a
-
2
-
P
240 -

160-

I I I I I I I I

0 30 60 90 120 150 I80

T i m e (minutes)
XBL794- 6129

Fig. 7 . The product distributions in weight percent after 2 hr of CO hydro-

genation over pretreated Rh(ll1) catalysts at various reaction con-

ditions. See Fig. 4 for explanation of symbols.

42
 CATALYTIC METHANATION OVER SINGLE CRYSTAL NICKEL AND RUTHENIUFI:
REACTION KINETICS ON DIFFERENT CRYSTAL PLANES

R. 0 . Kelley and D. Wayne Goodman

Surface Science Division

National Bureau o f Standards

Washington, D . C . 20234

introduction
A s p e c i a l l y designed u l t r a h i g h vacuum system has been used t o s t u d y
t h e k i n e t i c s o f t h e hydrogenation of CO over low s u r f a c e a r e a , s i n g l e
c r y s t a l c a t a l y s t s . In a r e c e n t p u b l i c a t i o n (11, we have r e p o r t e d r e a c t i o n
r a t e measurenients f o r a Ni(100) c a t a l y s t and compared those r e s u l t s with
k i n e t i c d a t a , derived from t h e l i t e r a t u r e , f o r small p a r t i c l e N i supported
on A1203. There was remarkable agreement between the two c a t a l y s t systems
i n regard t o s p e c i f i c r e a c t i o n r a t e s ( t h e r a t e normalized t o t h e number
o f s u r f a c e metal atoms), t h e a c t i v a t i o n energy, and t h e product d i s t r i b u -
t i o n . In t h e p r e s e n t r e p o r t , we compare r e a c t i o n r a t e s measured on two
c r y s t a l planes o f Ni--the (100) and the close-packed (111)--and two
c r y s t a l planes o f Ru--the zig-zag, open (110) and t h e c l o s e packed (001).
We a l s o r e p o r t t h e v a r i a t i o n o f t h e r e a c t i o n r a t e and t h e s u r f a c e carbon
c o n c e n t r a t i o n w i t h t o t a l p r e s s u r e and w i t h t h e H2:C0 r a t i o . The s u r f a c e
carbon c o n c e n t r a t i o n (an a c t i v e " c a r b i d i c " carbon s p e c i e s ) v a r i e s w i t h
the t o t a l pressure and w i t h t h e r e a c t a n t gas r a t i o . A s t r i k i n g c o r r e l a -
t i o n has been found between t h e s u r f a c e c a r b i d e level and t h e c a t a l y t i c
reaction rate.

Experimental

The apparatus used f o r t h e s e s t u d i e s c o n s i s t s of two connected u l t r a -

h i g h vacuum chambers--one f o r s u r f a c e a n a l y s i s (Auger Electron Spectroscopy
(AES)) and t h e o t h e r s u i t a b l e f o r high p r e s s u r e c a t a l y t i c r a t e s t u d i e s . A
d e t a i l e d d e s c r i p t i o n o f t h e a p p a r a t u s , t h e c r y s t a l cleaning procedure, and
the techniques used t o o b t a i n k i n e t i c r a t e data have been published ( 1 ) .
I t should be noted t h a t t h e number o f metal s u r f a c e atoms exposed t o t h e
r e a c t a n t gas (used t o normalize r e a c t i o n r a t e d a t a ) i s derived from t h e
geometrical s u r f a c e a r e a o f t h e a r y e a l e d c r y 2 t a l and t h e zppropri75e s u r f a c e
a t 9 d e n s i t y [Ni(100): j 5 6 2 x 10 2atoms/cm ; N i ( l l 1 ) : ls86 x 10 -gtoms
cm ; Ru(ll0): 1.00 x 10 atoms/cm ; Ru(001): 1 . 5 5 x 10 atom5 cm 3 . The
Ru samples were cleaned using h i g h temperature oxidation a t 10- t o r r O2
followed by heating i n vacuum t o 1570K. ( 2 )
R e s u l t s a n d Discussion
The o b s e r v a t i o n (1) t h a t t h e r a t e of the r e a c t i o n
3 H2 t CO -t CHq + H 2 0

(expressed as CH4 molecules/surface s i t e / s e c ) measured over a low s u r f a c e

a r e a , s i n g l e c r y s t a l c a t a l y s t i s n e a r l y i d e n t i c a l t o t h a t measured over a
supported small p a r t i c l e Ni c a t a l y s t (2) i s a s t r o n g i n d i c a t i o n t h a t t h e r e i s
l i t t l e r e a c t i v i t y d i f f e r e n c e between those c r y s t a l planes commonly found
i n p o l y c r y s t a l l i n e m a t e r i a l ( i . e . , t h e low index p l a n e s ) . This e x p e c t a t i o n
i s confirmed i n t h e d a t a presented in Fig. 1 , which i s a plot of t h e
s p e c i f i c r a t e (or t u r n o v e r number) of CH4 production versus t h e r e c i p r o c a l
temperature. The s i m i l a r i t y between the open (100) and the close-packed
(111) c r y s t a l planes o f Ni i s evident in b o t h e!! value of t h e s p e c i f i c
r a t e and the a c t i v a t i o n energy ( 2 4 . 7 kcal mole derived from the Ni(100)
d a t a ) . For comparison t h r e e s e t s o f data f o r nickel (supported on alumina)
c a t a l y s t s a r e r e p l o t t e d from t h e l i t e r a t u r e . Thus f o r the H 2 + CO r e a c t i o n
over N i , t h e r e i s e s s e n t i a l l y no v a r i a t i o n i n t h e r e a c t i o n r a t e a s the
c a t a l y s t changes from small metal p a r t i c l e s t o bulk s i n g l e c r y s t a l planes.
Analysis of a n a c t i v e c r y s t a l c a t a l y s t s u r f a c e with AES i n d i c a t e s a
low level of a carbon s p e c i e s and the absence of oxygen ( 1 ) . Measurements of
t h e r a t e o f production of t h i s s u r f a c e carbon s p e c i e s ( i n pure CO) a n d the
r a t e of r e a c t i o n ( i n pure H2) have i n d i c a t e d t h a t both processes ( i . e . , the
production a n d t h e removal of t h e s u r f a c e carbon s p e c i e s ) proceed a t very
s i m i l a r r a t e s . ( 3 ) A mechanism f o r t h e H 2 + CO r e a c t i o n c o n s i s t e n t w i t h the
k i n e t i c data and t h e f i n i t e s u r f a c e carbon level during r e a c t i o n was developed
which involves t h e hydrogenation of an a c t i v e carbon s p e c i e s formed from
t h e d i s s o c i a t i o n . o f CO. F i g . 2a shows t h e changes in t h e r e a c t i o n r a t e a s
t h e pressure i s increased from 1-120 torr a t a f i x e d H2:C0 r a t i o . A t low
temperatures t h e r a t e s f a l l on the same s t r a i g h t l i n e a t a l l p r e s s u r e s . As
t h e temperature i s i n c r e a s e d a d e v i a t i o n from l i n e a r i t y i s seen--the higher
t h e pressure t h e h i g h e r t h e d e v i a t i o n temperature. Accompanying t h i s non-
l i n e a r r a t e behavior i s an i n c r e a s e i n t h e a c t i v e carbon l e v e l on the
s u r f a c e of t h e c a t a l y s t c r y s t a l . \le have proposed t h a t t h i s behavior ( t h e
d e p a r t u r e from t h e l i n e a r i t y pf the r a t e in F i g . 2a and the accompanying
i n c r e a s e i n t h e s u r f a c e carbon l e v e l ) i s due t o a decrease in t h e s u r f a c e
coverage of hydrogen and t h u s a decrease i n the r a t e of hydrogenation o f
s u r f a c e carbon. Fig. 2 b shows s i m i l a r data f o r a R u ( l l 0 ) c r y s t a l . The
v a r i a t i o n of t h e r e a c t i o n r a t e w i t h p r e s s u r e i s very s i m i l a r t o t h e Ni(100)
c r y s t a l - - i . e . , a d e p a r t u r e from l i n e a r i t y o f the r a t e and accompanying t h i s
d e p a r t u r e a n i n c r e a s e i n t h e s u r f a c e carbon level (see reference ( 4 ) f o r
d e t a i l s of t h e AES measurement of c a r b o n on R u ) . We presume t h a t t h e
explanation o f t h i s behavior i s the same o f f e r e d f o r t h e Ni c r y s t a l . I n
f a c t , since t h e binding energy of H on Ru i s lower t h a n on Ni ( 2 ) the
d e v i a t i o n from l i n e a r i t y should be expected a t a lower temperature. This
i s p a r t i c u l a r l y e v i d e n t i n the 1 torr data of Fig. 2a a n d 2 b .

44
 In addition t o t h e r a t e data f o r t h e R u ( l l 0 ) c r y s t a l , F i g . 2b a l s o
contains limited data f o r t h e basal plane of ruthenium, Ru(001). While
the comparison i s l i m i t e d , i t i s c l e a r t h a t t h e H2 + CO r e a c t i o n i s quite
s i m i l a r i n regard t o the s p e c i f i c r e a c t i o n r a t e and t h e a c t i v a t i o n energy
f o r t h e s e two c r y s t a l planes of ruthenium.
The data o f Fig. 2 i n d i c a t e t h a t t h e e f f e c t of t h e t o t a l p r e s s u r e
on t h e reaction r a t e i s dependent on t h e temperature a t which t h e measure-
ments a r e made. Fig. 3 shows t h e v a r i a t i o n o f t h e s p e c i f i c r a t e a s a
function of pressure a t two temperatures over a Ni(100) c a t a l y s t w i t h the
H /CO = 4. Many a u t h o r s ( 5 ) have f i t t e d r e a c t i o n r a t e v a r i a t i o n w i t h
pgessure t o a power r a t e law o f t h e form

The exponents, f i t t e d from experimental d a t a , have been used t o d e r i v e

information about t h e r e a c t i o n mechanism ( 6 ) . I t i s c l e a r from Fig. 3
t h a t , while power r a t e law exponents can be derived and used t o s c a l e
r a t e data a t fixed r e a c t i o n c o n d i t i o n s , such exponents a r e very s e n s i t i v e
t o t h e r e a c t i o n temperature. I t i s doubtful t h a t any fundamental s i g n i f i -
cance can be attached t o values o f t h e exponents derived a t one temperature.
We have attempted t o determine t h e dependence o f t h e methanation r a t e
on the p a r t i a l pressure of both H and C O . In conducting t h i s s t u d y , we
have measured t h e r a t e o f CH4 pro2uction w i t h H :CO r a t i o s which varied
from 0.1 t o 1000 and w i t h a t o t a l pressure whic2 varied from 1 t o 1500
torr. The r e s u l t s o f this study i n d i c a t e t h a t even a t one temperature a
power r a t e law such a s equation 1 i s not adequate t o describe t h e p a r t i a l
pressure dependence o f t h e r e a c t i o n r a t e . However, fl r e a c t i o n r a t e
d a t a measured over a Ni(100) c a t a l y s t can be c o r r e l a t e d , on a smooth
curve, w i t h t h e concentration of " a c t i v e " carbon on t h e Ni s u r f a c e .
Figure 4 i s a p l o t o f t h e measured carbon s u r f a c e coverage and t h e
measured s p e c i f i c r e a c t i o n r a t e f o r various H 2 : C 0 r a t i o s and t o t a l pressures
a t a temperature of 625K. I t should be noted t h a t t h e r e a c t i o n r a t e s are
s t e a d y - s t a t e r a t e s with no evidence f o r d e a c t i v a t i o n and t h a t t h e carbon
AES lineshape i s always t h a t o f a "carbide" w i t h no evidence f o r g r a p h i t e
formation. The e s t i m a t e o f carbon s u r f a c e coverage from the AES carbon
i n t e n s i t y i s based on AES data obtained from a CO monolayer ( 4 ) .
Since t h e r e i s no pressure e f f e c t - - i n t h e pressure range o f t h e s e
measurements--in t h e r a t e o f c a r b i d e production from pure CO ( 3 ) and s i n c e

45
a t any H2:C0 r a t i o an i n c r e a s e i n pressure r e s u l t s i n a decrease i n s u r f a c e
carbon, we conclude t h a t t h e data o f Figure 4 i s a manifestation o f t h e
change i n t h e hydrogenation r a t e of t h e s u r f a c e c a r b i d e with t o t a l pressure
and w i t h t h e H2:C0 r a t i o . We have previously concluded ( 1 ) t h a t t h e methana-
t i o n r e a c t i o n r a t e i s determined by a d e l i c a t e balance of the formation and
removal of surface c a r b i d e and t h a t n e i t h e r o f t h e s e processes a r e r a t e
determining in t h e usual sense. T h u s , a s i n d i c a t e d i n Figure 4 under
r e a c t i o n c o n d i t i o n s unfavorable f o r t h e hydrogenation r a t e ( e . g . , low
p a r t i a l presjure o f H2 a t a high temperature) t h e r e a c t i o n r a t e should
decrease and be accompanied by an i n c r e a s e in t h e s u r f a c e carbon l e v e l .
A t lower temperatures t h e s u r f a c e concentration of hydrogen (and thus t h e
hydrogenation r a t e ) becomes 1 ess s t r o n g l y dependent on pressure. For
example, t h e r a t e o f CH production f o r a 4:l H2:C0 r a t i o a t 503K ( l o t t e d
i n F i g . 3 ) i s only s l i g i t l y dependent on p r e s s u r e (from 1-1500 torr!. The
measured s u r f a c e carbon l e v e l under t h e s e c o n d i t i o n s i s approximately 10%
of a monolayer and does n o t change s i g n i f i c a n t l y over t h e e n t i r e pressure
range.
Thus i t appears t h a t changes i n temperature, H /CO r a t i o , and t o t a l
p r e s s u r e have a common e f f e c t on t h e methanation rage--namely, t o change
t h e s u r f a c e concentration of hydrogen. Although t h e s e e f f e c t s have been
observed predominately on the Ni(100) c r y s t a l , the s i m i l a r i t i e s between Ni
and Ru w i t h regard t o r e a c t i o n r a t e v a r i a t i o n w i t h pressure and w i t h
s u r f a c e carbide level ( F i g . 2 ) s t r o n g l y suggest a s i m i l a r explanation f o r
r u t h e n i urn.
The results o f t h e s e pressure s t u d i e s suggest considerable c a u t i o n i n
drawing the conclusion t h a t c r y s t a l l o g r a p h i c e f f e c t s a r e absent i n t h e
methanation r e a c t i o n over Ni o r R u . While this r e s u l t appears v a l i d under
r e a c t i o n c o n d i t i o n s i n which s u r f a c e c a r b i d e level i s low, as r e a c t i o n
conditions change e f f e c t s due t o d i f f u s i o n of carbon, s t a b i l i t y o f the
s u r f a c e carbide, hydrogen s u r f a c e concentation and o t h e r e f f e c t s which can
have a strong c r y s t a l l o g r a p h i c dependence can become dominant f a c t o r s
influencing the r e a c t i v i t y .

46
 FIGURE CAPTIONS
Figure 1. Arrhenius plot comparing CH4 s y n t h e s i s on Ni(100), N i ( l l l ) ,
and supported Ni c a t a l y s t s . Reaction c o n d i t i o n s : 120 torr,
H2/C0 = 4 . Ni(ll1) - t h i s work; Ni(100) - ref. (1);
supported Ni - ref. 7.
Figure 2. a . ) Arrhenius plot o f CH4 s y n t h e s i s on a N i ( 1 0 0 ) c a t a l y s t
a t t o t a l r e a c t a n t pressures of 1 , 10, 120 t o r r . H2C0 = 4.
b . ) Arrhenius plot of CH4 s y n t h e s i s on a Ru(ll0) c a t a l y s t

a t t o t a l r e a c t a n t pressures of 1 , 10, 120 torr. H2C0 = 4.

Data a t two temperatures f o r a Ru(001) c a t a l y s t a t 120
t o w i s plotted w i t h the symbol, x .
Figure 3 . Methane production r a t e (molecules/surface s i t e / s e c ) versus
pressure a t 503K a n d 625K over a Ni(100) c a t a l y s t .
Figure 4. Methane production r a t e (molecules/surface s i t e / s e c ) a t
625K over a Ni(100) c a t a l y s t versus s u r f a c e carbon concentra-
t i o n (under steady s t a t e r e a c t i o n c o n d i t i o n s ) . The H2:C0
r a t i o and the t o t a l pressure ( t o r r ) f o r each point p l o t t e d
i s indicated in the i n s e r t .

47
 REFERENCES

1. D. W . Goodman, R . D . Kelley, T. E . Madey, and J . T , Yates, J r . ,

accepted f o r p u b l i c a t i o n i n J . C a t a l y s i s .
2. D. W . Goodman, T. E . Madey, M. Ono, and J . T. Yates, J r . , J . C a t a l . ,
-
50 279 (1977).
3. 0. W . Goodman, R . D. Kelley, T . E . Madey, and J . M . White, accepted
for publication i n J . Catalysis.
4. D . W . Goodman and J. M. White, accepted f o r p u b l i c a t i o n i n S u r f a c e
Sc 1e n t e .
5. For example, M. A . Vannice, J . C a t l . , 37, 449 (1975).
6. D. F. O l l i s and 14. A. Vannice, J . C a t a l . , 38, 514 (1975).
7. M. A . Vannice, C a t a l . Rev. S c i . Eng. 1 4 ( 2 ) , 153 (1976).

48
 -
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49
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7-
 Fig. 3

Methane Production Versus Pressure

Over A Ni(100) Catalyst
10

10-2

503K
w W

I 0-3
1 10 100 1000
Pressure (Torr)

51
 0
0

II
I-

I I I 1 I
m d c9 cv T:
0 0 0 0 0

(s~aAqouoy\l)uoqJe3 aaej~ng

52
 THE EFFECTS OF POTASSIIJM PROMOTION ON THE CHARACTERISTICS OF IRON FISCHER-TROPSCH
CATALYSTS. H. Arakawa and A. T. B e l l . M a t e r i a l s and M o l e c u l a r Research D i v i s i o n ,
Lawrence Berkeley L a b o r a t o r y and Department of Chemical E n g i n e e r i n g , U n i v e r s i t y of
C a l i f o r n i a , Berkeley, CA 94720.

The a d d i t i o n of potassium i s w e l l known t o a l t e r t h e performance of i r o n c a t a l y s t s

used f o r Fischer-Tropsch s y n t h e s i s . The o b j e c t i v e s of t h i s i n v e s t i g a t i o n were t o charac-
t e r i z e t h e deFendence o f t h e a c : i v i t y , s e l e c t i v i t y , and s t a b i l i t y of alumina-supported
i r o n c a t a l y s t s on t h e K/Fe r a t i o and t o s e e k e x p l a n a t i o n s f o r t h e , i n f l u e n c e o f p o t a s s i m
on t h e ca:aiysts performance. L s p e r i z e n t s were conducted w i t h ?OL Fe/i.l,O, catz::-s-.s
c o n t a i n i n g 0 t o 1 2 o f p o t a s s i u n . hYth i n c r e a s i n g p o t a s s i u m concent r L 6 f a t a l y s t a c t i v -
i:j' c e i r e a s e d , t h e o l e f i n t o p2;affin r a t i o o f t h e p r ' s t u c t i n c r e a s e d sc!stantial:y, t?,e
methane s e l e c t i v i t y d e c r e a s e d , and t h e c a t a l y s t s t a b i l i t y v a s ennanced. ;'ne interprc:a-
t i o n o f t h e s e r e s u l t s w i l l b e d i s c u s s e d i n terms of t h e i n f l u e n c e of p o t a s s i u m on t h e
a d s o r p t i o n of H,, CO, and C02, and i n f r a r e d o b s e r v a t i o n s o b t a i n e d under r e a c t i o n
conditions.

53
 DEACTIVATION BY CARBON OF NICKEL AND NICKEL-MOLYBDENUM
METHANATION CATALYSTS

A. Douglas M o e l l e r and C a l v i n H. Bartholomew

Brigham Young U n i v e r s i t y
Department of Chemical E n g i n e e r i n g
Provo, U t a h 84602

INTRODUCTION

A s e r i o u s p r o b l e m i n t h e c a t a l y t i c m e t h a n a t i o n o f c o a l s y n t h e s i s gas i s
f o u l i n g of t h e c a t a l y s t b y carbon deposition. This problem can be avoided by i n c r e a s i n g
t h e hydrogen content o f t h e feed stream so t h a t thermodynamic e q u i l i b r i u n i s u n f a v o r a b l e
t o w a r d carbon d e p o s i t i o n (1); however, p r o c e s s economics f a v o r m i n i m i z i n g hydrogen
usage. S i n c e most g a s i f i e r s p r o d u c e a hydrogen d e f i c i e n t gas t h e a p p l i c a t i o n o f
a m e t h a n a t i o n c a t a l y s t w h i c h d e p o s i t s c a r b o n a t n e g l i g i b l e r a t e s would be h i g h l y
desirable, since i t would e l i m i n a t e t h e need f o r the s h i f t r e a c t o r p r i o r t o methanation.
Except f o r a few r e c e n t s t u d i e s i n t h i s l a b o r a t o r y ( 2 - 5 ) t h e r e has been v e r y l i t t l e
r e s e a r c h t o d e t s r m i n e t h e e f f e c t s of c a r b o n d e p o s i t i o n o n a c t i v i t y o r t h e k i n e t i c s
and mechanism o f c a r b o n d e p o s i t i o n on v a r i o u s c a t a l y s t s d u r i n g m e t h a n a t i o n . Such
i n f o r m a t i o n would be v a l u a b l e i n determining t h e b e s t c a t a l y s t s and optimum o p e r a t i n g
c o n d i t i o n s f o r m e t h a n a t i o n o f hydrogen-poor s y n t h e s i s gas.

A p r e v i o u s s t u d y i n t h i s l a b o r a t o r y ( 6 ) showed t h a t Ni-Mo catalysts are

p r o m i s i n g f o r u s e i n t h e BI-GAS p r o c e s s s i n c e t h e y a r e as a c t i v e as N i b u t more
r e s i s t a n t t o s u l f u r p o i s o n i n g . The p r e s e n t s t u d y was u n d e r t a k e n t o determine t h e
b e h a v i o r o f N i and Ni-Mo c a t a l y s t s under r e a c t i o n c o n d i t i o n s which are characteristic
o f combined s h i f t / m e t h a n a t i o n and which f a v o r massive carbon formation. The o b j e c t i v e s
o f t h i s s t u d y were t o :

1. D e t e r m i n e t h e e f f e c t s o f c a r b o n d e p o s i t i o n o n t h e a c t i v i t y o f t h e s e
c a t a l y s t s u n d e r h i g h t e m p e r a t u r e c o n d i t i o n s ( b o t h l o w and h i g h p r e s s u r e s ) which
promote carbon f o r m a t i o n .

2. Determine i f t h e carbon f o u l e d c a t a l y s t s c o u l d be regenerated by t r e a t m e n t

i n a i r o r O2 a t h i g h temperatures.

The r e s u l t s o f a c t i v i t y , a d s o r p t i o n , c a r b o n d e p o s i t i o n and r e g e n e r a t i o n
t e s t s t o a c c o m p l i s h t h e s e o b j e c t i v e s a r e p r e s e n t e d and d i s c u s s e d i n t h i s paper.

EXPERIMENTAL METHODS

Materials

C a t a l y s t composition and suppliers are l i s t e d i n Table 1. C a t a l y s t p r e p a r a t i o n

and p r e t r e a t m e n t was t h e same as d e s c r i b e d p r e v i o u s l y ( 6 ) .

Hydrogen gas (99.99% W h i t m o r e ) was p u r i f i e d u s i n g a Pd c a t a l y s t f o l l o w e d

b y a m o l e c u l a r s i e v e t r a p . Gases f o r t h e r e a c t i o n m i x t u r e s , N2 (99.99% Whitmore),
CO (99.9% Matheson) CH4 (99.97% Matheson), O2 (99.8% Whitmore) were used as d e l i v e r e d .
The r e a c t i o n m i x t u r e f o r t h e carbon d e p o s i t i o n r u n s was passed t h r o u g h an a c t i v a t e d
c h a r c o a l t r a p h e a t e d t o 473 K and a Z n O / m o l e c u l a r s i e v e t r a p heated t o 353 K t o
rBnOVe any i r o n carbonyl and s u l f u r i m p u r i t i e s before undergoing methanation. C a t a l y s t
p r e s u l f i d i n g t r e a t m e n t s were c a r r i e d out u s i n g a 66 ppm H2S i n H2 m i x t u r e prepared
i n t h i s l a b o r a t o r y d i l u t e d t o 9 ppm w i t h hydrogen.
54
Procedure
--
H Chemisorption. P r i o r t o each t e s t s e r i e s , s m a l l samples ( 0 . 2 - 0 . 5 g )
of reduce2catalysts were rereduced a t 773 K as previously described ( 6 ) . H2 adsorption
isotherms were then measured a t 298 K f o l l o w i n g procedures r e p o r t e d p r e v i o u s l y
( 7 - 9 ) . H chemisorption measurements were a l s o performed following each s e r i e s
of t e s t s Eo d e t e c t any changes in t h e c a t a l y s t s u r f a c e a r e a , and in the case of
catalysts analyzed f o r carbon content H2 chenisorption measurements were made d i r e c t l y
a f t e r carbon deposition.
S p e c i f i c Rate Measurement. Except f o r t h e f l u i d i z e d bed t e s t s s p e c i f i c
r a t e s were measured i n a Pyrex, fixed-bed r e a c t o r a t 498 K before and a f t e r the
steady s t a t e carbon deposition runs and a f t e r r e g e n e r a t i o n in the same manner as
in our previous study ( 6 ) . S p e c i f i c r a t e measurements f o r c a t a l y s t s d e a c t i v a t e d
in the f l u i d i z e d bed r e a c t o r were performed only a f t e r regeneration. Except f o r
the measurements before and a f t e r high pressure carbon deposition these t e s t s were
performed with 0.2 t o 0 . 6 gram samples and a r e a c t a n t mixture c o n s i s t i n g o f 1%
CO, 4% HE and 95% N . To avoid lengthy reduction and passivation steps, t h e s p e c i f i c
r a t e measurements Eefore and a f t e r the high p r e s s u r e carbon deposition runs were
c a r r i e d o u t in the s t a i n l e s s s t e e l high pressure r e a c t o r described previously ( 6 )
using 1 ml samples. The r e a c t a n t mixture f o r these measurements was 4.3% CO, 5.6%
H2 and 90.1% Np.

Steady S t a t e (24 h ) Carbon Deposition R u n s . A f t e r i n i t i a l s p e c i f i c r a t e

measurements, each c a t a l y s t was operated in a f i x e d bed f o r approximately 24 hours
under steady s t a t e c o n d i t i o n s a t 723 K and p r e s s u r e s of 138 kPa or 2600 kPa t o
observe i t s behavior under severe carbon d e p o s i t i o n c o n d i t i o n s . Two samples of
each c a t a l y s t were run a t t h e lower pressure. One was used f o r regeneration t e s t s
and one was analyzed f o r carbon cont n t . The space v e l o c i t y f o r a l l steady s t a t e
carbon deposition runs was 100,000 h-P .
Operation in t h e carbon deposition region
of the equilibrium diagram was ensured by using a 4.2% CO mixture ( i n a N di'luent)
and a H /CO r a t i o of 1 . 3 . F i g u r e 1 shows t h i s composition on a carbon-5ydrogen-
oxygen {riaxial p l o t along with our 1%CO mixture (H2/C0 = 4 ) and the 61-GAS nminal
f e e d gas composition ( H /CO - 1 . 4 ) . Sample s i z e s were again 0.2-0.6 g f o r low
pressure runs and 1 ml ?or high pressure runs. Reactant and producr. sampling was
performed in t h e same way as i n our previous in s i t u d e a c t i v a t i o n measurements
(6).
Ni-Mo-Cu (0.57 g ) and Ni-Mo (0.51 g ) were operated in a fluidized bed r e a c t o r
( 6 ) f o r 24 hours a t 723 K and 138 kPa. A f l u i d i z e d bed was used in order t o simulate
more c l o s e l y t h e 81-GAS p r o c e s s . The r e a c t i o n mixture was a d i l u t e BCR mixture
of the following composition: 5.3% CO, 6.5% H2, 1.6% CHq, 3.6% CO , 83.0% N These .
runs were repeated using f r e s h samples (0.5-0.6 g ) and a 4.2% EO, 5.5% tf2, 90.3%
N2 mixture t o obtain samples f o r carbon analysis.

Re;eneration T e s t s and P a s s i v a t i o n . R e g e n e r a t i o n t e s t s were performed

with a 1-3 a i r i n N2 mixture at 138 k P a c a t a l y s t s deactivated a t low pressure
and a 1-4% O 2 i n N m i x t u r e a t 2600 kPa f o r t h o s e d e a c t i v a t e d a t high pressure.
In b o t h c a s e s the Zemperature was 573 K . C a t a l y s t s d e a c t i v a t e d in a f l u i d i z e d
bed were a l s o regenerated in a f l u i d i z e d bed. During regeneration CO and C o g con-
centrations in the product strean were monitored continuously with t h e chromatograph
f o r 15 t o 30 minutes. After 30 minutes the CO concentration was negligible indicating
completion of carbon removal. The c a t a l y s t s &ich had undergone e i t h e r high pressure
r e g e n e r a t i o n or low p r e s s u r e f l u i d i z e d bed r e g e n e r a t i o n were p a s s i v a t e d with a
d i l u t e air/N2 mixture and t r a n s f e r r e d t o t h e f i x e d bed r e a c t o r c e l l t o f a c i l i t a t e
subsequent s p e c i f i c r a t e and H 2 chemisorption measurements.

55
 R e g e n e r a t i o n o f t h e N i c a t a l y s t was a t t e m p t e d u s i n g a 50% H20/H2 m i x t u r e
a t 723 K and 2600 kPa f o r 6.5 hours, b u t i t r e s u l t e d i n severe a t t r i t i o n and t h e r e
was n o t enough c a t a l y s t l e f t i n t h e r e a c t o r t o p e r f o r m any m e a n i n g f u l t e s t s . F o r
t h i s r e a s o n a d i l u t e 0 /N2 m i x t u r e a t h i g h p r e s s u r e was used f o r r e g e n e r a t i o n o f
c a t a l y s t s d e a c t i v a t e d a$ h i g h pressure.

P r e - s u l f i d i n g Runs. 0.5 m l samples o f t h e N i and Ni-Mo-Cu c a t a l y s t s were

loaded i n t o t h e Pyrex f l u i d i z e d bed r e a c t o r and r e - r e d u c e d as d i s c u s s e d p r e v i o u s l y .
The f l u i d i z e d b e d was used t o assure u n i f o r m p o i s o n i n g o f t h e c a t a l y s t p a r t i c l e s .
These c a t a l y s t s were t h e n exposed t o 375 ml/min o f a gas m i x t u r e o f 9 ppm H S i n
H2 a t 725 K f o r s u f f i c i e n t t i m e t o s u l f i d e 50% o f t h e c a t a l y s t s u r f a c e ( 6 ) . i f t e r
exposure f o r t h e r e q u i r e d t i m e , t h e c a t a l y s t s were c o o l e d t o room t e m p e r a t u r e and
p a s s i v a t e d . A c t i v i t y t e s t s were t h e n r u n as d e s c r i b e d below.

RESULTS

S p e c i f i c R a t e and H2 C h e m i s o r p t i o n Measurements
-
R e a c t i o n r a t e s p e r a c t i v e s i t e o f c a t a l y s t , i . e . methane t u r n o v e r numbers
(N ), and p r o d u c t y i e l d s ( f r a c t i o n s o f c o n v e r t e d CO o c c u r r i n g as v a r i o u s p r o d u c t s )
ob!%ined i n d i f f e r e n t i a l r e a c t o r t e s t s o f N i , Ni-Mo, and Ni-Mo-Cu c a t a l y s t s a r e
presented i n T a b l e 2 a l o n g w i t h H2 c h e m i s o r p t i v e uptakes.

The d a t a i n T a b l e 2 show t h a t a l l t h r e e c a t a l y s t s s u f f e r e d s i g n i f i c a n t
decreases i n m e t a l s u r f a c e a r e a measured b y H2 a d s o r p t i o n a f t e r c a r b o n d e p o s i t i o n
a t e i t h e r l o w o r h i g h p r e s s u r e . However, t h e r e w e r e s i g n i f i c a n t v a r i a t i o n s i n
t h e m a g n i t u d e o f changes o b s e r v e d f o r t u r n o v e r numbers a f t e r c a r b o n d e p o s i t i o n
a t low pressure. The CH t u r n o v e r numbers o f N i and Ni-Mo-Cu d i d n o t change s i g n i -
f i c a n t l y w h i l e t h a t o f di-Mo dropped o v e r 90%. CH4 y i e l d d r o p p e d f o r Ni and N i -
Mo b u t remained unchanged f o r Ni-Mo-Cu. Ni-Mo-Cu and Ni-Mo e x h i b i t e d s i g n i f i c a n t
i n c r e a s e s i n COP y i e l d a f t e r c a r b o n d e p o s i t i o n , whereas N i showed no s i g n i f i c a n t
COz y i e l d e i t h e r b e f o r e o r a f t e r carbon d e p o s i t i o n .

The c a t a l y s t s a l s o r e s p o n d e d d i f f e r e n t l y t o r e g e n e r a t i o n . N i and Ni-Mo

r e g a i n e d a c t i v i t y a f t e r r e g e n e r a t i o n h a v i n g CH4 t u r n o v e r numbers near those f o r
t h e f r e s h c a t a l y s t s ; CH4 y i e l d was a l m o s t c o m p l e t e l y r e s t o r e d f o r N i b u t o n l y i n
p a r t f o r Ni-Mo. R e g e n e r a t i o n d i d n o t improve t h e a c t i v i t y o r s e l e c t i v i t y o f N i -
Mo-Cu, b u t r a t h e r caused decreases i n CH4 and C02 y i e l d s . A l l o f t h e s u l f u r - f r e e
c a t a l y s t s a p p a r e n t l y s u f f e r e d a decrease i n s u r f a c e a r e a a f t e r r e g e n e r a t i o n .

The r e s u l t s o f d i f f e r e n t i a l runs f o r c a t a l y s t s subjected t o c a r b o n d e p o s i t i o n

a t h i g h p r e s s u r e d e m o n s t r a t e d s i m i l a r t r e n d s . T h a t i s , CH4 t u r n o v e r numbers as
w e l l as CH4 y i e l d s decreased f o r a l l c a t a l y s t s . I n f a c t NCH4 decreased by a f a c t o r
o f 2 f o r N i and a f a c t o r o f 10 f o r Ni-Mo-Cu and Ni-Mo.

Despite a decrease i n s u r f a c e a r e a t h e regeneration treatment a t h i g h pressure

w i t h a d i l u t e 0 m i x t u r e seemed t o g r e a t l y j m p r o v e c a t a l y s t performance f o r a l l
c a t a l y s t s . CH4 { u r n o v e r numbers f o r t h e t h r e e c a t a l y s t s ranged from 1.5 t o 8 times
t h e v a l u e b e f o r e c a r b o n d e p o s i t i o n and CH4 y i e l d s were 37 t o 66 p e r c e n t h i g h e r
t h a n p r e - c a r b o n d e p o s i t i o n v a l u e s . To d e t e r m i n e i f t h i s e f f e c t was permanent t h e
N i c a t a l y s was t e s t e d f o r an a d d i t i o n a l 20 h o u r s a t 6 2 3 K and space v e l o c i t y o f
I .
100,000 h - w i t h 1%C O and H2/C0 = 4, a f t e r w h i c h t h e t u r n o v e r number r e v e r t e d
t a the pre-carbon deposition value.

T a b l e 2 a l s o shows t h e r e s u l t s o f d i f f e r e n t i a l t e s t s on two c a t a l y s t s ,
Ni-Mo-Cu and N i , which were p r e - s u l f i d e d and exposed t o carbon d e p o s i t i n g environment
a t low Pressure. These r e s u l t s show t h a t carbon d e p o s i t i o n i s e x t r e m e l y d e t r i m e n t a l
t o Ni-Ma-Cu when i t has been p r e v i o u s l y exposed t o H2S. On t h e o t h e r hand N i i s
56
r e l a t i v e l y u n a f f e c t e d showing s i m i l a r a c t i v i t y p e r f o r m a n c e t o t h e n o n - s u l f i d e d
C a t a l y s t . Both c a t a l y s t s showed l i t t l e change i n H2 u p t a k e as a r e s u l t of c a r b o n
d e p o s i t i o n and/or regeneration. However, regeneration apparently caused a s i g n i f i c a n t
i n c r e a s e i n CH4 y i e l d f o r p r e - s u l f i d e d N i .

Steady S t a t e (24 h ) Carbon D e p o s i t i o n Tests

Values of CO conversion, r a t e s o f methane p r o d u c t i o n and normalized a c t i v i t i e s

a r e l i s t e d i n T a b l e 3 f o r N i , Ni-Mo and Ni-Mo-C c a t a l y s t s b e f o r e and a f t e r 24
h o u r s t e a d y s t a t e t e s t s a t 773 K and 100,000 h - Y.
Typical p l o t s o f normalized
a c t i v i t y versus t i m e are shown i n F i g u r e s 2 and 3. Normalized a c t i v i t y i s d e f i n e d
as t h e r a t i o o f t h e i n s t a n t a n e o u s r a t e o f methane p r o d u c t i o n t o t h e i n i t i a l r a t e ;
t h e h a l f l i f e corresponds t o a n o r m a l i z e d a c t i v i t y o f 0.5.

Based o n t h e n o r m a l i z e d a c t i v i t y a f t e r 24 hours t h e o r d e r o f d e c r e a s i n g
r e s i s t a n c e t o c a r b o n d e p o s i t i o n a t l o w p r e s s u r e was N i , N i ( p r e - s u l f i d e d ) , N i -
Mo-Cu, Ni-Mo, Ni-Mo-Cu ( p r e - s u l f i d e d ) . The o r d e r o f i n c r e a s i n g c o n t e n t o f c a r b o n
d e p o s i t e d a f t e r 24 h o u r s f o l l o w e d t h i s same t r e n d . However, when t h e Ni-Mo and
Ni-Mo-Cu c a t a l y s t s were operated i n a f l u i d i z e d bed, Ni-Mo m a i n t a i n e d an a c t i v i t y
o f 0.38 compared t o z e r o f o r Ni-Mo-Cu a f t e r t h e 24 h o u r c a r b o n d e p o s i t i o n t e s t ,
even though 10 t i m e s more carbon was d e p o s i t e d on Ni-Mo compared t o Ni-Mo-Cu. In
f a c t , t h e Ni-Mo-Cu c a t a l y s t l o s t a l l m e a s u r a b l e a c t i v i t y w i t h i n 15 hours i n t h e
f l u i d i z e d bed. The p r e - s u l f i d e d Ni-Mo-Cu a l s o d e a c t i v a t e d v e r y r a p i d l y as shown
i n F i g u r e 2. F i g u r e 3 shows f a i r l y s i g n i f i c a n t f l u c t u a t i o n s i n t h e d a t a a t 8 hours
f o r t h e Ni-Mo f l u i d i z e d bed r u n . M a i n t e n a n c e o f a s t e a d y f l o w d u r i n g t h i s r u n
r e q u i r e d constant a t t e n t i o n , and t h i s f l u c t u a t i o n can be a t t r i b u t e d t o f l o w v a r i a t i o n s
d u r i n g t h e evening and n i g h t hours when t h e r u n was unattended.

Data i n Table 3 o b t a i n e d at h i g h p r e s s u r e show t h a t Ni-Mo l o s t no a c t i v i t y

d u r i n g t h e 24 h o u r p e r i o d . O n l y a s l i g h t d e c r e a s e i n a c t i v i t y was o b s e r v e d f o r
N i , whereas t h e a c t i v i t y f o r Ni-Mo-Cu decreased b y almost 40%.

F o r the low pressure f i x e d bed carbon & p o s i t i o n rtms t h e decrease i n normalized

a c t i v i t y w i t h t i m e i s r e p r e s e n t e d b e s t b y t h e f o l l o w i n g expression:

a
0
a = 1)
1+ e x d - kaor) [exp( kd[COo] t)-1 3

where a = n o r m a l i z e d a c t i v . t y a t t i m e t ,
1
r e a c t i o n r a t e c o n s t a n t ( h - ), k d = d e c a y
[COO] c o n c e n t r a t i o n of CO a t bed entrance
( h ) . An expression f o r t h e h a l f l i f e ( t
a/ao = 0.5 and r e a r r a n g i n g . The r e s u l t
a, = n o r m a l i z e d c t i i t y a t t = 0, k =
c o n s t a t ( 1 mol-' h-'), t = t i m e ( h ) ,
r
(mol 1- ), and T = i n v e r s e space v e l o c i t y
) i s o b t a i n e d from Equation 1 b y s e t t i n g
!L2

Equations 1 and 2 were used t o p l o t the s o l i d l i n e s i n Figures 2 and 3 and t o c a l c u l a t e

t h e h a l f l i v e s shown i n Table 3.

The d a t a f r o m t h e f l u i d i z e d b e d r u n s a r e c o r r e l a t e d f a i r l y w e l l b y t h e
f o l l o w i n g e x p r e s s i o n a f t e r about 5 hours:

-kdt
a = aoe 3)
57
where the symbols have t h e same meaning as b e f o r e . From E q u a t i o n 3 t h e h a l f l i f e
can be o b t a i n e d as f o l l o w s :

t1/2 = 0.693 ( k d ) - l 4)

T h i s e x p r e s s i o n was u s e d t o c a l c u l a t e t h e h a l f l i v e s o f N i - M o and Ni-Mo-Cu i n a

f l u i d i z e d bed w h i c h a r e shown i n Table 3.

DISCUSSION

E f f e c t s o f Carbon D e p o s i t i o n - o n Methanation A c t i v i t y

E f f e c t s on I n t r i n s i c A c t i v i t y l Se l e c t i v i t P r o p e r t i e s . S e v e r a1 r e c e n t
in ves t i g ~ % ~ ~ f i a 2 )m~ p- r ov~ided ev~idence ~ n
t h a t a d s o r b e d c a r b o n i s an a c t i v e r e a c t i o n i n t e r m e d i a t e . McCarty and Wise (11)
r e p o r t e d f o u r t y p e s o f c a r b o n which a r e adsorbed on t h e N i s u r f a c e a f t e r exposure
t o CO. Two s p e c i e s d e s i g n a t e d a ' - c a r b o n and a - c a r b o n ( b o t h atomic carbon) were
e a s i l y removed b y H2 and another d e s i g n a t e d 5 -carbon ( p o l y m e r i z e d carbon) was about
1/100 as a c t i v e toward H2. G r a p h i t i c carbon, t h e f o u r t h t y p e i s a p p a r e n t l y formed
b y h i g h t e m p e r a t u r e c o n v e r s i o n o f t h e B-form. M c C a r t y and Wise i n d i c a t e d t h a t
a - c a r b o n ( C ) i s s l o w l y t r a n s f o r m e d t o 5 - c a r b o n ( C 5 ) a t t e m p e r a t u r e s above 600
K . Thus, cafbon f o u l i n g of methanation c a t a l y s t s i s l i k e l y t h e r e s u l t o f Cg f o r m a t i o n
from , C, t h e r a t e o f t r a n s f o r m a t i o n p r o b a b l y depending on t h e n a t u r e o f t h e a c t i v e
s i t e . The more a c t i v e s i t e s a r e more l i k e l y t o promote b o t h r a p i d d e p o s i t i o n and
g a s i f i c a t i o n o f &. I f d e p o s i t i o n o c c u r s more r a p i d l y t h a n g a s i f i c a t i o n , C, w i l l
b u i l d up on t h e s u r f a c e and Cg f o r m a t i o n w i l l be f a v o r e d .

Assuming c a r b o n i s an a c t i v e i n t e r m e d i a t e , t h e d e a c t i v a t i o n r a t e i s then
d e t e r m i n e d b y t h e r e l a t i v e c o n t r i b u t i o n s o f t h e r a t e o f a c t i v e carbon f o r m a t i o n
and t h e r a t e o f g a s i f i c a t i o n . The r e l a t i o n s h i p between r a t e s o f c a r b o n f o r m a t i o n
and g a s i f i c a t i o n forms t h e b a s i s o f t h e f o l l o w i n g d i s c u s s i o n o f i n d i v i d u a l c a t a l y s t
b e h a v i o r under low p r e s s u r e c o n d i t i o n s . A p p a r e n t l y under t h e low p r e s s u r e c o n d i t i o n s
of t h i s s t u d y N i shows v e r y l i t t l e d e a c t i v a t i o n and accumulates v e r y l i t t l e carbon.
T h i s behavior suggests t h a t the r a t e o f g a s i f i c a t i o n e q u a l i z e s the r a t e o f d e p o s i t i o n
f o r n i c k e l u n d e r t h e s e c o n d i t i o n s . The s m a l l amount o f c a r b o n f o u l i n g t h a t d i d
o c c u r appears t o be m a i n l y due t o blockage o r loss o f s i t e s s i n c e carbon d e p o s i t i o n
d i d n o t change t h e t u r n o v e r number. The a d d i t i o n o f Mo t o N i a p p a r e n t l y f a v o r s
t h e massive d e p o s i t i o n o f carbon as evidenced b y t h e very s i g n i f i c a n t loss o f s p e c i f i c
a c t i v i t y and g r e a t e r c a r b o n c o n t e n t o f Ni-Mo. Indeed, r e c e n t l y o b t a i n e d d a t a f r o m
a g r a v i m e t r i c s t u d y i n t h i s l a b o r a t o r y ( 4 , 5 ) show t h a t t h e r a t e o f carbon d e p o s i t i o n
a t 773 K on a 5.5% Ni-Mo/A1203 c a t a l y s t i s 5 t i m e s g r e a t e r t h a n f o r a 3% Ni/A1203
c a t a l y s t . The m a j o r d i f f e r e n c e i n b e h a v i o r o f t h e s e t w o c a t a l y s t s appears t o be
t h e s i g n i f i c a n t l y h i g h e r r a t e o f g a s i f i c a t i o n o f carbon f o r t h e 3% Ni/A1203. Perhaps
Mo b e l i e v e d t o be present as Mooe d i s s o c i a t e s CO b u t n o t H2, t h u s c a t a l y z i n g f o r m a t i o n
b u t n o t removal o f .C,

The a d d i t i o n o f Cu t o Ni-Mo a p p e a r s t o c a u s e a r e d u c t i o n i n t h e amount

Of C a formed as i n d i c a t e d b y t h e s i g n i f i c a n t l y l o w e r t u r n o v e r number o f Ni-Cu-
Mo. Consequently l i t t l e Cg i s formed, r e s u l t i n g i n t h e r e l a t i v e l y l o n g h a l f - l i f e
O f Ni-Mo-Cu r e l a t i v e t o Ni-Mo. Ponec (10,12) suggests t h a t i n o r d e r t o d i s s o c i a t e
a d s o r b e d CO and f o r m t h e a c t i v e s u r f a c e c a r b o n s p e c i e s an.ensemble o f a c t i v e N i
s i t e s i s necessary, and t h a t a d d i t i o n o f Cu, i t s e l f i n a c t i v e towards methanation,
d i l u t e s t h e a c t i v e N i s i t e s c a u s i n g l o w e r m e t h a n a t i o n a c t i v i t y o f Ni-Cu c a t a l y s t s
as compared t o N i c a t a l y s t s .

58
 The change i n s e l e c t i v i t y o b s e r v e d f o r a l l c a t a l y s t s a f t e r low p r e s s u r e
c a r b o n d e p o s i t i o n s u g g e s t s some t y p e o f m o d i f i c a t i o n o f t h e a c t i v e s i t e s . It i s
a l s o reasonable t o e x p e c t t h a t a carbon covered s u r f a c e w i l l behave c a t a l y t i c a l l y
more l i k e a metal c a r b i d e than a c l e a n metal surface. T h i s i s supported by previous
work of McCarty e t a l . (13,14) and Sexton e t a l . ( 1 5 ) . I n a d d i t i o n , massive d e p o s i t s
O f c a r b o n i n f i l a m e n t o u s f o r m have been shown b y p r e v i o u s w o r k e r s t o s e p a r a t e and
encapsulate metal c r y s t a l l i t e s . Thus f o r m a t i o n o f l a r g e amounts o f Cg may p l a c e
t h e metal c r y s t a l l i t e s i n a new s u p p o r t environment, t h e subsequent change i n metal-
s u p p o r t i n t e r a c t i o n s i n d u c i n g changes i n a c t i v i t y / s e l e c t i v i t y p r o p e r t i e s . I n t h e
case of b i m e t a l l i c c a t a l y s t s metal-carbon i n t e r a c t i o n s may induce changes i n s u r f a c e
c o m p o s i t i o n w h i c h a f f e c t s e l e c t i v i t y . Ponec ( 1 2 ) , f o r example, p r e s e n t s evidence
f o r t h e s u r f a c e m o d i f i c a t i o n o f a Ni-Cu f i l m b y repeated a d s o r p t i o n and temperature
programmed d e s o r p t i o n o f CO.

The d a t a i n T a b l e 2 suggest t h a t c a r b o n d e p o s i t i o n a t h i g h p r e s s u r e may

i n c r e a s e t h e amount o f Cg formed i n t h e case o f N i and Ni-Mo c a t a l y s t s . That i s ,
t h e percentage decrease i n CH4 t u r n o v e r number observed a f t e r h i g h p r e s s u r e carbon
d e p o s i t i o n i s e q u a l t o o r g r e a t e r t h a n t h a t o b s e r v e d i n t h e low p r e s s u r e r u n s .
T h i s o b s e r v a t i o n can be e x p l a i n e d on t h e b a s i s o f C O p a r t i a l pressure. A t h i g h
p r e s s u r e t h e minimum p a r t i a l p r e s s u r e o f CO was 10 kPa (assuming 90% c o n v e r s i o n )
whereas t h e maximum p a r t i a l p r e s s u r e o f CO i n t h e l o w p r e s s u r e carbon d e p o s i t i o n
t e s t s was 6 kPa. A t a h i g h e r p a r t i a l p r e s s u r e o f CO t h e a d s o r p t i o n and d i s s o c i a t i o n
of CO on t h e c a t a l y s t s u r f a c e proceeds a t a much g r e a t e r r a t e (4,5). I f t h e carbon
f o r m a t i o n r a t e i s g r e a t e r t h a n t h e g a s i f i c a t i o n r a t e more w i l l result.

E f f e c t s o f Carbon D e a c t i v a t i o n on Apparent A c t i v i t y / S e l e c t i v i t y P r o p e r t i e s
i n a F i x e d Bed a t High Temperature, Conversion C o n d i t i o n s . Even though c o n s i d e r a b l e
c a r b o n f o u l i n s was e v i d e n t . r e l a t i v e l v l i t t l e d e a c t i v a t i o n was o b s e r v e d d u r i n a
s t e a d y s t a t e i e p o s i t i o n t e s t s f o r m o s t c a t a l y s t s e x c e p t Ni-Mo-Cu ( s e e F i g s . 2 a n i
3 ) . T h i s was p a r t i c u l a r l y t r u e a t h i g h p r e s s u r e . T h i s b e h a v i o r i n d i c a t e s t h a t
o n l y a p o r t i o n o f t h e a c t i v e s i t e s are necessary t o m a i n t a i n a h i g h r e a c t i o n r a t e .
I t i s t h e r e f o r e reasonable t o assume t h a t i n a f i x e d bed r e a c t o r most o f t h e r e a c t i o n
takes place i n a small zone at the entrance t o the bed, c r e a t i n g a l a r g e c o n c e n t r a t i o n
g r a d i e n t over t h e r e a c t o r . I n t h i s s m a l l zone, t h e CO p a r t i a l p r e s s u r e i s l a r g e
and t h e r a t e o f f o r m a t i o n o f Cg i s high; f u r t h e r downstream t h e c a t a l y s t i s s u b j e c t e d
t o a l o w e r C O p a r t i a l p r e s s u r e and l e s s Q i s formed. Thus a r e a c t i o n zone i s
c r e a t e d which g r a d u a l l y moves downstream as t h e c a t a l y s t becomes f o u l e d . Therefore,
a t h i g h temperature, h i g h c o n v e r s i o n c o n d i t i o n s and e s p e c i a l l y a t h i g h pressure,
we would expect t o observe v e r y l i t t l e d e a c t i v a t i o n u n t i l t h e r e a c t i o n zone reaches
t h e end o f t h e bed. The c a t a l y s t would then e x h i b i t an extremely r a p i d d e a c t i v a t i o n
s i m i l a r t o t h e d e p l e t i o n o f an ion-exchange column. Thus, t h e t r u e d e a c t i v a t i o n
b e h a v i o r i n a f i x e d bed a t h i g h t e m p e r a t u r e s and e s p e c i a l l y a t h i g h p r e s s u r e s i s
masked b y heat and mass t r a n s f e r l i m i t a t i o n s .

Ni-Mo-Cu e x h i b i t s a d i f f e r e n t type o f b e h a v i o r f r o m t h e o t h e r c a t a l y s t s
a t h i g h p r e s s u r e . D u r i n g t h e f i r s t t h r e e hours a v e r y r a p i d d e a c t i v a t i o n o c c u r s .
A f t e r t h i s time the d e a c t i v a t i o n r a t e i s s i m i l a r t o t h a t observed d u r i n g the low
p r e s s u r e carbon d e p o s i t i o n r u n . The t u r n o v e r number d a t a i n T a b l e 2 and t h e l a r g e r
amount o f c a r b o n f o r Ni-Mo-Cu r e l a t i v e t o N i ( T a b l e 3) s u g g e s t t h a t t h e r a t e o f
g a s i f i c a t i o n o f t h e d e p o s i t e d carbon i s slower a t h i g h p r e s s u r e r e s u l t i n g i n more
C f o r m a t i o n and more r a p i d d e a c t i v a t i o n . The p r e s e n c e o f Cu p r o b a b l y i n h i b i t s
t i e g a s i f i c a t i o n s t e p b y l i m i t i n g t h e a r e a a v a i l a b l e f o r H2 t o adsorb and s i n c e
h i g h e r CO p a r t i a l p r e s s u r e i n c r e a s e s t h e r a t e of C, f o r m a t i o n , a n e t i n c r e a s e i n
$, occurs. Ponec (12) showed t h a t f o r CO a d s o r p t i o n on Ni-Cu/Si02 powder t h e s u r f a c e
1 concentration increased w i t h time. Assuming s u c h a change i n Ni-Mo-Cu, t h e
i n c r e a s i n g c o n c e n t r a t i o n o f N i on the surface would i n c r e a s e t h e r a t e o f g a s i f i c a t i o n
w i t h t h e n e t e f f e c t of s l o w i n g down t h e r a t e of $ f o r m a t i o n , t h u s a c c o u n t i n g f o r
t h e lower d e a c t i v a t i o n r a t e observed a f t e r t h r e e hours.
59
 E f f e c t s of P r e - s u l f i d i n . Separate g r a v i m e t r i c s t u d i e s i n t h i s laboratory
(4,s) h a v m t h a t pre-su1fidi;g t h e c a t a l y s t s u b s t a n t i a l l y reduces the gasification
r a t e w i t h o u t s i g n i f i c a n t l y a f f e c t i n g t h e r a t e o f i n a c t i v e carbon d e p o s i t i o n . The
r e s u l t i s i n c r e a s e d Cg f o r m a t i o n (4,5) and more r a p i d d e a c t i v a t i o n of pre-sulfided
Ni-Mo-Cu and N i r e l a t i v e t o t h e f r e s h c a t a l y s t s ( s e e T a b l e 3).

Carbon D e p o s i t i o n i n a F l u i d i z e d Bed. As m i g h t be e x p e c t e d Ni-Mo-Cu and

Ni-Mo d e a c t i v a t e d more r a p i d l y i n a f l u i d i z e d bed t h a n i n a f i x e d b e d due t o more
u n i f o r m exposure t o t h e r e a c t i o n m i x t u r e . However, Ni-Mo-Cu d e a c t i v a t e d more r a p i d l y
t h a n Ni-Mo, a r e s u l t o p p o s i t e t o t h a t o b t a i n e d i n t h e f i x e d bed. Perhaps t h i s can
be a c c o u n t e d f o r b y t h e l o w e r space v e l o c i t i e s and l o w e r c o n v e r s i o n s a s s o c i a t e d
w i t h t h e f l u i d i z e d bed r e a c t o r . The r a t e o f c a r b o n f o r m a t i o n i s p r o p o r t i o n a l t o
t h e p a r t i a l p r e s s u r e o f CO. The lower c o n v e r s i o n would t r a n s l a t e t o a h i g h e r C O
p a r t i a l p r e s s u r e a t t h e c a t a l y s t s u r f a c e which would a f f e c t each c a t a l y s t d i f f e r e n t l y
because o f t h e i r d i f f e r e n t c o m p o s i t i o n s . C a r e f u l e x a m i n a t i o n o f t h e l o w p r e s s u r e
f i x e d bed data o f Tables 2 and 3 r e v e a l s t h a t Ni-Mo and Ni-Mo-Cu s u f f e r e d approxiinately
t h e same p e r c e n t a g e l o s s o f s u r f a c e area, b u t t h a t Ni-Mo c o n t a i n e d t e n t i m e s more
c a r b o n a f t e r t h e s t e a d y - s t a t e c a r b o n d e p o s i t i o n r u n . Thus u n d e r t h e h i g h e r CO
p a r t i a l p r e s s u r e Ni-Mo-Cu m i g h t b e e x p e c t e d t o d e a c t i v a t e more r a p i d l y t h a n N i -
Mo s i n c e i n c r e a s e d carbon d e p o s i t i o n would have more e f f e c t on Ni-Mo-Cu. A possible
a d d i t i o n a l e f f e c t i s t h a t under u n i f o r m exposure t o t h e r e a c t a n t m i x t u r e a g r e a t e r
m o d i f i c a t i o n o f t h e s u r f a c e o c c u r r e d f o r Ni-Mo-Cu t h a n f o r Ni-Mo. Since large
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 g r a d i e n t s a r e a b s e n t i n t h e f l u i d i z e d bed, t h e s e
r e s u l t s a r e much more i n d i c a t i v e o f t h e t r u e d e a c t i v a t i o n b e h a v i o r . Moreover,
t h e y model b e t t e r t h e b e h a v i o r a n t i c i p a t e d i n t h e BI-GAS process.

Regeneration o f Carbon F o u l e d C a t a l y s t s i n Air/Oxygen

The r e s t o r a t i o n o f a c t i v i t y f o l l o w i n g r e g e n e r a t i o n p r o v i d e s s t r o n g evidence
t h a t c a r b o n f o u l e d c a t a l y s t s c a n be r e g e n e r a t e d w i t h d i l u t e m i x t u r e s o f a i r o r
oxygen. I n f a c t , t h i s may be t h e o n l y p r a c t i c a l approach since i n i n d u s t r i a l equipment
t h e r e g e n e r a t i o n t e m p e r a t u r e i s u s u a l l y l i m i t e d t o 700 K, and s i g n i f i c a n t carbon
g a s i f i c a t i o n b y steam, H2 o r C02 does n o t occur a t temperatures below 800 K (16,17).
The i n c r e a s e i n CH4 t u r n o v e r number f o r t h e c a t a l y s t s a f t e r t h e h i g h p r e s s u r e d i l u t e
O2 t r e a t m e n t was more t h a n c o u l d be accounted f o r b y s i m p l e removal o f t h e deposited
c a r b o n . T h i s c o u l d b e t h e r e s u l t o f a s u r f a c e m o d i f i c a t i o n b y t h e O2 t r e a t m e n t
a n d / o r a m o d i f i c a t i o n w h i c h o c c u r r e d d u r i n g r e a c t i o n as d i s c u s s e d p r e v i o u s l y .

Palmer and V r o m (18) showed t h a t t h e a c t i v i t y o f n i c k e l i s i n c r e a s e d b y

h i g h t e m p e r a t u r e t r e a t m e n t w i t h 0 as a r e s u l t o f i n c o r p o r a t i n g d i s s o l v e d O2 j u s t
below t h e surface. Sexton and Somzrjai ( 1 5 ) r e p o r t e d s i m i l a r r e s u l t s . U n f o r t u n a t e l y
t h i s e f f e c t appears t o b e o n l y temporary, s i n c e t h e s p e c i f i c a c t i v i t y o f regenerated
Ni/A1 0 r e t u r n e d t o t h e same v a l u e as t h e f r e s h c a t a l y s t a f t e r 24 h o u r s o f r e a c t i o n
a t 625 ;i< H2/C0 = 4, a c o n d i t i o n c h o s e n t o e n s u r e t h a t f u r t h e r d e a c t i v a t i o n d i d
n o t occur.

Regeneration o f methane a c t i v i t y b y oxygen i s n o t w i t h o u t a p r i c e , however.

The r e s u l t s show an o v e r a l l d e c r e a s e i n s u r f a c e area a f t e r c a r b o n d e p o s i t i o n and
r e g e n e r a t i o n o f 18 t o 71%. T h i s s u r f a c e a r e a l o s s i s u n d o u b t e d l y a consequence
of s i n t e r i n g and even l o s s o f t h e c a t a l y s t c r y s t a l l i t e s themselves. Rostrup-Nielsen
( 1 9 ) r e p o r t s t h a t d e p o s i t e d c a r b o n grows i n l o n g h o l l o w f i l a m e n t s w i t h t h e N i c r y -
s t a l l i t e at t h e end. T r a n s m i s s i o n e l e c t r o n m i c r o s c o p y s t u d i e s i n t h i s l a b o r a t o r y
(20) c o n f i r m t h i s o b s e r v a t i o n . The N i c r y s t a l l i t e i s t h u s removed f r o m t h e support
b y t h e carbon f i l a m e n t and when t h e carbon i s removed by o x i d a t i o n t h e c r y s t a l l i t e
i s p r o b a b l y c a r r i e d o u t o f t h e r e a c t o r w i t h t h e gas s t r e a m . I n f a c t , c h e m i c a l
a n a l y s i s of f r e s h and r e g e n e r a t e d Ni/A1203 samples r e v e a l e d a 7% l o s s o f n i c k e l .
It may be, t h e r e f o r e , i m p r a c t i c a l t o r e g e n e r a t e c a r b o n - f o u l e d c a t a l y s t s w i t h a i r
o r oxygen s i n c e a f t e r a few c y c l e s o f d e a c t i v a t i o n and r e g e n e r a t i o n a l a r g e p a r t

60
of t h e a c t i v e s u r f a c e o f t h e c a t a l y s t w o u l d b e g o n e . I t depends, o f course, o n
how much N i i s removed p e r t r e a t m e n t and t h e f r e q u e n c y o f t r e a t m e n t s .

A Model f o r D e a c t i v a t i o n by Carbon

We p r o p o s e a model t o a c c o u n t f o r d e a c t i v a t i o n o f n i c k e l b y 6 - c a r b o n i n
a f i x e d bed d u r i n g methanation. The proposed model f o r d e a c t i v a t i o n i s a m o d i f i c a t i o n
of t h a t proposed by Wise e t a l . (21) f o r i n t e r a c t i o n o f s u l f u r w i t h N i . A m o d i f i c a t i o n
i n t h e r e a c t i o n mechanism i s a l s o made t o a c c o u n t f o r t h e t r a n s f o r m a t i o n of Ca
t o Cg and t h e l o s s o f a c t i v i t y f o r s u r f a c e r e a c t i o n between C and H as t h e number
of a v a i l a b l e n i c k e l s i t e s d i m i n i s h e s . Our proposed model i s

cos 4 cas + 0, 5)

,C + H, -+ (CH4)g stepwise 6)
2cas 3 C2BS 7)

where t h e s u b s c r i p t " s " denotes an adsorbed s p e c i e s . Since t h e a s t a t e r e p r e s e n t s

s i n g l e c a r b o n atoms w h i c h a r e e a s i l y g a s i f i e d and t h e B s t a t e r e p r e s e n t s p o l y -
a t a n i c carbon lrhich i s nuch l e s s a c t i v e i t i s reasonable t o assume t h a t t h e d i m e r i z a t i o n
o f s i n g l e CCC atoms t o Cg causes t h e d e a c t i v a t i o n observed f o r N i and N i b i m e t a l l i c
methanation c a t a l y s t s .

A c c o r d i n g t o o u r p r o p o s e d model t h e r a t e o f d e a c t i v a t i o n due t o carbon

f o u l i n g i s p r o p o r t i o n a l t o t h e r a t e o f Cg f o r m a t i o n w h i c h i s p r o p o r t i o n a l t o t h e
n e t r a t e o f CCC f o r m a t i o n . The r a t e o f &X f o r m a t i o n i s i n t u r n p r o p o r t i o n a l t o
the p a r t i a l p r e s s u r e o f CO and t h e a c t i v i t y o f t h e c a t a l y s t . Assuming f i r s t o r d e r
dependence o n b o t h o f t h e s e v a r i a b l e s , an e x p r e s s i o n f o r t h e d e a c t i v a t i o n r a t e
can be w r i t t e n as d a / d t = -kd[CO]a w h e r e k d e a c t i v a t i o n r a t e constant, [CO]
= c o n c e n t r a t i o n o f CO, a = n o r m a l i z e d a c t i v i $ y = a t t i m e t . The d e a c t i v a t i o n model
proposed b y Wise e t a l . f o r s u l f u r p o i s o n i n g ( 2 1 ) can be adapted b y assuming t h e
r e a c t i o n r a t e t o be f i r s t o r d e r i n CO c o n c e n t r a t i o n and t h a t t h e r e a r e no r a d i a l
c o n c e n t r a t i o n g r a d i e n t s . Simultaneous s o l u t i o n o f t h e d e a c t i v a t i o n r a t e e x p r e s s i o n
and t h e e q u a t i o n o f c o n t i n u i t y i n t h e z d i r e c t i o n ( d i r e c t i o n o f f l o w ) y i e l d s Equation
1. The f o l l o w i n g e x p r e s s i o n a l s o r e s u l t s i f z/V<<l, where V i s t h e v e l o c i t y i n t h e
z direction.

In[(---- '
-xco
)-13 = ln[exp(kaoz/V)-l]-kd[COo]t 8)

By p l o t t i n g '
I n [(- l - X c o I-'' versus t i m e t, v a l u e s f o r k and k d can be d e t e r m i n e d
f r o m t h e i n t e r c e p t at!d s l o p e r e s p e c t i v e l y .

E q u a t i o n 1 i s p l o t t e d as a s o l i d l i n e i n F i g u r e 2 u s i n g t h e s e parameters.
I t f i t s t h e data very w e l l f o r t h e low pressure f i x e d bed runs. A s i m i l a r development
assuming no c o n c e n t r a t i o n g r a d i e n t i n t h e z d i r e c t i o n l e a d s t o t h e e x p o n e n t i a l
r e l a t i o n s h p o f E q u a t i o n 3 f o r f l u i d i z e d beds. U s i n g Equations 1 and 3 we e s t i m a t e
t h a t h a l f o f t h e a c t i v e s i t e s f o r Ni-Mo w o u l d be f o u l e d i n 37 days i n a f i x e d bed
and o n l y 30 h o u r s i n a f l u i d i ed bed based on p r o c e s s c o n d i t i o n s o f H2/C0 = 1.4
and a space v e l o c i t y o f 3000 h- . I
The f a c t t h a t t h e p r o p o s e d model f o r d e a c t i v a t i o n b y carbon d e p o s i t i o n
p r e d i c t s experimental behavior q u i t e w e l l indicates t h a t i t i s consistent w i t h
t h e observed d e a c t i v a t i o n b e h a v i o r - - i . e . , t h e r a t e o f d e a c t i v a t i o n increases
as t h e p a r t i a l p r e s s u r e of CO i s i n c r e a s e d and d e c r e a s e s as t h e s u r f a c e o f t h e
61
c a t a l y s t i s f o u l e d b y i n c r e a s i n g accumulations o f i n a c t i v e carbon.

CONCLUSIONS

1. A t 7 2 3 K a n d a t m o s p h e r i c p r e s s u r e d e a c t i v a t i o n o f n i c k e l c a t a l y s t s
b y carbon e x h i b i t e d f i r s t order dependence on CO c o n c e n t r a t i o n (second o r d e r o v e r a l l ) .
H a l f - l i v e s of N i and Ni-Mo c a t a l y s t s v a r i e d from 13-170 hours. Based on t h e s p e c i f i c
i n t r i n s i c a c t i v i t i e s (CH t u r n o v e r numbers) a f t e r r e a c t i o n under carbon d e p o s i t i n g
c o n d i t i o n s t h e o r d e r o f I e c r e a s i n g r e s i s t a n c e t o carbon d e p o s i t i o n a t l o w p r e s s u r e
was: N i , N i ( p r e - s u l f i d e d ) , Ni-Mo-Cu, Ni-Mo, Ni-Mo-Cu ( p r e - s u l f i d e d ) .

2. D u r i n g r e a c t i o n i n a f i x e d bed a t h i g h temperatures and pressures l i t t l e

a p p a r e n t d e a c t i v a t i o n was o b s e r v e d e x c e p t i n t h e case o f Ni-Mo-Cu. The e f f e c t s
o f d e a c t i v a t i o n were masked b y t h e f a s t r a t e o f r e a c t i o n o c c u r r i n g i n a p o r t i o n
o f t h e bed. Thus t h e t u r n o v e r numbers d e t e r m i n e d under r e a c t i o n l i m i t e d c o n d i t i o n s
reveal the true e f f e c t s o f deactivation.

3. Ni-Mo i s more r e s i s t a n t t o c a r b o n d e p o s i t i o n i n a f l u i d i z e d bed t h a n

Ni-Mo-Cu. The f l u i d i z e d bed e x p e r i m e n t s p r o v i d e more r e a l i s t i c i n d i c a t i o n o f t h e
t r u e d e a c t i v a t i o n b e h a v i o r because t e m p e r a t u r e and r e a c t a n t c o n c e n t r a t i o n s a r e
more u n i f o r m than i n a f i x e d bed.

4. P r e - s u l f i d i n g t h e c a t a l y s t s does n o t improve t h e i r t o l e r a n c e t o carbon

deposition. I n f a c t , p r e - s u l f i d i ng Ni-Mo-Cu s e v e r e l y d e g r a d e d i t s p e r f o r m a n c e
under severe carbon d e p o s i t i o n c o n d i t i o n s . I t i s b e l i e v e d t h a t s u l f u r poisons
t h e g a s i f i c a t i o n o f a c t i v e carbon leading t o a b u i l d up and t r a n s f o r m a t i o n t o i n a c t i v e
carbon.

5. A l o w p r e s s u r e d i l u t e a i r m i x t u r e a t 5 7 3 K r e g e n e r a t e s most carbon
f o u l e d c a t a l y s t s . Using a d i l u t e O2 m i x t u r e a t h i g h pressure r e s u l t s i n CH4 t u r n o v e r
numbers and CH4 y i e l d s w h i c h a r e t e m p o r a r i l y h i g h e r t h a n f o r f r e s h c a t a l y s t s . Regen-
e r a t i o n u s i n g a i r o r O2 r e s u l t s i n a s i g n i f i c a n t l o s s o f s u r f a c e area, b u t i t may
be t h e o n l y p r a c t i c a l method due t o temperature l i m i t a t i o n s o f i n d u s t r i a l equipment.

ACKNOWLEDGEMENTS

The a u t h o r s g r a t e f u l l y acknowledge f i n a n c i a l s u p p o r t f r o m B i t u m i n o u s Coal

Research, I n c . u n d e r t h e i r C o n t r a c t No. EF-76-C-01-1207, U.S. D e p t . o f Energy;
p e r m i s s i o n t o p u b l i s h c a t a l y s t d a t a from t h e C1 imax Molybdenum Company o f M i c h i g a n
and t h e Harshaw C h e m i c a l Co.; and t e c h n i c a l a s s i s t a n c e f r o m D r . R o b e r t S t r e e t e r
o f BCR.

62
 REFERENCES

1. M.J. Whalen, "Carbon F o r m a t i o n i n M e t h a n a t o r s , " F i n a l R e p o r t t o ERDA, FE-

2240-10 ( J u l y 1976).

2. G.D. Weatherbee, G.A. J a r v i , and C.H. Bartholomew, Presented a t the 8 5 t h N a t i o n a l

AIChE Meeting, June 4-8, 1978, P h i l a d e l p h i a .

3. C.H. Bartholomew, F i n a l R e p o r t t o DOE, FE-1790-9, Sept. 6, 1977.

4. 0.C Gardner, M.S. Thesis, Brigham Young U., 1979.

5. D.C Gardner and C.H. Bartholomew, paper i n p r e p a r a t i o n .

6. R.W. F o w l e r , J r . and C.H. Bartholomew, I & E C P r o d . Res. & Dev., i n press.

7. C.H. Bartholomew, " A l l o y C a t a l y s t s w i t h M o n o l i t h Supports f o r D e r i v e d Gases,"

Q u a r t e r l y T e c h n i c a l Progress R e p o r t t o ERDA, FE-1790-1, (Aug. 6, 1975).

8. C.H. Bartholomew and R.J. F a r r a u t o , J. C a t a l . 5, 4 1 (1976).

9. R.B. P a n n e l l , K . S . Chung, and C.H. Bartholomew, J. C a t a l . 46, 340 ( 1 9 7 7 ) .

10. M. A r a k i and V. Ponec, J. C a t a l . , 44, 439 ( 1 9 7 6 ) .

11. J.G. McCarty and H. Wise, J. C a t a l . , 57, 406 (1979).

12. V. Ponec, C a t a l . Rev. - S c i . Eng., E ( l ) , 151 (1978).

13. J.G. McCarty and R.J. Madix, J. C a t a l . 3,402 ( i 9 7 5 ) .

14. J.G. McCarty and R.J. Madix, Surface S c i . , 54, 121 (1976).

15. B.A. Sexton and G.A. Somorjai, J. C a t a l . , 5, 167 (1977).

16. J.L. F i g u e i r d o and D.L. Trim, J. C a t a l . , 40, 154 (1975).

17. D.L. T r i m , C a t a l . Rev. - S c i . Eng. E ( 2 ) , 155 (1977).

18. R.L. Palmer and D.A. Vroom, J. C a t a l . 50, 244 (1977).

19. J.R. Rostrup-Nielsen, J. C a t a l . 27, 343 (1972).

20. D. Mustard and C.H. Bartholomew, paper i n p r e p a r a t i o n , (1979).

21. H. Wise, B.J. G i k i s , W.E. Isakson, J.G. McCarty, K.M. S a n c i e r , S. S c h e c h t e r ,

P.R. W e n t r c e k , and B . J . Wood, S R I , F i n a l R e p o r t PERC-0060-8 (ERDA), Sept.
30, 1977.

63
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Figure 1. Equilibrium Diagram a t 723 K and 138 kPa Showing
BI-GAS and Test Feed Gas Compositions. A = BI-GAS,
B = Fluidized Bed Runs, C = High and Low Pressure
Runs plus some D i f f e r e n t i a l R u n s , D = D i f f e r e n t i a l
Runs. Curve 1 i s the equilibrium curve based on
graphite. Curve 2 i s based on "non-ideal" carbon
a s reported by J.R. Rostrup-Nielsen i n J . Cat. 27,
343-356 (1972).

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70
 F u r t h e r R e s u l t s on t h e R e a c t i o n of H2/C0 on Fused I r o n
by t h e T r a n s i e n t Method

J. P. Reymond, P. Mgriaudeau,
B. Pommier, and C . 0. Bennett*

L a b o r a t o i r e de Thermodynamique e t C i n e t i q u e Chimiques
U n i v e r s i t 6 Claude B e r n a r d , Lyon I
69621 V i l l e u r b a n n e , F r a n c e

Introduction

J n a p r e v i o u s s t u d y (1) i t h a s been proposed t h a t t h e s u r f a c e of a promoted

f u s e d i r o n c a t a l y s t i s l a r g e l y covered w i t h carbon d u r i n g t h e s t e a d y - s t a t e r e a c t i o n
o f hydrogen and c a r b o n monoxide (90% H 2 . 10% CO) a t a t m o s p h e r i c p r e s s u r e and 2 5 O O C .
T h i s same c a t a l y s t , a commercial ammonia s y n t h e s i s c a t a l y s t (CCI), w a s a l s o e v a l u -
a t e d ( a t 2 . 0 MPa) i n a more a p p l i e d way i n c o n n e c t i o n w i t h t h e s t u d y of a scheme
f o r energy s t o r a g e i n a c e n t r a l power p l a n t ( 2 , 3 ) . I t i s now c l e a r t h a t it is
n e c e s s a r y t o c o n s i d e r t h a t each c a t a l y s t ( < . e . , even t h e same m e t a l on d i f f e r e n t
s u p p o r t s ) may o p e r a t e f o r r e a c t i o n s of H2/CO t h r o u g h a unique sequence of s t e p s ,
or a t l e a s t w i t h a p a r t i c u l a r r a t e - d e t e r m i n i n g s t e p . Thus a l t h o u g h t h e hydrogena-
t i o n o f s u r f a c e c a r b o n seems t o b e r a t e - l i m i t i n g on i r o n (l), on r u t h e n i u m t h e d i s -
s o c i a t i o n o f adsorbed CO h a s been proposed as r a t e l i m i t i n g ( 4 ) . The p r e s e n t work
i s a c o n t i n u a t i o n o f t h a t of r e f e r e n c e (1); t h i s t i m e t h e r o l e of C02 and H30 h a s
been i n v e s t i g a t e d , and i n t e r e s t i n g i n f o r m a t i o n h a s been o b t a i n e d on t h e c h a i n
growth p r o c e s s .

Experimental

The r e a c t o r was made o f Ulr-inch s t a i n l e s s s t e e l t u b e and f i l l e d w i t h 1 0 0 mg

Of c a t a l y s t ( p a r t i c l e s of 300 pm) mixed w i t h 500 mg of g l a s s b e a d s o f t h e same s i z e .
The r e a c t o r and t h e g l a s s b e a d s were confirmed t o produce no p r o d u c t s a t t h e r e a c -
t i o n c o n d i t i o n s . Feed r a t e s of H2/CO ( 9 / 1 ) between 20 and 120 ml/min were e x p l o r e d
b u t i f n o t o t h e r w i s e n o t e d , 40 ml/min was u s e d ; t h e c o n v e r s i o n was always less t h a n
5% o f t h e CO f e d .

Hydrogen (99.99%, A i r L i q u i d e ) was p u r i f i e d by a m o l e c u l a r s i e v e (SA) t r a D ,

followed by a deoxo r e a c t o r , f o l l o w e d by a second m o l e c u l a r s i e v e 5 A . Carbon mon-
o x i d e ( 9 9 . 9 % , A i r L i q u i d e ) was passed t h r o u g h a g l a s s t u b e h e a t e d t o 22O0C t o d e -
compose c a r b o n y l s and t h e n t h r o u g h a t r a p of a c t i v a t e d carbon a t 25OC.

4 n a l y s i s of t h e r e a c t i o n p r o d u c t s was by g a s chromatography. F o r t h e s e p a r a -
t i o n o f t h e h y d r o c a r b o n s , a Poropak Q (80-100 mesh) 6-m, 1 / 8 - i n c h s t a i n l e s s s t e e l
column was u s e d w i t h a f l a m e i o n i z a t i o n d e t e c t o r . Column t e m p e r a t u r e was 195OC,
and t h e c a r r i e r g a s (He) w a s used a t 30 ml/min. The C02 and H20 were measured by
a second i d e n t i c a l Poropak 0 column a t 175OC, l e a d i n g t o a t h e r m a l c o n d u c t i v i t y
d e t e c t o r . F o r t h e r e a c t i o n c o n d i t i o n s u s e d , o n l y a l k a n e s were found among t h e
hydrocarbon p r o d u c t s .

Results

The B a s i c R e a c t i o n

A f t e r a n i n i t i a l r e d u c t i o n i n f l o w i n g hydrogen a t 60 ml/min f o r 60 h o u r s
a t 500°C, t h e r e a c t o r is c o o l e d t o 250°C, and t h e f e e d i s s w i t c h e d a t t i m e z e r o t o
10% CO i n H2. The c u r v e 1 of F i g . 1 r e s u l t s . The d e a c t i v a t i o n i s r a p i d and t h e
p r o d u c t i o n r a t e o f methane p a s s e s through a maximum. A r e a c t i v a t i o n i n H 2 a t 5 0 0 O C

*
Now a t U n i v e r s i t y of C o n n e c t i c u t , S t o r r s , C o n n e c t i c u t 06268.
71
f o r 1 5 hours i n c r e a s e s t h e a c t i v i t y o f t h e c a t a l y s t t o a l e v e l above what it was a t
t h e end of t h e f i r s t run, b u t below what i t was a t its maximum. T h i s p r o c e s s con-
t i n u e s w i t h f u r t h e r r e a c t i v a t i o n s , and F i g . 1 shows c u r v e s a f t e r 1 0 r e a c t i v a t i o n s
and a f t e r 20 r e a c t i v a t i o n s . However, it was found t h a t a s h o r t ( 3 0 min) t r e a t m e n t
b y oxygen a t 5 O O O C and 1 a m b e f o r e t h e u s u a l r e d u c t i o n by hydrogen produced a r e l -
a t i v e l y s t a b l e c a t a l y s t , a s shown by t h e c u r v e 0 2 of F i g . 1. The a c t i v i t y of t h e
c a t a l y s t - i s o b v i o u s l y v e r y s e n s i t i v e t o i t s s t a t e of o x i d a t i o n and t o t h e concen-
t r a t i o n of r e f r a c t o r y c a r b o n a t or n e a r i t s s u r f a c e . I t may be r e c a l l e d t h a t
Matsumoto and Bennett (1) found t h a t s h o r t t r e a t m e n t s i n helium a t 2 5 O O C c o n v e r t e d
t h e a c t i v e carbon i n t e r m e d i a t e t o a form i n a c t i v e a t t h i s t e m p e r a t u r e . S i m i l a r
e f f e c t s a r e observed f o r n i c k e l ( 5 ) .

F i g u r e 2 shows t h e o t h e r hydrocarbons produced c o r r e s p o n d i n g t o t h e c u r v e

l a b e l l e d 02 o n F i g . 1. The numbers by t h e c u r v e s a r e t h e s t e a d y - s t a t e r a t e s of
p r o d u c t i o n d i v i d e d by t h a t for methane. These s e l e c t i v i t i e s a r e i n s e n s i t i v e t o t h e
a c t i v i t y l e v e l and a r e a b o u t t h e same f o r a l l t h e c a t a l v s t c o n d i t i o n s of F i g . 1.
Water and carbon d i o x i d e a r e also produced, b u t t h e s e p r o d u c t i o n r a t e s a r e l e s s
r e p r o d u c i b l e . The c a t a l y s t h a s a f r a c t i o n exposed of o n l y about 5 p e r c e n t , and i t
h a s been shown t h a t t h e e n t i r e mass of i r o n is c a r b u r i z e d (1). Thus small changes
i n carbon c o n c e n t r a t i o n i n t h e b u l k may produce C 0 2 and H 2 0 a t r a t e s a t l e a s t a s
h i g h a s t h e c a t a l y t i c r e a c t i o n . F i g u r e 3 shows t h e h i s t o r y of a f r e s h l y reduced
c a t a l y s t a f t e r exposure t o CO/H2 a t 2 5 0 ° C , H2 a t 2 5 0 ° C , and f i n a l l y H2 programmed
t o 5 0 0 O C . The f i r s t peak r e u r e s e n t s t h e removal o f a s u r f a c e carbon i n t e r m e d i a t e
a s methane, and t h e second l a r g e peak comes from t h e d e c a r b u r i z a t i o n o f t h e b u l k
of t h e c a t a l y s t . T h i s r e s u l t h a s a l r e a d y been d i s c u s s e d (1).

Another a s p e c t of t h e r e a c t i n g system can be s e e n i n F i g . 4 . Experiments were

s t a r t e d w i t h a f e e d r a t e o f 120 ml/min, b u t t h e c o n v e r s i o n ( 0 . 0 0 3 t o CH4) was n o t
s u f f i c i e n t t o o b t a i n r e l i a b l e a n a l y s e s f o r H20 and COP by chromatography ( t h e r m a l
c o n d u c t i v i t y d e t e c t o r ) . The hydrocarbons, however, were a n a l y z e d c o r r e c t l y ( f l a m e
ionization d e t e c t o r ) . When t h e c o n v e r s i o n was i n c r e a s e d ( 0 . 0 0 6 t o C H 4 ) by r e d u c i n g
t h e f e e d r a t e t o 20 ml/min, a much lower f o r m a t i o n r a t e of methane was o b s e r v e d .
T h i s r e d u c t i o n i n a c t i v i t y c a n o n l y b e e x p l a i n e d by i n h i b i t i o n o f t h e r a t e s b y pro-
d u c t s of t h e r e a c t i o n ; t h e r e a c t a n t c o n c e n t r a t i o n s a r e of c o u r s e a l m o s t unchanged.
In o t h e r words, even a t t h e s e low c o n v e r s i o n s t h e r e a c t o r i s n o t t r u l y d i f f e r e n t i a l .

We a r e t h u s l e d t o i n v e s t i g a t e t h e e f f e c t of t h e p r o d u c t s of r e a c t i o n on t h e
r e a c t i o n r a t e s , and t h e s e e x p e r i m e n t s w i l l be d e s c r i b e d l a t e r . I n o r d e r n o t t o be
m i s l e a d by s e c u l a r changes i n t h e c a t a l y s t , a s t e a d y s t a t e c o n d i t i o n i s f i r s t e s -
t a b l i s h e d w i t h 10% CO t H 2 f e e d . The f e e d i s t h e n changed t o one c o n t a i n i n g H20,
C O q . e t c . a s d e s i r e d , and f i n a l l y it is changed back t o 10% CO t Y2.

The base r e a c t i o n h a s been s t u d i e d a t s e v e r a l t e m p e r a t u r e s ( 2 3 0 ° , 2 5 0 ° , 270°,

a n d 3 O O 0 C ) , and a n a c t i v a t i o n energy of 2 0 . 4 kcal/mole i s observed, s i m i l a r t o t h e
v a l u e found a t 2.0 MPa ( 2 ) .

I n f l u e n c e o f C02

To t h e r e a c t i o n m i x t u r e 10% CO t H2 was added 5% C O 2 . The CHq p r o d u c t i o n

d i m i n i s h e d by about E%, and when t h e C 0 2 was removed t h e methane f o r m a t i o n r a t e r e -
gained i t s i n i t i a l value. This e f f e c t is not s u f f i c i e n t t o explain Fig. 4 .

If t h e CO i n t h e f e e d gas i s r e p l a c e d by C 0 2 , t h e methanation r e a c t i o n con-

tinues a t a lower r a t e , as shown i n Table 1. The f o r m a t i o n of h i g h e r hydrocarbons,
however, 1 s d r a s t i c a l l y r e d u c e d . I h e C02 i s d i s s o c i a t i v e l y a d s o r b e d , b u t t h e s u r -
f a c e oxygen concentration is increased.
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 I n f l u e n c e o f Water

A c o n c e n t r a t i o n of 0.6% w a t e r vapor was added t o t h e 1 0 % CO t H2 f e e d

m i x t u r e a t s t e a d y - s t a t e r e a c t i o n , and F i g . 5 shows t h e r e s u l t . The i n h i b i t i n g e f -
f e c t Of w a t e r i s c l e a r , and i t i s p r o b a b l e t h a t t h e lower r a t e s a t h i g h e r conversion
shown i n F i g . 4 a r e e x p l a i n e d by t h e i n c r e a s e d w a t e r c o n c e n t r a t i o n a t h i g h e r con-
version.

It i s a l s o i n t e r e s t i n g t o evaluate t h e c a p a b i l i t y of t h e s t e a d y - s t a t e c a t a l y s t
s u r f a c e t o c a t a l y z e t h e s h i f t r e a c t i o n . F i g u r e 6 i n d i c a t e s t h a t when t h e H2 i n
t h e 10% CO t H2 m i x t u r e i s r e p l a c e d by 0.6% water, a l l p r o d u c t i o n o f hydrocarbons
s t o p s , and a l a r g e r a t e o f C02 f o r m a t i o n i s o b s e r v e d . These r e s u l t s a r e f u r t h e r
e v i d e n c e o f t h e power o f t h e i r o n c a t a l y s t t o a d s o r b d i s s o c i a t i v e l y H 2 a s w e l l a s
co.
I n f l u e n c e of Ethane

The a d d i t i o n o f 1 0 % C2H6 t o t h e r e a c t a n t s d o e s n o t change t h e r a t e s of

r e a c t i o n . However, i r o n h a s some a c t i v i t y f o r h y d r o g e n o l y s i s ( 6 ) . I f t h e 10% CO t
H2 m i x t u r e is changed t o 1 0 % C2H6 t H2. methane is formed a t 0.65 u mole/g min ( s e e
F i g . 71, l e s s t h a n 10% o f a t y p i c a l m e t h a n a t i o n r a t e .

Influence of O l e f i n s

When 10% C2H4 t H2 i s f e d t o t h e r e a c t o r j u s t a f t e r t h e r e d u c t i o n o f t h e

c a t a l y s t a t 5OO0C, t h e c u r v e s of F i g . 7 a r e o b t a i n e d . There i s immediate p r o d u c t i o n
of methane, propane, n-butane, and n-pentane. Ethane i s confounded w i t h t h e l a r g e
e t h y l e n e peak i n t h e a n a l y s i s by chromatography. The r a t e s do n o t i n c r e a s e f r o m
z e r o as i n F i g . 2. A s w i t c h t o hydrogen ( n o t shown on F i g . 7 ) uroduces no methane
peak a t 25OoC, and programming t h e t e m p e r a t u r e t o 5OOOC r e s u l t s i n t h e p r o d u c t i o n
of o n l y 4 u moles of CHq/g o f i r o n . Thus t h e C2H4/H2 m i x t u r e does n o t c a r b u r i z e
t h e i r o n a t 25OOC. The r e a c t i o n r a t e s a f t e r 4 h o u r s w i t h e t h y l e n e a r e a b o u t t w i c e
t h o s e w i t h C O , and t h e i n i t i a l r a t e s a r e a n o r d e r o f magnitude h i g h e r . F i g u r e 7
shows a l s o t h e s w i t c h from C ~ H L + / Ht ~o CO/H2 and t h e n t o C&/H2.

F i g u r e 8 shows t h e u s u a l c u r v e s f o r CO/H2 o v e r a reduced c a t a l y s t , f o l l o w e d

by a s w i t c h t o C ~ H I + / Ho~v e r t h e now c a r b u r i z e d c a t a l y s t . These r e s u l t s a r e c o n s i s -
t e n t w i t h t h e i d e a t h a t t h e r a t e - d e t e r m i n i n g s t e p w i t h CO i s t h e hydrogenation o f
s u r f a c e c a r b o n . Subsequent c h a i n growth o c c u r s through CH2 g r o u p s ( o r CH), and if
t h e s e groups a r e formed d i r e c t l y from e t h y l e n e , t h e p r o d u c t i o n r a t e s o f t h e p r o -
d u c t s a r e h i g h e r ; t h e r a t e l i m i t i n g s t e p coming from CO is no l o n g e r r e l e v a n t . The
C2H4/H2 r e a c t i o n o c c u r s on i r o n , and a f t e r exposure of t h e c a t a l y s t t o CO/H2, much
of t h e s u r f a c e i s covered w i t h carbon, s o t h e r a t e o f CH4 p r o d u c t i o n w i t h C ~ H I + / H ~
of F i g . 8 is lower t h a n t h a t of Fig. 7.

F i g u r e 9 shows t h e r e a c t i o n of 10% C3H6 + H~ o v e r t h e reduced c a t a l y s t . The

r e s u l t s a r e q u a l i t a t i v e l y t h e same a s w i t h e t h y l e n e . Butene-2/H2 r e a c t s as shown
i n F i g . 1 0 , and butene-1/H2 (always 90% H2) g i v e s r a t e s t h a t a r e a l l a b i t lower
t h a n for butene-2, as shown. A l l t h e s e r e s u l t s emphasize t h a t on t h e i r o n s u r f a c e
t h e CH2 or CH fragments come r a p i d l y t o a s t e a d y s t a t e ; t h e r a t e s of p r o d u c t i o n of
t h e a l k a n e p r o d u c t s (no o l e f i n s were o b s e r v e d ) a r e n o t a p p r e c i a b l y i n f l u e n c e d b y
t h e s o u r c e o f t h e CH2 groups o n t h e s u r f a c e . However, t h e r e a r e some d i f f e r e n c e s ,
a s shown i n Table 2 , which g i v e s t h e r a t i o s of t h e p r o d u c t i o n r a t e s a f t e r 4 h o u r s .
S t a r t i n g from a g i v e n o l e f i n , t h e p r o d u c t s a r e m o s t l y of s h o r t e r c h a i n l e n g t h , and
c l o s e t o t h e c h a i n l e n g t h of t h e r e a c t a n t . I n any e v e n t , we a r e j u s t i f i e d i n sup-
p o s i n g t h a t , s t a r t i n g from CO/H2, a l l t h e s t e p s a f t e r CH2 or CH f o r m a t i o n a r e r a p i d ,
and l i t t l e o f t h e s u r f a c e i s covered by c h a i n fragments a t 25OoC and 100 kPa.

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Discussion

The n e w r e s u l t s of t h e p r e s e n t s t u d y confirm most a s p e c t s o f t h e s e q u e n c e o f

s t e p s proposed by Matsumoto and B e n n e t t (1). CO is adsorbed a s C + 0 , and t h e
f r e s h l y formed s u r f a c e c a r b o n i s t h e most abundant s u r f a c e i n t e r m e d i a t e ; i t s hydro-
g e n a t i o n by adsorbed hydrogen p r e s e n t a s H i s t h e r a t e - d e t e r m i n i n g p r o c e s s . Carbon
d i o x i d e added t o CO/H:, i s n o t s t r o n g l y enough adsorbed t o a f f e c t t h e r a t e a p p r e c i -
a b l y . However, i n t h e a b s e n c e o f C O , CO2/H2 makes methane a t a lower r a t e ; t h e
s u r f a c e i s more o x i d i z e d , and t h e a c t i v e C i s p r e s e n t i n lower c o n c e n t r a t i o n t h a n i n
t h e p r e s e n c e of CO.

However, w a t e r c a n compete w i t h CO f o r t h e s u r f a c e , and it o x i d i z e s t h e s u r -

f a c e w h i l e r e d u c i n g t h e a c t i v e C coverage by forming C02. The h i g h r e a c t i o n r a t e
of CO/H20 t o C02 r a t h e r t h a n CHq shows t h e s t r o n g a f f i n i t y of t h e s u r f a c e of t h e
i r o n c a t a l y s t f o r oxygen ( F i g s . 5-61.

We r e c a l l t h a t t h e r a t e of hydrocarbon p r o d u c t i o n o v e r a f r e s h l y r e d u c e d c a t a -
l y s t rises from a n i n i t i a l v a l u e o f zero. The c a r b o n formed from CO r e a c t s w i t h
t h e b u l k i r o n of t h e c a t a l y s t , and t h e s u r f a c e c a r b o n n e c e s s a r y for hydrocarbon pro-
d u c t i o n g r a d u a l l y i n c r e a s e s i n coverage a s t h e b u l k of t h e i r o n i s c a r b u r i z e d t o
Fe2 C a t 250OC. However, when C2H4/H2 is passed o v e r t h e reduced c a t a l y s t , no
a c t i v e C i n t e r m e d i a t e seems t o b e n e c e s s a r y . The r a t e s t a r t s a t a maximum v a l u e ,
and t h e i r o n i s n o t c a r b u r i z e d . Thus t h e observed f o r m a t i o n of CHq and C3H8 shown
in F i g . 7 a r i s e s t h r o u g h a CH, fragment. No oxygen i s p r e s e n t . I r o n t h u s behaves
d i f f e r e n t l y from c o b a l t , for which oxygen is a p p a r e n t l y n e c e s s a r y f o r c h a i n growth
(7, 8).

When a CO/H2 f e e d i s changed t o C2Hq/H2 ( F i g . E ) , t h e r a t e o f hydrocarhon pro-

d u c t i o n i s h i g h e r from e t h y l e n e t h a n from CO. Methane is an i m p o r t a n t p r o d u c t from
C2Hq/H2. T h i s r e s u l t i s n o t i n c o n s i s t a n t w i t h t h e l a c k o f 14CHq formed when 14C2H4
i s added i n s m a l l q u a n t i t y t o CO/H2 (9). With CO p r e s e n t t h e C I H n g r o u p s must
o r i g i n a t e p r i n c i p a l l y from C O , so t h a t t h e added l ' + C w i l l be c o n c e n t r a t e d p r i n c i -
p a l l y i n CxHy g r o u p s of x 2 2 .

I t i s c l e a r t h a t t h e r e a c t i o n of e t h y l e n e t a k e s p l a c e on t h e i r o n s u r f a c e ,
s i n c e t h e r a t e d e c r e a s e s a s t h e i n e r t g r a p h i t i c c a r b o n b u i l d s up ( F i g s . 7 and 8 ) .
I t w a s shown p r e v i o u s l y (1) t h a t t h e r e a c t i o n from CO a l s o o c c u r s on t h e i r o n p a r t
of t h e s u r f a c e ; a f t e r s t e a d y s t a t e under CO/H2, a b r i e f e x p o s u r e t o H 2 a l o n e and
t h e n a s w i t c h back t o CO/H2 l e a d s t o a temporary i n c r e a s e i n t h e r a t e . If t h e ex-
p o s u r e t o hydrogen is l o n g enough t o d e c a r b u r i z e some of t h e b u l k , t h e s u b s e q u e n t
CO/H2 r e a c t i o n r a t e i s lowered a s r e c a r b u r i z a t i o n l o w e r s t h e c o n c e n t r a t i o n o f t h e
a c t i v e s u r f a c e carbon.

A f r e s h l y r e d u c e d c a t a l y s t is c a r b u r i z e d by t h e H2/CO m i x t u r e i n a b o u t an
hour ( r e c a l l t h a t c a r b u r i z a t i o n i n CO a l o n e i s much s l o w e r (1)). During t h i s p e r -
i o d t h e hydrocarbon f o r m a t i o n r a t e g r a d u a l l y i n c r e a s e s as t h e s u r f a c e c a r b o n con-
c e n t r a t i o n rises, as i n f l u e n c e d by t h e b u l k c a r b o n ( c a r b i d e ) c o n c e n t r a t i o n . A
s w i t c h t o p u r e H2 g i v e s a methane peak, meaning t h a t hydrogen reacts a s H on t h e
s u r f a c e and t h a t t h e s u r f a c e c o v e r a g e by C is h i g h . The r a t e - d e t e r m i n i n g p r o c e s s
i s t h e f o r m a t i o n o f CH, from t h e s u r f a c e C ; s u b s e q u e n t c h a i n growth i s r a p i d and
o c c u r s t h r o u g h t h e s e g r o u p s , and t h e p r o d u c t d i s t r i b u t i o n i s determined by t h e
r a t e of p r o p a g a t i o n and t e r m i n a t i o n ( d e s o r p t i o n ) of c h a i n s a r i s i n g from CH,. The
p r e s e n c e of H20 and t o some e x t e n t C02 i n t h e g a s phase i n c r e a s e s s u r f a c e 0 a t
t h e expense of C a n d / o r H , i n h i b i t i n g t h e r e a c t i o n . However, a c t i v e s u r f a c e c a r -
bon i s g r a d u a l l y c o n v e r t e d t o i n e r t ( a t 250'C) g r a p h i t e , and a c t i v i t y s l o w l y de-
c l i n e s a s t h e p a r t of t h e i r o n covered w i t h l a b i l e C d e c r e a s e s . For a much re-
g e n e r a t e d c a t a l y s t , oxygen f o l l o w e d by hydrogen c l e a n s o f f a h i g h e r f r a c t i o n of
i n e r t g r a p h i t e than H2 a l o n e .
74
References

1. Matsumoto, H . , and B e n n e t t , C . O . , J. C a t a l . 53, 331 (1978).

2. Atwood, H . E . , and Bennett, C . O . , I n d . Eng. Chem. P r o c e s s Des. Dev. 18,
163 ( 1 9 7 9 ) .
3. Borghard, W. G . , and B e n n e t t , C . O . , I n d . Eng. Chem. P r o d u c t Res. Dev. 2,
18 (1979).
4. D a l l a B e t t a , R . A . , and S h e l e f , M . , J. Catal. 4 9 , 383 ( 1 9 7 7 ) .
5. McCarty, J. G . , and Wise, H . , J. Catal. 57. 4 0 F ( 1 9 7 9 ) .
6. Montarnel, R . , and Martino, G . , Rev. I n s t , F r a n S a i s du P Q t r o l e 32, 367 (1977)
7. Gibson, E. J., and C l a r k e , R . ! d . , J. Appl. Chem. 11 293 (1962).
8. 60,
E i d u s , Y a T . , Z e l i n s k i i , N. D . , and Ershov, N . I . , Dokl. Akad. Nauk SSSR
599 (1948).
9. H a l l , W. K . , Kokes, R . J . , and E m m e t t , P . H . , J. Am. Chem. SOC. 82, 1027
(1960).

75
 Table 1

Reaction of C02 a n d H:,

Feed
F o r m a t i o n Rate,
Before After
1-1 m o l e / g min.
7.0 4.4 7.4
CH4
3.2 0.52 3.5
‘ZH6
1.5 0.065 1.5
C3H8

Table 2

R e l a t i v e P r o d u c t i o n Rates
( 4 h o u r s on s t r e a m )

-
C2 -
c3 c11
- c5
-
Feed M i x t u r e c1

10% CO + H2 0.6 0.29 0.10 0.02

10% C2Hq + H2 0.15 0.06 0.001

1 0 % C3H6 + H2 0.49 0.087 0.002

10% b u t e n e - 1 + H
2
0.19 0.76 0.08

10% b u t e n e - 2 + H
2
0.20 0.92 0.09

76
-
0
0
I
VU

>

> - 9

>
N

L ?
J = 2
> Y

>

3
3
0

0
N

L
.
I=

'2

0
 0 0 0
in -r N
I I I

.
v
0

CJ
L

t c
.r(
tJ
m
a
e,
m c
tJ
C
"l

79
 .b
L

d
 N
I
-+
I -

X
 Synthesis Gas Reactions Using Catalysts Formed by Oxidizing
Ni-Containing Intermetallic Compounds

H. Imamura and W. E. Wallace

Department of Chemistry
University of Pittsburgh
Pittsburgh, PA. 15260

I. Introduction

Intermetallic compounds containing rare earths or actinides in chemical union

with the transition metals Fe, Co or Ni are transformed when exposed to synthesis
gas at elevated temperatures into mixtures of rare earth or actinide oxides and
elemental Fe, Co or Ni. It has been found that these mixtures are exceptionally
active for syngas conversion (1-12). The converted alloys have been character-
ized by Auger spectroscopy (1,13), x-ray diffraction, ESCA (14) and electron
microscopy ( 7 ) . These studies showed that the surface regions consisted of
transition metal nodules growing out of or dispersed on a substrate of rare earth
or actinide oxide. The decomposed materials rather than the original alloy appear
to be the catalytically active species for the reaction.

Additionally, it has been found that thorium-containing intermetallics such

as ThNi5 readily reacted with elemental oxygen to form a mixture of metallic Ni
and ThOp (12). The oxidation of ThNi5 occurred with a predominant formation of
Tho2 because of the strong chemical affinity of thorium for oxygen. During the
oxidation reaction metallic Ni aggregates precipitated out in a fashion similar
to that observed when the intermetallic is exposed to syngas. The reaction of
ThNi5 with a stoichiometric amount of oxygen required for the formation of thoria-
supported Ni catalysts (Ni/ThOp) brought about complete transformation into a mix-
ture of Ni and T h O p . This mixture had higher activity for methane formation by an
order of magnitude than oxide-supported catalysts (15) prepared by conventional
wet chemical procedures. Accordingly, it appears that the oxidation treatment of
intermetallics constitutes a novel way for forming oxide-supported catalysts with
high activity for syngas conversion.

In this work, the character of catalysts formed by the oxidation of several

rare earth-nickel intermetallic compounds was studied in the manner used earlier
to study the Th intermetallics. They were evaluated using x-ray diffraction,
ESCA and CO chemisorption techniques. The resulting materials, which are probably
new supported catalysts, were examined as syngas conversion catalysts.

11. Experimental

The intermetallic compounds (LaNiS, CeNi5, PrNi5, NdNi5, HoNi5, ErNi5 and
ThNis) were prepared by induction melting the metal components in a water-cooled
copper boat under an atmosphere of purified helium. These intermetallics were
subjected to remelting several times or annealing at a prescribed temperature to
insure homogeneity. The formation of the desired compounds was established by
x-ray diffraction analysis.

The oxidation treatment of the intermetallics, which had been previously

powdered in a porcelain mortar followed by outgassing, was conducted in the
presence of oxygen at 610 d g . The amount of oxygen uptake by the compound was
determined by the pressure drop in a closed system.

TO establish the nature of the sample thus treated x-ray diffraction, x-ray
photoelectron spectroscopy (ESCA) and CO chemisorption techniques were used.
82
Powder x-ray diffraction patterns were obtained using a Picker model 3488K
diffractometer with Cu radiation. ESCA spectra were recorded on an AEI ES200
electron spectrometer using A1 Ka radiation (1486.6 eV). The spectrometer was
operated at 1 2 KV and 25 mA with base pressure torr in the sample chamber.
The binding energy was determined by reference to the contamination C Is line at
285.0 eV. The CO chemisorption measurements were made at room temperature by
means of an adsorption flow method (16). The procedures used have been described
in detail previously (12).

111. Results and Discussion

1. Characterization of Catalysts Formed by Oxidation

X-RAY DIFFRACTION

The previous work (12) on the oxidation of thorium-containing intermetallic

compounds showed that the oxidation reaction occurred in a stepwise fashion. At
first, thorium in the alloy was oxidized largely to form the oxide, during which
process finely divided Ni aggregates precipitated out on the resulting oxide
surface. Accompanying this there was a remarkable enlargement in the surface
area, by up to 200-fold. After completion of the oxidation of thorium further
oxygen was taken up by the reaction of Ni to form NiO.

All the compounds studied in the present work readily reacted with consider-
able amounts of oxygen at 350°C. It was confirmed from x-ray diffraction studies
that the oxidation steps approximated that of the thorium intermetallics just
mentioned. For example, as depicted in Fig. 1, CeNi5 was completely transformed
into a mixture of Ni phase and CeOp, i.e., Ni/CeOp, when reacted with the
stoichiometric amount of oxygen required to oxidize the Ce present in the alloy.
When the CeOp-Ni mixture was exposed to oxygen there was an additional uptake of
oxygen. This occurred by the oxidation of Ni to form NiO. However, after reduc-
tion with hydrogen there was no evidence of NiO peaks in the pattern.

From x-ray line broadening measurements of the Ni (111) peak at 28 = 44.5

(Cu Ka radiation) it was possible to establish the Ni particle sizes dispersed
on the resulting oxide using the Sherrer equation (18). As shown in Table 1, the
particle sizes ranged from 90 to 350 1. The particle sizes usually but not always
showed an increase with increasing oxygen uptake for LaNi5, CeNi5 and ThNi5.

ESCA
-
X-ray diffraction studies in the preceding section provided an overall image
of the alloy transformed by the oxidation. ESCA measurements were made on the
oxidized CeNi5 to examine the chemical state of the surface species participating
in the reaction. ESCA spectra of the oxidized CeNi5 showed Ni, Ce, 0 and C signals
within the probing depth of ESCA (several atomic layers). Confirming the results
obtained by x-ray diffraction analysis, the Ce present in the surface region was
found to exist largely in an oxide form. For Ni species the oxidized CeNi5 (C-4)
exhibited the Ni 2 ~ 3 1 2peaks at 853.9 and 856.6 eV. These binding energies are
characteristic of Ni and NiO, respectively (19). Hence Ni is present in the sur-
face region, consisting of several atomic layers, as metal and oxide. Since the
ESCA peak intensity is directly correlated with the surface concentration, the
composition of the surface can be roughly established from the ESCA information.
The intensity ratio of Ni 2 ~ 3 1 2to Ce 3d5/p, a7.5, indicates that the surface is
largely metallic Ni.
83
 Table 1. Characterization of Catalysts Formed by Oxidation

Precursor
Intermetallic O2 Uptake Surface Areaa) CO Chemisorption Partigle Size
Compound (mmol/g) (m2/g) (umol/g) (A)
LaNi5 - 0.10* 0.17*
" (L-1) 1.71 0.55 1.2 90
" (L-2) 2.99 0.66 2.6 100
" (L-3) 6.57 3.5 7.1 100
CeNi5 - 0.08* 0.13
*
" (C-1) 2.32 1.1 4.8 110
" (C-2) 3.74 15.7 31.7 300
" (C-3) 4.47 25.4 45.7 200
" (C-4) 5.14 23.7 51.8 350
PrNi5 - 0.15
* 0.10
*
" (P-1) 1.73 0.79 2.8 170

NdNi5 (N-1) 1.71 1.1 1.2 140

HoNi5 (H-1) 1.64 0.76 2.0 330

ErNi5 (E-1) 1.61 1.0 2.0 280

ThNi5 - 0.09* 0.2*
" (T-1) 1.91 12.0 19.0 200
" (T-2) 3.35 18.0 105.7 270
a) Surface areas were measured at liquid nitrogen temperature by means of argon
adsorption (17).
* These values were obtained for the original intermetallic compounds.

CO CHEMISORPTION

Although ESCA studies revealed existence of metallic Ni in the surface region,

to obtain the information about the amount of metallic surface area or the number
of active sites present on the surface room temperature CO chemisorption measure-
ments were made. The results obtained are summarized in Table 1. It is informa-
tive to notice that the oxidized samples (L-l, C-l, P-l, N-l, H-l, E-l and T-l)
contain elemental oxygen corresponding to the complete formation of Ni/oxide
assuming a stoichiometric reaction. It is evident that the oxidation led to an
increase in the number of active sites along with a rise in the surface area. The
extent of the increase was observed to be dependent upon the particular rare earth
or actinide involved in the original compound. CeNi5 and ThNi5 exhibited striking
changes in chemisorption during the stages of oxidation. CO chemisorption
increases by up to 500-fold compared t o the original compound were observed. In
contrast, increases for LaNi5 were much less pronounced. The differing behavior
of CeNi5 and ThNi5 on the one hand and LaNi5 on the other undoubtedly reflects
important physicochemical differences. The most significant difference between
LaNi5 and the other two compounds is that La is tripositive and Ce and Th are
quadripositive. This leads t o a different electron concentration and perhaps a
difference in chemical stability. This may be responsible for variation in
84
 behavior of the systems produced by oxidation, but the precise factors and their
operation are as yet unclear.

2. Reaction of CO and H2

The reaction was carried out in the range of 150 to 300°C over the alloys,
which had been oxidized to varying extents. The data obtained are summarized in
Table 2. Activity for the present reaction was represented by the rate of CO

Table 2. Activity of Various Catalysts

Precursor 3
Intermetallic CO Conversion Activity T .N.x10
Compound (%) (ml/sec.g) (sec-l)

LaNi5 (L-1) 1.2 1.S X ~ O - ~ 48

CeNi5 (C-1) 2.0 2.~ x I O - ~ 18
" (C-2) 1.0* 1.2x1~-3*
I " (C-3) 2.6
*
3.7~10-~* 1.7
*
-3"
" (C-4) 5.0" 6.1~10 3.8"
PrNi5 (P-1) 1.8 2. 2x1~-3 26
NdNi5 (N-1) 0.5 6.l ~ l O - ~ 19
HoNiS (H-1) 1.6 2.0~10-~ 31
ErNi5 (E-1) 4.2 5. 2x1~-3 59
ThNi5 (T-1) 9.0
* 1.1x10-
2* 10.6"
-2" *
" (T-2) 7.0(at 190OC) 3.5~10 5.6
* The values correspond to the results measured at 205OC;
the others were obtained at 275"C, except as noted.

consumption per gram-catalyst. This kind of comparison seems valid since the
catalysts were used under very similar conditions. Taking into account the fact
that the catalytically active species is metallic Ni dispersed on the surface, it
is also of interest to specify the turnover number (T.N.), representing the
specific activity per site. The turnover number as molecules CH4 produced per site
per second was determined from CO chemisorption measurements assuming a 1:l ratio
of a CO molecule to surface Ni atom in the surface complex. Among the catalysts
studied the oxidized CeNiS and ThNi5 exhibited exceptional activity (Table 2). The
oxidized CeNi5 and ThNis showed T.N. measured at 205°C about an order of magnitude
higher than conventional silica- or alumina-supported Ni catalysts (15). It is
therefore apparent that the supported catalysts derived using the oxidation treat-
ment of intermetallics are exceptionally active for the conversion of CO and Hg to
methane. T. Inui et al. (20) have reported that activity for methanation was sub-
stantially enhanced when a3% rare earth oxide such as Lap03 or Ce2O3 was added t o
Ni-supported catalysts. It was found (21) that Tho2 was also operative as a
promoter for supported Ni catalysts.

It should be emphasized that the effectiveness of rare earth or actinide

oxide-supported catalysts for syngas conversion is very dependent upon the prepara-
tion method. As noted in the Introduction, for example, a ThOg-supported catalyst
(6) prepared using the conventional impregnation procedure followed by calcining
and reducing processes exhibited very poor activity compared to that obtained by
the oxidation technique. It thus appears that the oxidation treatment of inter-
metallics plays a decisive role in formation of active catalysts and this method
constitutes a new way of producing superior oxide-supported catalysts.
85
 A s shown i n Table 2, f o r t h e oxidized C e N i g and ThNi5 i n c r e a s e i n t h e e x t e n t
of o x i d a t i o n r e s u l t s i n an i n c r e a s e i n t h e a c t i v i t y . There i s a good correspon-
dence between t h e CO chemisorption and a c t i v i t y and i n t h i s r e s p e c t t h e p r e s e n t
systems c l o s e l y resemble behavior observed earlier f o r oxidized Ni5Si2 (22).

Hydrocarbon p r o d u c t s i n t h e r e a c t i o n were l a r g e l y methane. S m a l l amounts of

Cp t o C,, hydrocarbons were a l s o observed. S e l e c t i v i t y of hydrocarbon products over
v a r i o u s oxidized a l l o y s i s l i s t e d i n Table 3. The s e l e c t i v i t y w a s determined i n

Table 3. S e l e c t i v i t y of C a t a l y s t s

Precursor
Intermetallic Conversion Composition ( X )
Compound
(%) c1 c2 c3 c4

L a N i 5 (L-1) 1.8 92.0 7.0 1.0 -

C e N i 5 (C-1) 3.4 86.3 7.0 5.3 -
" (C-4) 5.0 77.3 15.9 6.8 -
PrNi5 (P-1) 3.1 88.4 6.6 5.0 -
NdNi5 (N-1) 1.8 91.3 4.3 4.3 -
HoNi5 (H-1) 2.5 82.4 8.1 9.5 -
E r N i 5 (E-1) 4.2 74.0 10.9 15.0 -
ThNi5 (T-1) 12.5 80.0 12.1 6.8 1.4

t h e conversion range below 10%. It is unclear from t h i s study whether t h e s e l e c -

t i v i t y is dependent upon e x t e n t of t h e t o t a l conversion. It i s t o b e noted t h a t
t h e s e l e c t i v i t y depends upon t h e n a t u r e of t h e rare e a r t h o r a c t i n i d e i n t h e pre-
c u r s o r compound. Oxidized LaNi5 revealed very high s e l e c t i v i t y f o r methane forma-
t i o n . This accords w i t h t h e o b s e r v a t i o n of T. I n u i e t a l . (20) r e f e r r e d t o above.

References

1. V. T. Coon, T. T a k e s h i t a , W. E. Wallace and R. S . Craig, J. Phys. Chem. E,

1878 (1976).
2. A. Elattar, T. T a k e s h i t a , W. E. Wallace and R. S . C r a i g , Science 196,1093
(1977).
3. V. T. Coon, W. E. Wallace and R. S . Craig, i n "The Fare E a r t h s i n Science and
Technology," e d s . G . J . McCarthy and 3 . J . Rhyne, Plenum Press, NY (1978),
p. 93.
4. A. E l a t t a r , W. E . Wallace and R. S . Craig, w., (1978), p . 87.
5. W. E. Wallace, i n Hydrides f o r Energy Storage, A. F . Andressen and A . J .
Maeland, e d s . , Pergamon Press Inc. (1978), p. 33.
6. A . E l a t t a r , W. E . Wallace and R. S . Craig, Advances i n Chemistry, i n p r e s s .
7 . V. T . Coon, Ph.D. T h e s i s , U n i v e r s i t y of P i t t s b u r g h , August, 1977.
8. C . A . Luengo, A . L. Cabrera, H. B. MacKay and M. B. Maple, J. C a t a l . 47, 1
(1977).
9. G. B. Atkinson and L. J . Nicks, J. Catal. 46, 417 (1977).
10. A . Elattar and W. E . Wallace, i n "The Rare E a r t h s i n Modern Science and
Technology" (1979), i n p r e s s .
11. A. E l a t t a r and W. E . Wallace, Science, submitted.
12. H. Imamura and W. E . Wallace, J. C a t a l , submitted.
13. A. G. Moldovan, A. E l a t t a r , W. E . Wallace and R. S. C r a i g , J . S o l i d S t a t e
Chem. 5, 2 3 (1978).
86
14. R. Chin, A. E l a t t a r , W . E. Wallace and D. Hercules, J . Catal., submitted.
15. M. A. Vannice, J. C a t a l . 37, 449 and 462 (1975); 60, 1 2 9 (1975); fi, 1 5 2
(1976); so, 2 2 8 (1977).
16. H. L . Gruber, Anal. Chem. 34, 1828 (1962).
17. F. M. Nelsen and F. T. Eggertsen, E., 3,1387 (1958).
18. H. P . Klug and L. E . Alexander, i n s a y D i f f r a c t i o n Procedures f o r Poly-
c r y s t a l l i n e & Amorphous M a t e r i a l s , 2nd ed.,p. 68, Wiley, NY (1974).
19. K. S. K i m and N . Winograd, Surf. S c i . 43, 625 (1974).
20. T. I n u i , M. Funabiki, M. Suehiro and T. Sezume, J . C . S . Faraday 1 7 5 , 787
(1979).
21. S. Medsforth, J . Chem. SOC. 123,1 4 5 2 (1923).
22. H . Imamura and W. E. Wallace, J . Phys. Chem., i n p r e s s .

87
 N i (2001 CeO,( II I)
Oxidized
CeNi, C - I )
I I I 1 i
60 50 40 30 20
29

F i g . 1 Comparison of x-ray d i f f r a c t i o n (Cu Ka r a d i a t i o n ) of t h e oxidized

and o r i g i n a l C e N i 5 .

ss
 CATALYTIC ASPECTS OF H I G H TEMPERATURE METHANATION

K a r s t e n P e d e r s e n , A l l a n Skov and J . R . Rostrup-Nielsen

Haldor Topsgie R e s e a r c h L a b o r a t o r i e s
NymGllevej 5 5 , DK-2800 Lyngby, Denmark

INTRODUCTION

Methanation o f s y n t h e s i s g a s m i x t u r e s i s an e s s e n t i a l s t e p i n t h e
m a n u f a c t u r e o f s u b s t i t u t e n a t u r a l g a s (SNG):
CO + 2 H 2 = CH4 + H20 (-AHo298= 2 0 6 kJ/mol)
C02 + 4 H 2 = CH4 + 2 H 2 0 = AH^^^^ 1 6 5 kJ/mol)

The r e a c t i o n s a r e c a t a l y z e d b y v a r i o u s m e t a l s of which s u p p o r t e d
nickel is preferred.

M e t h a n a t i o n f o r SNG p r o d u c t i o n i s complex b e c a u s e t h e h i g h con-

c e n t r a t i o n s of CO and C 0 2 i n v o l v e d r e s u l t i n l a r g e p o t e n t i a l t e m -
p e r a t u r e i n c r e a s e s . T h i s may c a u s e s i n t e r i n g of t h e c a t a l y s t or
f o r some cases a p o t e n t i a l f o r c a r b o n f o r m a t i o n .

One s o l u t i o n i s t o i n c l u d e a r e c y c l e s t r e a m of p r o d u c t g a s a s a
d i l u e n t . I t i s e v i d e n t t h a t t h i s s o l u t i o n i n v o l v e s a loss of energy
i n t h e r e c y c l e o p e r a t i o n , and t h a t a n economic p r o c e s s s h o u l d a l l o w
minimum r e c y c l e . F o r a n a d i a b a t i c p r o c e s s , however, t h i s is e q u i v a -
l e n t to a l a r g e temprature increase.
Another s o l u t i o n i s t o c a r r y o u t the m e t h a n a t i o n i n a c o o l e d r e a c -
t o r i n which t h e h e a t o f r e a c t i o n i s t r a n s f e r r e d from t h e r e a c t i o n
zone i n t o a c o o l i n g m e d i u m , e . g . b o i l i n g w a t e r . F o r a c o o l e d reac-
t o r , i t a p p e a r s a d v a n t a g e o u s t o d e s i g n f o r h i g h " h o t zone" tempera-
t u r e s , because t h i s g i v e s a b e t t e r h e a t t r a n s f e r .

When d e c r e a s i n g t h e o p e r a t i n g t e m p e r a t u r e , t h e need f o r h i g h e r ca-

t a l y s t a c t i v i t y i n c r e a s e s . Below a c e r t a i n t e m p e r a t u r e t h e r e a c t i o n
w i l l n o t " i g n i t e " . T h i s problem may b e a g g r a v a t e d b e c a u s e t h e c a t a -
l y s t h a v i n g been exposed t o t h e h i g h t e m p e r a t u r e , may h a v e t o o p e r -
a t e a t t h e l o w temperature a f t e r ageing or poisoning of t h e c a t a l y s t
a t the reactor inlet.

Moreover, t h e s t e e p t e m p e r a t u r e p r o f i l e means t h a t o t h e o p e r a t i o n
t e m p e r a t u r e of a c a t a l y s t p e l l e t may change 50-100 C w i t h i n s e c o n d s
i n c a s e of v a r i a t i o n s i n l o a d , r e c y c l e r a t i o and p r e h e a t ternpera-
t u r e . T h i s r e q u i r e s h i g h m e c h a n i c a l s t a b i l i t y of t h e c a t a l y s t .

Thus f o r a d i a b a t i c and f o r c o o l e d r e a c t o r s a s w e l l , i n o r d e r t o meet

t h e s e p r o c e s s r e q u i r e m e n t s , t h e c a t a l y s t s h o u l d b e a c t i v e and s t a b l e
b o t h a t h i g h and l o w t e m p e r a t u r e s . T h i s i s a key problem t o b e s o l v e d
when o p t i m i z i n g t h e m e t h a n a t i o n p r o c e s s f o r c o a l - b a s e d S N G .

The p a p e r summarizes c a t a l y s t s t u d i e s o f i m p o r t a n t phenomena t o b e

c o n t r o l l e d i n t h e development and u s e o f a n i n d u s t r i a l c a t a l y s t
meeting t h e s e r e q u i r e m e n t s .

89
 EXPERIMENTAL

The c a t a l y s t s were s t u d i e d i n v a r i o u s t e s t u n i t s . S i n t e r i n g s t u d i e s
were performed i n a t u b u l a r r e a c t o r (Di=32 mm) i n which v a r i o u s ca-
t a l y s t s a m p l e s were e x p o s e d s i m u l t a n e o u s l y t o s i n t e r i n g a t g i v e n
t e m p e r a t u r e , p r e s s u r e and a t m o s p h e r e . Low t e m p e r a t u r e d e a c t i v a t i o n
phenomena were s t u d i e d i n d i f f e r e n t i a l f l o w r e a c t o r s (Di=0.8 mm) .
The c a t a l y s t was u s e d a s 0 . 3 - 0 . 5 mm p a r t i c l e s d i l u t e d w i t h i n e r t
m a t e r i a l . S t a n d a r d a c t i v i t y t e s t s , and d e t e r m i n a t i o n o f n i c k e l s u r -
face areas were d e s c r i b e d e a r l i e r (1).The main p a r t o f t h e d e v e l -
opment work t o o k p l a c e i n a p i l o t p l a n t w i t h a 5 l i t r e a d i a b a t i c
reactor. The r e a c t o r h a d a f u l l bed l e n g t h ( u p t o 2m) and o p e r a t e d
a t i n d u s t r i a l mass v e l o c i t i e s , l e a v i n g t h e reactor d i a m e t e r as t h e
o n l y s c a l e - u p p a r a m e t e r . C a t a l y s t s a m p l e s from p i l o t t e s t s were
u s e d f o r p h y s i c a l and c a t a l y t i c a l e x a m i n a t i o n .

RESULTS

Si n t e ri n q

The m e t h a n a t i o n r e a c t i o n o n n i c k e l r e q u i r e s a l a r g e e n s e m b l e o f
n i c k e l atoms ( 2 ) , a n d t h e s p e c i f i c a c t i v i t y i s i n f l u e n c e d by n i c k e l
c r y s t a l l i t e s i z e ( 3 ) , b y t h e c o m p o s i t i o n o f t h e s u p p o r t (4,5,6),
and by n o n - l i n e a r p o i s o n i n g e f f e c t s ( 1 ) . T h e r e f o r e , t h e r e a c t i o n
a p p e a r s s e n s i t i v e t o t h e s t r u c t u r e o f t h e c a t a l y s t and t o i t s h i s -
t o r y of o p e r a t i o n .

S i n t e r i n g o f t h e n i c k e l c r y s t a l s r e s u l t s i n loss o f s u r f a c e a r e a ,
and i n p r i n c i p l e r e c r y s t a l l i z a t i o n may change t h e n i c k e l ensembles
a v a i l a b l e , and h e n c e c a u s e a d e c r e a s e o f t h e s p e c i f i c a c t i v i t y . We
showed p r e v i o u s l y ( 4 , 7 ) t h a t h e a t t r e a t m e n t o f n i c k e l c r y s t a l s ono
a s t a b l e l o w area ceramic s u p p o r t r e s u l t e d i n no s i n t e r i n g a t 550 C
o v e r a p e r i o d of 1 0 0 0 h o u r s , whereas t h e n i c k e l s u r f a c e a r e a dropped
t o a r o u n d 40 t o 25% o v e r t h e same p e r i o d a t 7OO0C and 85OoC r e s p e c t -
i v e l y , t h i s r e s u l t c o r r e s p o n d s t o t h e r u l e o f Tammann, a c c o r d i n g t o
which s i n t e r i n g i s e x p e c t e d above 0 . 5 t i m e s t h e m e l t i n g p o i n t ( K)
( 8 ) o f t h e m e t a l . The g r o w t h mechanism o f s u p p o r t e d m e t a l c r y s t a l s
a p p e a r s v e r y complex (9,101. The growth r a t e might b e i n f l u e n c e d
by t h e w e t t i n g p r o p e r t i e s o f t h e metal t o t h e s u p p o r t , and by t h e
micropores of t h e s u p p o r t m a t e r i a l . It w a s i l l u s t r a t e d t h a t t h e
d i f f u s i o n o f a m e t a l c r y s t a l l i t e i s impeded, when t h e s i z e o f t h e
m e t a l c r y s t a l l i t e i s of t h e o r d e r magnitude o f t h e d i a m e t e r o f t h e
pore (11,12). I n g e n e r a l , t h e m e t a l p a r t i c l e s may h a r d l y grow t o
a s i z e l a r g e r t h a n t h e pore d i a m e t e r o f t h e s u p p o r t . T h i s means
t h a t a s t a b i l i z e d micropore system of t h e support e f f e c t i v e l y pre-
vents s i n t e r i n g of t h e nickel crystals.

N i c k e l c a t a l y s t s d e s i g n e d f o r low t e m p e r a t u r e o p e r a t i o n a r e n o r m a l l y
b a s e d on h i g h a r e a s u p p o r t s s u c h a s gamma a l u m i n a , s i l i c a , c h r o m i a ,
e t c . These s u p p o r t s s u f f e r from s i g n i f i c a n t s i n t e r i n g , which ma
accompanied by w e a k e n i n g when exposed t o t e m p e r a t u r e s a b o v e 5 0 0 8Cbe
( 4 , 1 3 1 . The s i n t e r i n g may b e a c c e l e r a t e d by h i g h steam p a r t i a l p r e s -
s u r e ( 1 4 ) . F i g u r e 1 shows r e s u l t s from s i n t e r i n g t e s t s a t c o n d i t i o n s
f o r a c c e l e r a t e d s i n t e r i n g ( i . e . H O/H2=10, 30 a t m ) . T h r e e c a t a l y s t s
are compared: a l o w area steam r e z o r m i n g c a t a l y s t , a h i g h a r e a low

90
t e m p e r a t u r e m e t h a n a t i o n c a t a l y s t (Ni/y A 1 0 ) , and t h e Topsge
m e t h a n a t i o n c a t a l y s t MCR-type. The M C R c a z a j y s t m a i n t a i n s a h i g h
t o t a l s u r f a c e area and m e c h a n i c a l s t r e n g t h , whereas t h e y A l Z 0 3
b a s e d c a t a l y s t d e t e r i o r a t e s . ~ l c la t a l y s t s show s i g n i f i c a n t loss
i n n i c k e l s u r f a c e a r e a a t 800°C.

Carbon Formation

Thermodynamics p r e d i c t c a r b o n f o r m a t i o n f o r m e t h a n a t i o n a b o v e a
c e r t a i n t e m p e r a t u r e , d e p e n d i n g o n f e e d c o m p o s i t i o n and p r e s s u r e .
T h i s may i n f l u e n c e t h e minimum r e c y c l e r a t i o a l l o w e d , a s i l l u s -
t r a t e d i n F i g u r e 2 . However, t h e thermodynamic d a t a a r e i n f l u -
enced by t h e c a t a l y s t , b e c a u s e it m o d i f i e s t h e s t r u c t u r e o f t h e
c a r b o n . T h i s a l l o w s o p e r a t i o n a t c o n d i t i o n s more c r i t i c a l t h a n
t h o s e , which c o r r e s p o n d t o t h e l i m i t p r e d i c t e d o n t h e b a s i s o f
i d e a l g r a p h i t e . W e have shown p r e v i o u s l y (4,151 t h a t t h i s e f f e c t
i s f a v o r e d by s m a l l n i c k e l c r y s t a l s i n t h e c a t a l y s t .
I n p r a c t i c e , t h i s means t h a t t h e s o - c a l l e d p r i n c i p l e o f e q u i l i b r a t e d
g a s (1,4), ( i . e . c a r b o n f o r m a t i o n when t h e g a s shows a f f i n i t y f o r
c a r b o n , a f t e r t h e e s t a b l i s h m e n t o f t h e m e t h a n a t i o n and s h i f t e q u i -
l i b r i a ) p r e d i c t s no c a r b o n f o r m a t i o n f o r m e t h a n a t i o n . The v a l i d i t y
o f t h i s p r i n c i p l e i s i n d i c a t e d by t h e r e s u l t s i n T a b l e 1, o b t a i n e d
from t h e r m o g r a v i m e t r i c s t u d i e s (1). The c o n c l u s i o n h a s b e e n f u r t h e r
c o n f i r m e d by t h e e x p e r i e n c e i n t h e p i l o t t e s t s .

Low Temperature Problems

Low o p e r a t i n g t e m p e r a t u r e s f a v o r t h e a d s o r p t i o n of p o i s o n s , e .g
s u l f u r on t h e c a t a l y s t . W e h a v e shown t h a t t h e e f f e c t o f s u l f u r
.
i s s t r o n g l y n o n - l i n e a r (1) r e f l e c t i n g t h a t t h e m e t h a n a t i o n reac-
t i o n i s s t r u c t u r e s e n s i t i v e . T h i s , and o t h e r s t u d i e s ( 1 6 , 1 7 1 , show
t h a t a s u l f u r c o n t e n t i n t h e f e e d stream o f less t h a n 1 0 ppb i s
required t o o b t a i n a reasonable methanation a c t i v i t y a f t e r e q u i l i -
b r a t i o n of t h e s u l f u r adsorption. Therefore, t h e e f f e c t of s u l f u r
p o i s o n i n g s h o u l d r a t h e r b e a n a l y s e d i n t e r m s o f a dynamic model
f o r f i x e d bed a d s o r p t i o n ( 1 8 ) .

The o p e r a t i o n a t a l o w r e c y c l e r a t i o o r t h e s t r a i g h t - t h r o u g h
operation i n a cooled r e a c t o r , implies high p a r t i a l pressures
o f c a r b o n monoxide a t t h e r e a c t o r i n l e t . T h i s r e s u l t s i n t w o
problems.
A t t e m p e r a t u r e s below 23OoC, t h e r e i s a s u b s t a n t i a l r i s k t h a t car-
bon monoxide r e a c t s w i t h n i c k e l , f o r m i n g n i c k e l c a r b o n y l . O p e r a t i o n
i n t h i s t e m p e r a t u r e r a n g e , w i t h a p a r t i a l p r e s s u r e o f c a r b o n monox-
i d e o f 2.5 atm r e s u l t e d i n t r a n s p o r t o f n i c k e l i n t h e c a t a l y s t bed.
Moreover, t h e f o r m a t i o n o f n i c k e l c a r b o n y l r e s u l t e d i n a d r a s t i c
growth o f t h e n i c k e l c r y s t a l s , u p t o p a r t i c l e s o f 2 0 , 0 0 O f t , t h u s
e x c e e d i n g , by l a r g e , t h e p o r e s i z e o f t h e c a t a l y s t s u p p o r t . T h i s
growth r e s u l t e d i n break-down of t h e c a t a l y s t . The f o r c e s i n v o l v e d
appear much s t r o n g e r t h a n o b s e r v e d i n t h e r m a l s i n t e r i n g o f t h e
n i c k e l c r y s t a l s , as d e s c r i b e d above.
Another r e s u l t from o p e r a t i n g w i t h h i g h p a r t i a l p r e s s u r e o f c a r b o n
monoxide, a p p e a r s t o b e a d e a c t i v a t i o n phenomenon, c a l l e d B-deactiv-
v a t i o n d e v e l o p i n g s l o w l y i n some p i l o t t e s t s , and b e i n g r e f l e c t e d by
91
t h e appearance o f a n i n f l e c t i o n p o i n t i n t h e a x i a l t e m p e r a t u r e pro-
f i l e . F i g u r e 3 i l l u s t r a t e s t h e movement of t h e t e m p e r a t u r e p r o f i l e ,
and t h a t t h e 8 - d e a c t i v a t i o n d i s a p p e a r s above a c e r t a i n i n l e t t e m -
p e r a t u r e . The a c t i v i t y c o u l d be r e s t o r e d by t r e a t m e n t i n hydrogen,
as e x p l a i n e d below.
The low t e m p e r a t u r e d e a c t i v a t i o n phenomena were f u r t h e r d e m o n s t r a t e d
b y l a b o r a t o r y tests on a N i / q A 1 O3 c a t a l y s t i n a d i f f e r e n t i a l re-
a c t o r . A s shown i n F i g u r e 4 , no 3 e a c t i v a t i o n was o b s e r v e d i f CO was
r e p l a c e d by C02. The d e a c t i v a t i o n r a t e i n c r e a s e s s i g n i f i c a n t l y w i t h
t h e CO/H2 r a t i o and by t h e p r e s e n c e of s u l f u r . The r o l e o f s u l f u r on
o t h e r d e a c t i v a t i o n phenomena w a s i n d i c a t e d i n o u r e a r l i e r s t u d i e s
(1) -
The MCR-2X c a t a l y s t shows much less d e a c t i v a t i o n t h a n t h e N i / n A 1 O3
catalyst. A n a l y s i s of t h e s p e n t c a t a l y s t s i n d i c a t e d by t h e g r o w t i
of n i c k e l c r y s t a l s showed t h a t t h e N i / q A 1 O3 c a t a l y s t had a l s o been
exposed t o c a r b o n y l f o r m a t i o n i n c o n t r a s t $0 t h e MCR-2X c a t a l y s t .
The l a r g e i n f l u e n c e of c a t a l y s t c o m p o s i t i o n on d e a c t i v a t i o n r a t e
and c a r b o n y l f o r m a t i o n w a s a l s o r e p o r t e d by Vannice and G a r t e n ( 6 ) .

The 8 - d e a c t i v a t i o n i s p r o b a b l y due t o t h e f o r m a t i o n of a l e s s r e -
a c t i v e carbon s t a t e on t h e n i c k e l s u r f a c e , which might be t h e
6 - s t a t e i d e n t i f i e d by W i s e e t . a l . ( 1 9 , 2 0 ) .

The s i t u a t i o n c o r r e s p o n d s t o t h e d e a c t i v a t i o n observed i n steam

n a p h t h a r e f o r m i n g a t low t e m p e r a t u r e s ( 2 1 ) , and t o a g e n e r a l model
f o r carbon f o r m a t i o n o n n i c k e l ( 2 2 ) . The adsorbed i n t e r m e d i a t e
(a'-carbon)may e i t h e r be g a s i f i e d t o methane (2,19) o r be d i s -
s o l v e d i n n i c k e l a s c a r b o n and form c a r b o n w h i s k e r s (l), o r be
t r a n s f e r r e d i n t o e n c a p s u l a t i n g c a r b o n ( 6 - c a r b o n ) . For t h e p r e s e n t
c a s e , a p p a r e n t l y t h e c o n v e r s i o n o f a' i n t o is too s l o w a t very
low t e m p e r a t u r e s , e . g . 25OoC, whereas a t h i g h t e m p e r a t u r e s t h e r a t e
o f h y d r o g e n a t i o n of 6-carbon e x c e e d s t h e t r a n s f o r m a t i o n r a t e o f a'
i n t o 8-carbon ( 2 0 ) . These e f f e c t s a r e o v e r l a p p e d by t h e i n f l u e n c e
o f t h e s u r f a c e c o n c e n t r a t i o n of a ' - c a r b o n s u c h a s t h e h y d r o g e n a t i o n
r a t e of a ' - c a r b o n a n d t h e p a r a m e t e r s g o v e r n i n g t h e c h e m i s o r p t i o n of
c a r b o n monoxide. The CO c h e m i s o r p t i o n depends on t h e p a r t i a l p r e s -
s u r e of CO and t h e t e m p e r a t u r e a t a g i v e n p o s i t i o n i n t h e r e a c t o r ,
and it i s a l s o a f f e c t e d by t h e c o m p o s i t i o n of t h e c a t a l y s t ( 5 ) . .

MCR-2X Catalyst

The development program f o r m e t h a n a t i o n c a t a l y s t s a t T o p s 0 e ' s l a b o r a -

t o r i e s aimed s p e c i f i c a l l y a t s o l v i n g t h e problem of o p e r a t i n g over
a wide t e m p e r a t u r e r a n g e . The work r e s u l t e d i n t h e MCR-2X c a t a l y s t .
The s u p p o r t h a s a s t a b i l i z e d m i c r o p o r e s y s t e m t h a t e f f e c t i v e l y pre-
v e n t s s i n t e r i n g o f t h e n i c k e l c r y s t a l s . The r e s u l t i n g h i g h n i c k e l
s u r f a c e a r e a and t h e a b s e n c e of a l k a l i (sometimes added t o p r e v e n t
c a r b o n f o r m a t i o n ) l e d t o t h e d e s i r e d h i g h m e t h a n a t i o n a c t i v i t y . The
c a t a l y s t i s m e c h a n i c a l l y s t a b l e a t h i g h a s w e l l a s low t e m p e r a t u r e s .
The s t a b i l i t y was p r o v e n i n p i l o t tests w i t h a t o t a l run-time arnount-
i n g t o 1 5 , 0 0 0 h o u r s . T h i s i n c l u d e d 8 , 0 0 0 h o u r s o g e r a t i o n a t t h e same
c a t a l y s t f i l l i n g a t a maximum t e m p e r a t u r e of 6 0 0 C. Data i n T a b l e 2
d e m o n s t r a t e s t h e t h e r m o - s t a b i l i t y o f MCR-2X r e f l e c t e d by an a l m o s t
unchanged m e c h a n i c a l s t r e n g t h and t o t a l s u r f a c e a r e a . The a c t i v i t y
s t a b i l i z e d a f t e r 1,000-2,000 hours.
92
The mechanical and chemical p r o p e r t i e s of MCR-2X a l s o o f f e r f l e x i -
b i l i t y i n p r o v i d i n g t h e c a p a b i l i t y f o r r e g e n e r a t i o n of s p e n t c a t a -
l y s t s . T a b l e 3 shows r e s u l t s from r e g e n e r a t i o n tests performed o n
samples t a k e n a f t e r 4700 h o u r s o p e r a t i o n i n t h e p i l o t p l a n t . The
carbonaceous f i l m r e s p o n s i b l e f o r t h e 8 - d e a c t i v a t i o n c a n be removed
simply by t r e a t m e n t i n hydrogen, whereas s u l f u r i s more d i f f i c u l t
t o remove. However, t h e c a t a l y s t e a s i l y w i t h s t a n d s a h i g h tempera-
t u r e o x i d a t i o n and r e - r e d u c t i o n , which w i l l n o t o n l y remove s u l f u r ,
b u t a l s o r e s u l t i n r e d i s t r i b u t i o n of any s i n t e r e d n i c k e l c r y s t a l s .
A S shown i n Table 3 , more t h a n 50% o f t h e o r i g i n a l a c t i v i t y of a
new c a t a l y s t c a n b e r e g a i n e d by t h i s method.
The p r o p e r t i e s of MCR-2X c a n be u t i l i z e d i n d i f f e r e n t p r o c e s s
schemes o p t i m i z e d f o r t h e f e e d g a s i n q u e s t i o n . The c r i t i c a l s t e p
i s t h e f i r s t m e t h a n a t i o n s t a g e , where t h e f u l l p o t e n t i a l o f MCR-2X
i s u t i l i z e d , MCR-2X a l l o w i n g maximum p r a c t i c a b l e t e m p e r a t u r e i n -
c r e a s e from c a . 3OO0C t o 70OoC.

The m e c h a n i c a l s i n , t e r i n g problem c o u l d be s o l v e d by u s i n g steam r e -

forming c a t a l y s t s , which w i l l , o f c o u r s e , be a c t i v e a l s o f o r metha-
n a t i o n . However, t h e n i c k e l s u r f a c e a r e a s i n most steam r e f o r m i n g
c a t a l y s t s a r e t o o s m a l l t o p r o v i d e a d e q u a t e low t e m p e r a t u r e a c t i v i -
t y , thus d i c t a t i n g operating a t higher r e a c t o r i n l e t temperatures.
This w i l l n o t necessarily influence t h e o v e r a l l conversion i n t h e
r e a c t o r , which i s f i x e d by t h e e x i t t e m p e r a t u r e . However, f o r a d i a -
b a t i c o p e r a t i o n , t h e reduced t e m p e r a t u r e r i s e means a h i g h e r r e c y c l e
energy consumption. I n p r i n c i p l e t h i s c a n be overcomed by i n c r e a s i n g
a l s o t h e e x i t t e m p e r a t u r e , b u t t h i s means a g r e a t e r number of r e a c -
t o r s b e c a u s e of t h e s m a l l e r c o n v e r s i o n p e r reactor. T h i s s i t u a t i o n
i s i l l u s t r a t e d i n F i g u r e 5 , i n which t h e o p e r a t i o n , based on MCR-ZX,
i s shown ( s o l i d l i n e ) i n a s i m p l i f i e d example i n v o l v i n g t h r e e a d i a -
b a t i c r e a c t o r s , c o r r e s p o n d i n g t o a n o v e r a l l c o n v e r s i o n o f 95%.

The p r o c e s s p a t h , TREMP (Tops0e Recycle Methanation P r o c e s s ) i s

compared w i t h a l t e r n a t i v e r o u t e s of h i g h t e m p e r a t u r e m e t h a n a t i o n
(dashed l i n e s ) b a s e d on a r e f o r m i n g t y p e c a t a l y s t . A t e m p e r a t u r e
of 45OoC i s assumed a s t h e minimum i n l e t t e m p e r a t u r e f o r t h e re-
forming t y p e c a t a l y s t . T o a c h i e v e t h e same c o n v e r s i o n of t h e f i r s t
r e a c t o r a s o b t a i n e d i n TREMP, a r e c y c l e r a t i o 2 t i m e s h i g h e r a s i n
TREMP i s r e q u i r e d . T h i s means h i g h e r e n e r g y consumption. I f r e c y c l e
is excluded, four r e a c t o r s t a g e s a r e necessary with reforming cata-
l y s t s t o o b t a i n a c o n v e r s i o n e q u i v a l e n t t o t h a t o f t h e f i r s t TREMP
r e a c t o r , Moreover, t h i s s o l u t i o n i s d o u b t f u l b e c a u s e o f t h e e x c e s s -
i v e l y h i g h e x i t t e m p e r a t u r e of t h e f i r s t r e a c t o r .

By t h e u s e of a combined bed of a n o n - n i c k e l g a t a l y s t w i t h MRC-2X,

t h e i n l e t t e m p e r a t u r e can bg d e c r e a s e d t o 200 C , t h u s a l l o w i n g a
t e m p e r a t u r e i n c r e a s e of 500 C a t a reduced r e c y c l e r a t e . The wide
o p e r a t i n g r a n g e o f MCR-2X may be u t i l i z e d i n t h e d e s i g n o f b o i l i n g
w a t e r r e a c t o r s f o r z e t h a n a t i o n . With MCR-ZX, d e s i g n f o r " h o t zone"
t e m p e r a t u r e s of 7 0 0 C i s r e a l i s t i c , s i n c e t h i s l e a v e s a good s a f e t y
margin. An e x p l o r a t i v e t e s t w a s made i n t h e p i l o t p l a n t i n which
M c R - ~ X was exposed t o 78OoC i n t h e " h o t zone". F o r s i m p l i c i t y t h e
t e s t was made i n an a i r - c o o l e d r e a c t o r . The i n l e t t e m p e r a t u r e was
93
3OO0C and a f t e r t h e h o t zone, t h e r e a c t i o n t e m p e r a t u r e w a s d e c r e a s e d
t o a b o u t 25OoC. The t u b e w a l l t e m p e r a t u r e i n t h e h o t zone w a s be-
tween 300 and 4OO0C, which i s c l o s e t o t h e e x p e c t e d v a l u e i n an
i n d u s t r i a l b o i l i n g water r e a c t o r . Measured and c a l c u l a t e d tempera-
t u r e p r o f i l e s a r e shown i n F i g u r e 6 . N o s i g n i f i c a n t d e a c t i v a t i o n of
t h e c a t a l y s t was o b s e r v e d a t t h e t e s t , which s u p p o r t s t h e p o s s i b i l i -
t y f o r designing f o r high h o t s p o t temperatures, being important f o r
optimum r e a c t i o n and h e a t t r a n s f e r c o n d i t i o n s .

A s p e c i a l a p p l i c a t i o n o f m e t h a n a t i o n i s r e l a t e d t o t h e Long D i s t a n c e
Energy T r a n s p o r t System NFE or ADAM/EVA system, which i s b e i n g de-
v e l o p e d a t t h e German N u c l e a r Research C e n t e r KFA-Jclich, i n cooper-
a t i o n w i t h R h e i n i s c h e Braunkohlenwerke AG i n Cologne. I n t h i s system
( 2 3 , 2 4 ) , n u c l e a r e n e r g y released i n a helium-cooled h i g h t e m p e r a t u r e
r e a c t o r i s t r a n s f e r r e d t o steam r e f o r m e r (EVA) w i t h a h o t h e l i u m as
h e a t i n g medium. The p r o d u c t i s t r a n s p o r t e d by p i p e l i n e t o power
p l a n t s i n which t h e h e a t i s r e c o v e r e d i n a m e t h a n a t i o n p l a n t (ADAM).
The h i g h e x i t t e m p e r a t u r e which c a n be a c c e p t e d of MCR-2X makes it
p o s s i b l e t o raise s u p e r h e a t e d h i g h p r e s s u r e steam a t t h e d e s t i n a t i o n
f o r e l e c t r i c i t y p r o d u c t i o n a s r e q u i r e d i n t h e NFE system. TopsQe h a s
s u p p l i e d t h e semi-commercial d e m o n s t r a t i o n p l a n t ADAM-1 t o KFA -
J i i l i c h . The p l a n t i s b a s e d o n t h r e e a d i a b a t i c m e t h a n a t i o n s t e p 3 , and
i t i s p r o c e s s i n g s y n t h e s i s g a s manufactured from up t o 2 0 0 Nm p e r
h o u r o f n a t u r a l gas ( 2 3 ) . F i g u r e 7 shows t e m p e r a t u r e p r o f i l e s from
a n ADAM I r u n which was made by KFA i n c o o p e r a t i o n w i t h Tops@e ( 2 5 ) .
MCR-2X was i n s t a l l e d i n t h e f i r s t two m e t h a n a t i o n s t e p s , whereas t h e
t h i r d methanator o p e r a t e d on MCR-4 which i s a h i g h l y a c t i v e l o w t e m -
perature catalyst.

CONCLUSIONS

The u s e of a n i c k e l c a t a l y s t f o r m e t h a n a t i o n i s l i m i t e d t o a minimum
o p e r a t i n g t e m p e r a t u r e b e c a u s e of t h e r i s k of c a r b o n y l f o r m a t i o n and
d e a c t i v a t i o n , and t o a maximum o p e r a t i n g t e m p e r a t u r e b e c a u s e of s i n -
t e r i n g and i n c e r t a i n c a s e s t h e r i s k of c a r b o n f o r m a t i o n . B e t w e e n
t h e s e t e m p e r a t u r e l i m i t s , t h e a c t i v i t y and s t a b i l i t y of t h e c a t a l y s t
d e t e r m i n e s t h e optimum l a y o u t o f t h e m e t h a n a t i o n p r o c e s s . The TopsQe
MCR-2X c a t a l y s t a l l o w s o p e r a t i o n i n t h e t e m p e r a t u r e r a n g e 25OoC t o
w e l l above 70OoC. By c o m b i n a t i o n w i t h a non-nickel c a t a l y s t , t h e
o p e r a t i o n r a n g e c a n , f o r c e r t a i n c a s e s , be e x t e n d e d t o 2 0 0 t o 70OoC.
This c a p a b i l i t y of high temperature methanation o f f e r s t h e possibi-
l i t y o f d e s i g n f o r l o w r e c y c l e , o r f o r optimum b o i l i n g w a t e r r e a c t o r s .

REFERENCES

1. Rostrup-Nielsen, J.R., and P e d e r s e n , K . , J.Cata1. (in press).

2. Araki, M . , and Ponec, V . , J.Cata1. 44,439 (1976).

3. Coenen, J.W.E., S c h a t s , W . M . T . M . , and v a n Meerten, R . Z . C .

Bull.Sco.Chim.Belg. (1979) ( i n p r e s s ) .

4. Rostrup-Nielsen, J.R., "Steam Reforming C a t a l y s t s " , T e k n i s k

F o r l a g , Copenhagen 1 9 7 5 .
94
 REFERENCES ( C o n t ' d )

5. Schoubye, P . , J . C a t a 1 . 2 , 238 (1969).

6. Vannice, M.A., and Garten, R.L., J.Cata1. 56, 236 ( 1 9 7 9 ) .

7. Rostrup-Nielsen, J . R . , J.Cata1. 2, 171 (1971)

8. Garner S.W., "Chemistry of t h e S o l i d S t a t e " , B u t t e r w o r t h s ,

London 1955, p 307.

9. Ruckenstein, E . , and Pulvermacker, B . , AIChE J o u r n a l 2,356

(1973).

10. W y n b l a t t , P . , a n d Tae-Moon, Ahn, " S i n t e r i n g and C a t a l y s i s " ,

Materials S c i e n c e Research E, 83 ( 1 9 7 5 ) .

11. Ruckenstein, E . , and Pulvermacker, B . , J.Cata1. 3 , 416 (1975).

12. B o r i s o v a , M.S., Fenelonov, V . B . , Dzisko, V.A., Simonova, L . G . ,

Kinet.Kata1. 2,653 ( 1 9 7 6 ) .

13. Williams, W . , B u t l e r , G.A., and Hammonds, J . , J . C a t a 1 . E, 352

(1972).

14. Levy, R.M., Bauer, D . J . , Roth, J . F . , 1nd.Eng.Chem.Prod. Res.

Develop. 2, 217 ( 1 9 6 8 ) .

15. Rostrup-Nielsen, J . R . , J.Cata1. 21, 343 (1972) .

16. McCarty, J . G . , Wentrcek, P.R., Wise, H . and Wood, B . J .
DOE C o n t r a c t 76-C-03-115, Annual R e p o r t O c t . 26, 1978.

17. F i t z h a r r i s , W.D., PhD T h e s i s , U n i v e r s i t y of Delaware, 1978.

18. C h r i s t i a n s e n , L . J . , and Andersen, S . , P r o c . 6 t h I n t . Symp.

o n "Chemical R e a c t i o n E n g i n e e r i n g " , N i c e 1980 ( i n p r e s s ) .

19. McCarty, J . G . , and Wise, H . , J.Cata1. 57, 406 ( 1 9 7 9 ) .

20 McCarty, J . G . , Wentrcek, P.R., and Wise, H . , i n "Proc.Amer.

Chem.Soc.Symposium", Chicago, Aug. 28-Sept. 2 , 1 9 7 7 " , p 1315.

21 Moseley, F . , S t e p h e n s , R.W. , Stewart, K.D., and Wood, J . ,

J . C a t a 1 . 24, 18 ( 1 9 7 2 ) .

22. Rostrup-Nielsen, J . R . , and T r i m m , D . L . , J.Catal. 48, 155 (1977).

23. Harms, H.G., HGhlein, B . , and Skov, A . , Chem.Ing.Tech.(in press).

24. B o l t e n d a h l , V . , N i e s s e n , H.F., Theis, K.A., GWF-Gas/Erdgas,

-
117, 517 ( 1 9 7 6 ) .

25. Harms, H.G., HGhlein, B . , and Skov, A . , O i l and Gas J . (sub-

mitted).

95
 Table - 1
Carbon Formation, Thermogravimetric T e s t s

E x p e r i m e n t a l c o n d i t i o n s re ref (1)
C a t a l y s t , 13wt%N i , DNi= 300 - 3500 8,
Carbon l i m i t s c a l c u l a t e d from " p r i n c i p l e o f e q u i l i b r a t e d g a s "

1 2

0,33

PCO atm or2 0,33

Temp. OC 4 00- 47 0 400

Calc. carbon l i m i t s
C a r b o n f o r (Temp.OC) :
Graphite 415 c: T 4800 T 4 1069
C a t a l y s t (DNi=3 500A 6004 T4350 T c 684

1 Carbon Formation I NO Yes

Table - 2

High T e m p e r a t u r e S t a b i l i t y o f MCR2X
R e s u l t s from P i l o t T e s t s

O p e r a t i o n BET Area n2 A r e a DNi

Time a t Temp.
h OC
m2/s A

New MCR2X 52 7 220

8127 600 30 3 295

1895 600
f o l l o w e d by 35 3 345
860 700

96
 Table - 3

R e g e n e r a t i o n of MCR2X C a t a l y s t

Samples f r o m HTAS-run 5

Operating Regeneration Activation Intrinsic Activity

t i m e a t temp. Conditions Conditions r e l a t i v e to unused
h OC
cat.
Before After

4800 290-385 H2,15h,5000C - 0.006 0.05

4800 290-385 H2,4h,7000C - 0.006 0.15

3 9 0 0 280-300 H 2 0 , 16h, 7OO0C 80O-85O0C, Zh 0.025 0.42

3900 600 H20,16h,7000C 800-850°C,2h 0.11 0.50

97
 Figure 1

Sintering of catalysts
1

30 kg/an 2q, H20/H2=10, 140-170 hours

2
m-type. BET-area = 33 m /q
2
Ni/yA1203. BET-area = 101 m /q
2
Ni/Ceramic. BET-area = 1.2 i
n /q

Figure 2

Carton L i m i t s

Recycle r a t i o and o u t l e t
temperature of adiabatic
equilibration of gas. The
example r e f e r s to a feed-
gas containing 12 vol%
CH .Correction f o r car-
bA-structure on c a t a l y s t
moves carton l i m i t s to
950-lO5O0C.

UIO I
0 I 1 I 1 5 6 R l C I C L l RATIO
11 il O
I I I CARBON MOUOXlOt
A1 1W11
HOL'I. I W l l l

98
 Figure 3

B-deactivation i n P i l o t Test

McR-type c a t a l y s t .

O/C = l., H/C = 6., P = 30 kg/an2g,

PCO = 2 kg/an2g.
cg Zg7 = a x i a l distance f m top of
0

c a t a l y s t bed f o r 97% conversion

of max. adiabatic A T obtained.
0
0 0
0

Figure 4

Low Temperature Deactivation

Laboratory Tests
3OO0C, 21.2 kg/an2g, MW=106h-’
Fedgas ( ~ 0 1 %
: )

H2Q (35)
co (0-11)
co2 ( 5 )
H2 (rest)

99
 High Temperature Methanation
Sinplified Fxample
\ Canparison of TREMP reaction steps
(solid l i n e ) w i t h reaction routes
based on a reforming type c a t a l y s t
.
(dashed l i n e s )

Figure 6
Explorative P i l o t T e s t
w i t h Air-cooled Reactor

Measured and calculated

temperature profiles.
The calculation nxxlel
did not consider a x i a l
radiation i n the bed,
which explains the dif-
ference of the two pro-
files .

Figure 7

ADAM-1 T e s t Unit

Temperature Profiles

100
 ?.pplied Fischer-Tropsch Kinetics f o r a F l m Spray63 Iron Catalyst
W. J. Thanson, J. 11. Amdt, and K. L. Wright

University of Idaho, Department of Chenical wineerirq, Ibscow, IdaAo, 93843

INTRODUCTION

There has been a g r e a t deal o f previous work done of Fischer Tropsch

C a t a l y s i s but u n t i l r e c e n t l y , very l i t t l e r a t e data have been obtained
o t h e r than s e m i - q u a n t i t a t i v e r e s u l t s . A g r e a t deal of the previous l i t e r -
a t u r e d e a l s with t h e proposed and hypothetical mechanisms of Fischer
Tropsch c a t a l y s i s and i t s similarities/dissimilarities t o SNG methanation.
Despite t h e voluminous amount of work i n t h i s a r e a t h e r e i s s t i l l c o n t r o -
versy a s t o whether deposited carbon o r i r o n c a r b i d e ( i n t h e c a s e o f i r o n
c a t a l y s t s ) i s t h e a c t i v e intermediate i n t h e mechanistic scheme.' I n
a d d i t i o n t o t h i s t h e r e was a g r e a t deal o f work accomplished a t t h e Bureau
o f Mines in t h e 1 9 4 0 ' s and 5 0 ' s concerning t h e behavior o f Fischer Tropsch
c a t a l y s i s under various c o n d i t i o n s . ' Iron a s well a s c o b a l t and ruthenium
have been proposed and s t u d i e d a s p o s s i b l e Fischer Tropsch catalyst^.^'
There has a l s o been c o n s i d e r a b l e i n t e r e s t in t h e i n c o r p o r a t i o n o f various
promoters in Fischer Tropsch c a t a l y s i s in o r d e r t o a l t e r o l e f i n - t o - p a r a f f i n
r a t i o s , minimize CO2 make, e t c . An i n t e r e s t i n g study being conducted a t
the University of Utah' i s seeking t o s y s t e m a t i c a l l y a l t e r various pro-
moters i n order t o determine t h e b e s t combination i n o r d e r t o achieve a
maximum of Cz-Cg hydrocarbons. A s h o r t review of Fischer Tropsch technol-
ogy u p t o 1975 has been given by Shah and P e r r o t t a . 6
There have been two k i n e t i c s t u d i e s using i r o n c a t a l y s t s f o r Fischer
Tropsch a p p l i c a t i o n s . ' ~ Dry e t . a l . 7 used a t r i p l e promoted i r o n c a t a l y s t
in t h e pressure range of 10-20 atmospheres and a t temperatures from 240-
270C t o determine t h e r e a c t i o n o r d e r s of t h e CO consumption r a t e with re-
s p e c t t o both hydrogen and CO. He employed a d i f f e r e n t i a l r e a c t o r with
H2-toCO r a t i o s varying from 1 t o 7. They found t h a t t h e r e a c t i o n o r d e r
with r e s p e c t t o CO was e f f e c t i v e l y z e r o b u t t h e r e a c t i o n o r d e r with r e s p e c t
t o H2 was f i r s t o r d e r . Between 225 and 265C they a l s o determined an
a c t i v a t i o n energy o f 16.8 Kcal/mole. However a l l t h e i r d a t a were obtained
by measurements of t h e CO2 and water-make i n t h e e x i t stream. By assulii-
ing t h a t t h e r e was minimal oxygenated products (reasonable f o r i r o n

101
 c a t a l y s t s ) , then t h e summation o f t h e Cop and water-make should equal
t h e t o t a l CO consumption r a t e . I n a l l cases t h e r a t i o of Cop-to-water
was l e s s than 1 except a t t h e highest temperatures (265C, where i t equaled
1 . 1 5 ) . Since t h e e f f e c t o f i n c r e a s i n q space v e l o c i t y was t o d r a m a t i c a l l y
d e c r e a s e t h e COz/H20 r a t i o , they concluded t h a t CO2 was a secondary r e a c t i o n
produced by t h e water gas s h i f t r e a c t i o n . A more r e c e n t k i n e t i c study
was conducted by Atwood and Bennett.* I n t h i s c a s e they employed n o t only
a t u b u l a r flow r e a c t o r b u t a l s o a n i n t e r n a l l y r e c i r c u l a t e d r e a c t o r (simi-
l a r t o t h e r e a c t o r employed h e r e ) . They claimed i n t h e i r paper t h a t t h e r e
was l i t t l e d i f f e r e n c e in t h e r e a c t i o n k i n e t i c s whether t h e r e c i r c u l a t e d r e -
a c t o r o r t h e t u b u l a r flow r e a c t o r was employed. Based on our experience
I i t would appear t h a t t h i s was due t o t h e i r minimal H2 consumption ( H Z
i n e x c e s s ) and a zero o r d e r dependency of t h e r e a c t i o n with r e s p e c t t o
CO ( a s reported by Dry e t . a 1 . 7 ) . I n t h i s c a s e they reported t h a t with
t h e i r o n c a t a l y s t , the C02/H20 r a t i o was s i q n i f i c a n t l y o r e a t e r t h a n one
but i t should be pointed o u t t h a t t h e temperatures employed in t h i s study
ranged from 250C t o 315C; t h a t i s , s i g n f i c a n t l y h i a h e r than t h e temperatures
used by Dry e t . They proposed a k i n e t i c expression which i s based on
t h e r a t e being dependent on t h e hydrogen c o n c e n t r a t i o n and t h e f r a c t i o n of
reduced iron p r e s e n t . ’ A psuedo steady s t a t e balance between t h e oxida-
t i o n of iron by H20 and i t s reduction by CO l e a d s t o equation ( 1 ) .

.4 P H 2 )
rrn = (1)

Experimental d a t a a t t h r e e temperatures were used t o determine t h e con-

s t a n t s k a n d b a s a f u n c t i o n of temperature. However i t should be pointed
o u t t h a t t h e term i n v o l v i n g t h e r a t i o of water t o CO p a r t i a l p r e s s u r e s in
t h e denominator was only important f o r a very few data p o i n t s . Also, s i n c e
a c o n s t a n t feed mixture with a H2 t o CO r a t i o o f 2 . 0 was used and t h e authors
r e p o r t t h a t t h e mole f r a c t i o n o f Hp i n t h e product stream was e s s e n t i a l l y

102
independent of carbon monoxide conversion, t h e H p p a r t i a l p r e s s u r e was
c l o s e t o a constant f o r a l l runs. Although the a u t h o r s show an e x c e l l e n t
f i t when equation ( 1 ) i s rearranged t o t h e l i n e a r form o f equation (2),
note t h a t t h e e s s e n t i a l l y c o n s t a n t hydrogen p a r t i a l p r e s s u r e s and a small

e f f e c t of t h e water-to-C0 p a r t i a l p r e s s u r e would produce a c o n s t a n t r a t e

a t any tetiiperature.
Two o t h e r r a t e expressions based s o l e l y on o b s e r v a t i o n , havc a l s o
been p r o p ~ s e d . ~I n one, t h e r a t e was observed t o depend only o n the par-
t i a l p r e s s u r e of H2 ( f o r conversions l e s s t h a n 6 0 % ) and, i n t h e o t h e r an
adequate c o r r e l a t i o n f o r c o b a l t was obtained by equation ( 3 ) .

Fischer-Tropsch s y n t h e s i s i s highly exothermic and consequently a

good deal of a t t e n t i o n has been s p e n t on r e a c t o r design c o n s i d e r a t i o n s .
Designs ranging from s l u r r y r e a c t o r s t o f l u i d i z e d beds have been proposed’
and, in t h e l a t t e r c a s e , a c t u a l l y c o n s t r u c t e d . ” I t i s a l s o comrron t o
u t i l i z e r e c y c l e r e a c t o r s i n o r d e r t o r e s t r i c t t h e temperature r i s e a c r o s s
t h e c a t a l y s t bed, b u t a heavy p r i c e must be paid in terms o f compressor
c o s t s . A low pressure drop r e a c t o r u t i l i z i n g p a r a l l e l p l a t e s and i n s e r t s
coated w i t h c a t a l y s t was f i r s t proposed by DOE f o r t h e exothermic methana-
t i o n r e a c t i o n ” and a s i m i l a r design using i r o n c a t a l y s t s f o r Fischer
Tropsch has been discussed by Haynes, e t . a1.I’ The work r e p o r t e d here d e a l s
w i t h a n applied k i n e t i c s study u t i l i z i n g t h i s c a t a l y s t concept. blhile t h e
scope o f t h e p r o j e c t i s concerned with product d i s t r i b u t i o n s as well a s
r e a c t i o n r a t e s , in t h i s paper we w i l l only focus on r e a c t a n t a n d make-gas
rates.

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EXPERIMENTAL EQUIPMENT AN0 PROCEDURES
Berty Reactor System
All of t h e experiments were conducted i n an i n t e r n a l l y r e c i r c u l a t i n g
r e a c t o r ("Berty" t y p e ) and a schematic of t h i s equipment i s shown in
Figure 1 . Hydrogen and CO a r e monitored s e p a r a t e l y v i a c a p i l l a r y flow
meters equipped with p r e s s u r e drop t r a n s d u c e r s and t h e flows a r e ad-
j u s t e d with the r e a c t o r on by-pass t o o b t a i n t h e d e s i r e d i n l e t H2-to-CO
r a t i o and t o t a l flow. Once t h e d e s i r e d r a t i o i s o b t a i n e d , a sample i s
s e n t f o r a n a l y s i s v i a gas chromotography using a Carle :,lode1 111 H
gas chromotograph. The r e a c t o r i s then p u t on stream and t h e H2-CO
mix i s fed t o t h e r e a c t o r . The e x i t stream l e a v i n g t h e r e a c t o r passes
f i r s t through a "hot t r a p " ( a condenser maintained a t 120C) in o r d e r t o
condense waxes. The uncondensed portion of t h e stream then passes through
a c o l d trap ( a t O C ) where water and o i l a r e condensed. The gas e f f l u e n t
from t h i s condenser passes i n t o a knock-out p o t t o remove e n t r a i n e d l i q u i d s
and then proceeds v i a a wet t e s t meter t o vent. P r o v i s i o n s a r e made t o
sample this e x i t gas stream on l i n e and a g a i n , a n a l y s i s i s done via a
Carle 111 H gas chromotograph. The r e a c t o r p r e s s u r e i s a d j u s t e d and
maintained by means of a needle valve a t t h e r e a c t o r e x i t . Temperatures
w i t h i n the r e a c t o r a r e measured j u s t above and below t h e c a t a l y s t sample.
The mass v e l o c i t y a c r o s s t h e c a t a l y s t s u r f a c e can be a d j u s t e d by means of
r e g u l a t i n g the RPH o f t h e magnedrive u n i t equipped with t h e Berty r e a c t o r .
T y p i c a l l y a t RPM's above 750 t h e temperature d i f f e r e n c e a c r o s s t h e c a t a l y s t
i s w i t h i n 2 C and a l l d a t a r e p o r t e d here were obtained a t 1500 RPM.
The Carle A n a l y t i c a l Gas Chromatograph i s equipped with an o n - l i n e
hydrogen t r a n s f e r tube so t h a t reasonably a c c u r a t e hydroaen peaks a r e
obtained as p a r t o f t h e a n a l y s i s . A 2.5 rn poropak Q column a t 105C was
placed i n a s e r i e s - b y p a s s mode with a 2.5 m molecular s i e v e column main-
t a i n e d a t 30C. With the columns connected i n s e r i e s , H2, CO and CH4 pass
through the por0pa.k column and i n t o t h e molecular s i e v e column where t h e y
a r e temporarily reta.ined,. A valve i s then switched so t h a t t h e molecular

104
s i e v e i s bypassed and C02, H20 and C2-C4 compounds a r e separated and
analyzed. With t h e columns placed in s e r i e s once a g a i n , a n a l y s i s o f Hp,
CO a n d CH4 takes place.
The i r o n c a t a l y s t , supplied by t h e P i t t s b u r g h Energy Technology
Center ( P E T C ) of DOE, c o n s i s t e d of t a c o n i t e which was plasma-sprayed t o
an average thickness o f 0.56 mm on f l a t p l a t e s of i r o n s u b s t r a t e . I t
h a d a BET area of 2 m2/gm and a p o r o s i t y of 0.48. The c a t a l y s t assembly
c o n s i s t e d of 5 p l a t e s , each 7 . 6 cm h i g h and o f varying widths so a s t o
be compatible w i t h t h e d r a f t tube s i z e o f the Berty r e a c t o r . The p l a t e s
were bolted t o g e t h e r with two threaded rods and t h e assembly and dimen-
s i o n s a r e shown in Figure 2 . The c a t a l y s t was assembled, l e a k t e s t e d i n
He and then reduced by h e a t i n g t o 501)OC in flowing H2 over a 4-hour
period and then holding a t 450°C f o r 24 hours. Attempts were made t o
e s t i m a t e t h e water make during reduction i n o r d e r t o deteriiine t h e percen-
t a g e reduction o f t h e a v a i l a b l e i r o n . Unfortunately t h e slow reduction
rate and consequent low H20 c o n c e n t r a t i o n s d i d not allow f o r a c c u r a t e meas-
urements.
The need f o r a c a r b u r i z a t i o n pretreatment when usina i r o n Fischer
Tropsch c a t a l y s t s h as been t h e s u b j e c t o f a number of i n v e s t i g a t i o n s . l 3
In t h i s c a s e we u t i l i z e d a H2/CO feed of 1 . 5 a t 300°C and 1 . 6 MPa and ran
f o r a t o t a l o f 30 hours on-stream. This corresponded t o the time a t
which the a c t i v i t y and product d i s t r i b u t i o n s t a b i l i z e d . I t should be
pointed o u t however, t h a t t h e c a t a l y s t was i d l e d i n H2 a t 3OOOC and 1 . 6 MPa
a t t h e end o f each d a y ' s running. I n a d d i t i o n t h e conversions v a r i e d
during t h i s pretreatment a n d , s i n c e t h e r e a c t o r behaves a s a CSTR, t h e
c a t a l y s t was exposed t o varying H2/CO r a t i o s . This w i l l be discussed
below in more d e t a i l .
RESULTS
P r i o r t o e n t e r i n g i n t o a d i s c u s s i o n o f t h e r e s u l t s , i t i s important
t o emphasize the behavior of a CSTR r e a c t o r such as t h e one used h e r e ,

105
F i r s t of a l l , in d i s c u s s i n g r e a c t i o n r a t e s or product d i s t r i b u t i o n s , i t
i s t h e r e a c t o r exit c o n d i t i o n s which a r e t h e independent v a r i a b l e s . These
a r e brought about by independent control of t h e i n l e t flow r a t e , i n l e t
composition, r e a c t o r p r e s s u r e , and temperature. Consequently, in t h e sub-
sequent discussion o n l y t h e e x i t c o n d i t i o n s w i l l be r e f e r r e d t o . Another
important f a c t o r i s t h a t , s i n c e a f i x e d bed c a t a l y t i c r e a c t o r (s p l u g
flow) w i l l have c a t a l y s t exposed t o both i n l e t a n d o u t l e t c o n d i t i o n s , i t
i s important t o o b t a i n data over a wide range of conversions and i n l e t com-
p o s i t i o n s . For example, i n Fischer-Tropsch s y n t h e s i s the Hz/CO r a t i o w i l l
q e n e r a l l y i n c r e a s e a s conversion i n c r e a s e s . T h u s i t i s important t o vary
t h e conversion a s well a s t h e i n l e t H 2 / C O r a t i o so t h a t a wide range of
independent data a r e a v a i l a b l e f o r s t a t i s t i c a l a n a l y s i s . In t h i s work
t h e CO conversions v a r i e d from 15% t o 85% and t h e e x i t H2/CO r a t i o s were
v a r i e d independently from 0.8 t o 18. Total p r e s s u r e s ranged from 0.77 t o
3.1 MPa and temperatures from 250C t o 300C.

Induction Period
The f a c t t h a t Fischer-Tropsch c a t a l y s t s a e n e r a l l y r e q u i r e an induc-
t i o n ( o r " c a r b u r i z a t i o n " ) period has a l r e a d y been mentioned. Proper
c a r b u r i z a t i o n i s thought t o i n c r e a s e t h e c a t a l y s t l i f e t i m e and of course
t h i s i s exceedingly important f o r commercial s u c c e s s . I n o u r c a s e , we
wished t o o b t a i n r a t e d a t a corresponding t o t h e s t a b l e a c t i v i t y of t h e
c a t a l y s t a n d we were unable t o run continuously. Because of t h i s l a t t e r
r e s t r i c t i o n we followed a procedure of i d l i n q t h e c a t a l y s t i n Hp a t 1 . 0 HPa
whenever we were n o t running. Because of t h e s e d i f f e r e n c e s we e l e c t e d t o
u t i l i z e an a l t e r n a t e i n d u c t i o n method which was more compatible with our
day-to-day o p e r a t i o n and which appeared t o give t h e same s t a b l e a c t i v i t y ' "
a s t h e more t y p i c a l complex c a r b u r i z a t i o n procedure.
The procedure employed during t h e f i r s t 24 hours of induction was t o
expose the c a t a l y s t a t 300C and 1.6 MPa p r e s s u r e t o a 1 . 5 H 2 / C O mixture a t
an "exposure v e l o c i t y " ( J , volumetric flow r a t e a t standard c o n d i t i o n per
u n i t s u p e r f i c i a l c a t a l y s t a r e a ) of 2.6 m / h r . Some of the r e s u l t s obtained

106
d u r i n g t h i s p e r i o d a r e shown i n F i g u r e 3. F i r s t o f a l l i t s h o u l d be n o t e d
t h a t t h e c o n v e r s i o n was v e r y h i g h d u r i n g t h e f i r s t f o u r h o u r s on s t r e a m .
This points t o the importance o f conducting Fischer-Tropsch c a t a l y s t
s c r e e n i n g t e s t s o n l y a f t e r t h e c a t a l y s t s have been exposed t o s y n t h e s i s
gas f o r a t l e a s t f o u r h o u r s . Note t h a t d u r i n g t h e f i r s t 20 h o u r s o f i n d u c -
t i o n , t h e conversion s t a r t s o f f l o w and b u i l d s up d u r i n g t h e d a y ' s run. It
was h y p o t h e s i z e d t h a t t h e H2 i d l i n g p r o c e d u r e was e f f e c t i n g r e d u c t i o n o f
t h e a c t i v e i r o n c a r b i d e so t h a t t h e f i r s t few h o u r s o f t h e r u n a r e s p e n t
r e f o r m i n g FeC a t t h e expense o f h y d r o c a r b o n p r o d u c t i o n . As a r e s u l t , t h e
i n l e t c o n d i t i o n s were changed a t 24 h o u r s t i m e - o n - s t r e a m (TOS) t o 3.1 MPa
and H2/CO = 2.0. As c a n be seen f r o m F i g u r e 3, once t h i s change was
made, t h e v a r i a t i o n i n d a i l y c o n v e r s i o n s was m a r k e d l y r e d u c e d and t h e
c a t a l y s t reached a p p a r e n t s t a b i l i t y a f t e r a b o u t 35 h o u r s TOS.
W h i l e t h e r e s u l t s i n F i g u r e 3 show o n l y t h e t o t a l CO c o n v e r s i o n ,
some m e n t i o n o u g h t t o be made o f t h e s e l e c t i v i t y t o C5' during t h i s period.
D u r i n g t h e 24 h o u r s TOS, t h e C5' w e i g h t f r a c t i o n o f t o t a l h y d r o c a r b o n make
g r a d u a l l y i n c r e a s e d on a d a i l y b a s i s f r o m a b o u t 0.05 t o 0.20. After this
p e r i o d t h e f r a c t i o n remained e s s e n t i a l l y c o n s t a n t a t a b o u t 0 . 2 5 .

Product D i s t r i b u t i o n
I n p r i n c i p l e e i t h e r GO2 o r H20 c a n be p r o d u c e d f r o m t h e c h a i n g r o w t h
which occurs during Fischer-Tropsch synthesis. However, CO2 c a n a l s o be
p r o d u c e d v i a t h e r e v e r s i b l e w a t e r gas s h i f t r e a c t i o n

T y p i c a l l y t h e COP make was comparable t o t h e CH4 make a t 250C and was 50

t o 100% g r e a t e r t h a n CH4 a t 300C. I f t h e C02 i s produced f r o m a s i d e
r e a c t i o n such as e q u a t i o n (41, t h e n one w o u l d e x p e c t an i n c r e a s i n g CO/H2
r a t i o w i t h increased conversion. As T a b l e I shows, t h i s i s i n d e e d t h e case
a t b o t h t e m p e r a t u r e s as l o n g a s t h e H2/CO r a t i o i s a p p r o x i m a t e l y c o n s t a n t .
Also shown i n T a b l e I i s t h e e q u i l i b r i u m p a r a m e t e r , C$I,w h i c h i s d e f i n e d as

107
and w i l l o f course be equal t o 1 . 0 a t e q u i l i b r i u m (Keq i s t h e e q u i l i b r i u m
c o n s t a n t ) . I t i s apparent from the r e s u l t s shown in Table I t h a t t h e
water gas s h i f t r e a c t i o n i s well removed from e q u i l i b r i u m a t 250C b u t
c l o s e r a t 30OC. Some measure o f t h e r e v e r s i b l e n a t u r e o f the r e a c t i o n
r a t e can a l s o be obtained from Table I . That i s , a t c o n s t a n t conversion
the C02/H20 r a t i o decreases a s t h e H2/CO r a t i o i n c r e a s e s . This would
i n d i c a t e a n i n h i b i t i o n o f the forward r e a c t i o n r a t e o f equation ( 4 ) by
increased product-to-reactant r a t i o s .
Another important a s p e c t of Fischer-Tropsch s y n t h e s i s i s t h e o l e f i n -
t o - p a r a f f i n r a t i o of t h e hydrocarbon products. Table I 1 shows t h e C2Hq/C2Hg
r a t i o a s a function of t h e H2/C0 r a t i o and conversion a t two temperatures.
Note t h a t t h i s r a t i o d e c r e a s e s a s conversion i n c r e a s e s a t both temperatures
in agreement with K ~ g l e r ' s ' ~hypothesis t h a t t h e main elements i n chain
growth a r e o l e f i n s , not p a r a f f i n s . As expected, higher H 2 / C O r a t i o s a l s o
lower t h e C2Hq/CzHg r a t i o s i n c e t h e s e would tend t o proniote hydrogenation.
Comparing the d a t a a t two temperatures, i t can a l s o be seen t h a t higher
C2Hq/CzHg r a t i o s a r e favored a t t h e lower temperature.
The experiments conducted during t h i s p o r t i o n of the i n v e s t i g a t i o n
were designed p r i m a r i l y t o o b t a i n r e a c t i o n r a t e data and s i n c e a l a r g e
number o f s e p a r a t e runs were required t o accomplish t h i s g o a l , t h e r u n
times were g e n e r a l l y r e s t r i c t e d t o 3 hours o r l e s s . Unfortunately t h i s
i s not a s u f f i c i e n t l e n g t h o f time t o o b t a i n l a r g e enough q u a n t i t i e s of
o i l f o r a c c u r a t e measurements ( t h e o i l make varied from about 0.2 t o 4 . 0
m l / h r ) . Nevertheless, some i n s i g h t i n t o t h e parameters which favor o i l
make can be obtained from t h e d a t a shown i n Figure 4. Here t h e weight
f r a c t i o n o f C$ (Cg+/total hydrocarbon make) i s p l o t t e d a s a f u n c t i o n of
conversion f o r d i f f e r e n t H2/CO r a t i o s a t 250C. As expected, i n c r e a s i n g
conversions r e s u l t in h i g h e r C5+ f r a c t i o n s ( t h e chain has a chance t o
grow) and a p p a r e n t l y higher H2/CO r a t i o s r e t a r d t h e formation o f higher
carbon numbers. Within t h e accuracy l i m i t a t i o n s of the d a t a , t h e Cg
f r a c t i o n d i d not appear t o be a f u n c t i o n o f p r e s s u r e a t 2SOC. However t h i s

108
was not t h e case a t 300C where i t was found t h a t higher p r e s s u r e s tended
t o i n c r e a s e the C$ f r a c t i o n . Because o f t h i s , t h e r e were n o t enough 300C
d a t a a t s i m i l a r c o n d i t i o n s i n o r d e r t o o b t a i n a good coniparison w i t h t h e
d a t a a t 250C. Nevertheless the r e s u l t s i n Table 111 show a d e f i n i t e
decrease in t h e Cf f r a c t i o n a s t h e temperature i n c r e a s e s from 250C t o
300C.
Another parameter of i n t e r e s t in Fischer-Tropsch s y n t h e s i s i s t h e
product d i s t r i b u t i o n of the hydrocarbon make. Ourinq most runs a small
b u t d e t e c t a b l e wax was c o l l e c t e d from t h e h o t t r a p (see Figure 1 ) b u t
t h e q u a n t i t i e s were too small f o r a c c u r a t e a n a l y s i s . A number o f o i l -
make samples were a l s o s u b j e c t e d t o GC-MS a n a l y s i s and carbon numbers u p
t o about 18 were d e t e c t e d with t h e highest weight f r a c t i o n a t C8 o r C9.
The major c o n s t i t u e n t s of t h e o i l were t h e normal p a r a f f i n s with varying
q u a n t i t i e s of o l e f i n s and branched compounds a t each carbon number. L i t t l e
i n t h e way of oxygenated compounds were d e t e c t e d .
A common a n a l y s i s t o which Fischer-Tropsch hydrocarbons a r e s u b j e c t e d
i s t h e so c a l l e d "Schulz-Flory" d i s t r i b u t i o n . 1 6 I n t h i s case t h e log o f
t h e mass f r a c t i o n of each s p e c i e s divided by i t s carbon number would p l o t
l i n e a r l y a s a f u n c t i o n of carbon number i f Fischer-Tropsch s y n t h e s i s follows
equal p r o b a b i l i t y chain growth. Such a p l o t , t y p i c a l o f t h e d a t a c o l l e c t e d
h e r e , i s shown in Figure 5. As can be seen, while l i n e a r p l o t s a r e ob-
t a i n e d a t low and high carbon numbers, t h e r e i s a t r a n s i t i o n region between
C4 and c8 which does not p l o t l i n e a r l y . Since t h e C1-c4 compounds essen-
t i a l l y remain in t h e gas phase and t h e Cg compounds are c o l l e c t e d i n t h e
l i q u i d phase, i t was f i r s t t h o u g h t t h a t t h e behavior in Figure 5 was due
t o a material balance e r r o r . However when various a r b i t r a r y e r r o r s were
added, e i t h e r t o t h e gas o r l i q u i d q u a n t i t i e s , t h e same type o f p l o t
r e s u l t e d . Evidently t h e Schulz-Flory d i s t r i b u t i o n does n o t apply over
t h e complete carbon number range. I t i s i n t e r e s t i n g t o note t h a t s i m i l a r
r e s u l t s with t h i s c a t a l y s t have been obtained a t PETC using a t u b u l a r
flow r e a c t o r .
109
Reaction Rates
I d e a l l y we would l i k e t o measure i n t r i n s i c r e a c t i o n r a t e s ( t h a t i s ,
r a t e s i n t h e absence of a l l t r a n s p o r t l i m i t a t i o n s ) under proposed com-
mercial o p e r a t i n g c o n d i t i o n s such a s those used h e r e . For Fischer-Tropsch
s y n t h e s i s t h i s i s d i f f i c u l t t o do because of t h e production of higher
carbon number o i l s which could s a t u r a t e the c a t a l y s t pores and l e a d t o
t h e n e c e s s i t y of gaseous r e a c t a n t s having t o d i f f u s e through l i q u i d
f i l l e d pores. Although t h e t h i c k n e s s of t h e c a t a l y s t used here was only
0.56 mm, t h e very low d i f f u s i v i t i e s of gases in l i q u i d s (% cmZ/sec)
can s t i l l r e s u l t in pore d i f f u s i o n l i m i t e d r a t e s . This w i l l be discussed
i n more d e t a i l below. For high r e a c t i o n r a t e s i t i s a l s o p o s s i b l e t o
be limited by g a s - s o l i d t r a n s p o r t phenomena. This was avoided i n t h e s e
experiments by i n c r e a s i n g t h e r e a c t o r impeller speed u n t i l t h e r e was no
s e p a r a t e dependency o f t h e r a t e on impeller speed. This was found t o
occur a t 750 rpm and, a s mentioned e a r l i e r , a l l data were obtained a t
1500 rpm.
Because of t h e p o s s i b i l i t y of pore d i f f u s i o n l i m i t a t i o n s , t h e r a t e
data were n o t s u b j e c t e d t o thorough e v a l u a t i o n s of various mechanistic
k i n e t i c expressions. I n a d d i t i o n , because of the complexity of Fischer-
Tropsch s y n t h e s i s , i t was decided t o f i r s t attempt t o analyze t h e r a t e
of consumption of CO, independent o f t h e s p e c i e s , produced. Consequently
a simple power law model in terms o f CO and H2 p a r t i a l p r e s s u r e s was
evaluated but i t d i d not provide f o r a s u f f i c i e n t l y a c c u r a t e c o r r e l a t i o n .
Although a number o f more complex models were found t o give adequate
c o r r e l a t i o n s of t h e data i t was found t h a t t h e r a t e expression oiven by
equation ( 1 ) gave as good a c o r r e l a t i o n a s any. S p e c i f i c a l l y
k Pn2
rCO = 1 + b PH$PCO
4-

with k = 7 . 6 ~ 1 0exp
~

110
In t h e s e quations rCO i s expressed i n terms of the s u p e r f i c i a l a r e a o f the
c a t a l y s t , g moles/mZ-hr, pressure i s i n atmospheres and temperature i s in
degrees Kelvin.
I n comparing t h e s e values with those given previously by Atwood and
Bennett' f o r a potassium promoted fused iron c a t a l y s t , t h e major d i f f e r e n c e
i s in t h e apparent a c t i v a t i o n enerqy f o r k . Atwood and Bennet r e p o r t e d a
value of 20.3 Kcal/mole whereas we observe a much lower value o f 8.8 Kcal/mole.
Again t h i s miqht be due t o strong pore d i f f u s i o n e f f e c t s s i n c e i t i s well
known t h a t f o r near f i r s t order k i n e t i c s , p o r e d i f f u s i o n r a t e l i m i t a t i o n s
w i l l produce a n apparent a c t i v a t i o n energy equal t o one-half i t s true value.
I f t h i s were t h e c a s e , one w o u l d expect t h a t equation ( 1 ) would not g i v e
a s good a f i t a t t h e hipher temperature. Figure 6 shows a p l o t of t h e
p r e d i c t e d versus t h e measured values of rCO and, a s can be s e e n , t h e data
s c a t t e r i s d e f i n i t e l y l a r g e r a t 300C. I n f a c t t h e averaqe d e v i a t i o n a t
250C was approximately 10% whereas i t was 20% a t 300C.
As a l r e a d y mentioned, CH4 was t h e most s i q n f i c a n t product under a l l
c o n d i t i o n s . Consequently a s e p a r a t e determination was made of a r a t e ex-
pression which would d e s c r i b e i t s r a t e of formation. Due t o t h e f a c t t h a t
CH4 i s only one of many products, no attempt was made t o base t h e r a t e
expression on k i n e t i c mechanisms. Instead a simple power low model was
employed and t h e r e s u l t s a r e shown i n equation ( 8 )

Here again t h e r a t e i s given i n moles/m2hr a n d t h e p r e s s u r e in atmospheres.

As expected, an increased r a t e of CH4 production i s favored by higher tern-
p e r a t u r e s and higher H 2 / C O r a t i o s .
A s i m i l a r attempt was made t o o b t a i n a s u i t a b l e c o r r e l a t i o n f o r t h e
r a t e of CO2 production. Since i t i s hypothesized t h a t t h e C02 i s produced
via the water gas s h i f t r e a c t i o n , i t was a n t i c i p a t e d t h a t t h e r a t e here
would depend on t h e p a r t i a l pressures of CO and H20. S u r p r i s i n g l y however,

111
t h e r a t e was found t o be independent of Pco b u t r a t h e r t o be dependent on
t h e H20/H2 r a t i o a s shown in equation ( 9 ) .

rCo2 = 6 . 5 8 ~ 1 0exp --
~ [-,,500 ] (F) 1-3 (9)

This could be explained i n two ways: t h e r e v e r s e r e a c t i o n r a t e i s s i g n i f i -

c a n t and s t r o n g l y dependent on P H ~ ;and CO i s i n excess ( s i n c e H20 i s
a product o f t h e primary s y n t h e s i s r e a c t i o n s ) . The f i r s t p o r t i o n of t h i s
explanation can n o t be proven b u t seems t o be reasonable ( s t r o n o H2
adsorption could produce the same e f f e c t ) . Although t h e d a t a used i n
o b t a i n i n g equation ( 9 ) covered a wide range of CO/H20 r a t i o s ( 0 . 2 - 1 2 ) ,
t h e r e were only t h r e e runs ( o u t of 62) with CO/H20 l e s s than one. Since
t h e s e runs had very high COP production r a t e s and high CO conversions, i t
i s conceivable t h a t the r a t e of CO2 production does depend on Pco when i t
i s l e s s than o r equal t o PH20.
Diffusion L i m i t a t i o n s
The p o s s i b i l i t y o f s t r o n g pore d i f f u s i o n e f f e c t s has a l r e a d y been
mentioned and t h e d a t a f o r t h e CO consumption r a t e g i v e s some evidence of
i t s e x i s t e n c e . However t h e r a t e expression f o r C02 production had an
a c t i v a t i o n energy more t y p i c a l of k i n e t i c r e a t i o n s and s i n c e i t was found
t o depend on P H ~ o , the primary product of Fischer-Tropsch s y n t h e s i s , i t i s
somewhat s u r p r i s i n q t h a t i t d i d not have a lower apparent a c t i v i a t i o n
energy. A p o s s i b l e e x p l a n a t i o n could be t h a t t h e dominant r e a c t i o n i s
methanation and, i f i t were much f a s t e r and in p a r a l l e l with t h e o t h e r
slower r e a c t i o n s , i t could be t h e only pore d i f f u s i o n l i m i t e d r e a c t i o n .
Since equation ( 1 ) i s based on t h e t o t a l CO consumption r a t e and CH4 i s
t h e major product, t h i s would explain t h e apparent discrepancy i n t h e
apparent a c t i v a t i o n e n e r g i e s i n equations ( 6 ) and ( 9 ) . Some support of
this argument i s given by t h e low a c t i v a t i o n energy a s s o c i a t e d with CH4
production [equation (8)].

112
 Whereas s e p a r a t e e x p e r i m e n t s t o q u a n t i f y t h e r o l e o f p o r e d i f f u s i o n
were n o t conducted, e s t i m a t e s o f t h e e f f e c t i v e n e s s f a c t o r c a n be made
p r o v i d e d t h e r e i s some knowledge o f t h e v a l u e o f t h e e f f e c t i v e d i f f u s i v i t y .
Atwood and B e n n e t t , ' assuming t h a t CO d i f f u s i o n i n t h e l i q u i d f i l l e d p o r e s
was l i m i t i n g , used a v a l u e o f 1 . 6 ~ 1 0 - 5 cm'/sec f o r a fused i r o n c a t a l y s t .
U s i n g t h i s v a l u e and r e a r r a n g i n g e q u a t i o n ( 1 ) t o g i v e an e f f e c t i v e f i r s t
o r d e r r e a c t i o n , we e s t i m a t e t h e e f f e c t i v e n e s s f a c t o r be a b o u t 0.30 a t
300 C . Thus i t a p p e a r s t h a t we have s t r o n g p o r e d i f f u s i o n e f f e c t s w i t h
r e s p e c t t o t h e CO c o n s u m p t i o n r a t e . T h i s i s p r o b a b l y due t o t h e h i g h r a t e
o f f o r m a t i o n o f CH4 w h i c h was t h e m a j o r p r o d u c t ( s e l e c t i v i t y % 60%).

ACKNOWLEDGE
The f i n a n c i a l s u p p o r t o f t h i s work b y DOE u n d e r c o n t r a c t No.
DE-AS22-78ET00260 i s g r a t e f u l l y acknowledged.

113
 REFEREPJCES

1. Ponec, \/., CATAL. R E V . - SCI. ENG., s,p . 151 ( 1 9 7 8 ) .

2. S t o r c h , H. H . , ti. Golunibic, and R . E . Anderson, "The F i s c h e r - T r o p s c h and

R e l a t e d Syntheses," John W i l e y & Sons, New York ( 1 9 5 1 ) .

3. Dent, A. L . and 1.1. L i n , ACS P r e p r i n t s , D i v . o f P e t r . Cheiii., Anaheim, C A . ,

-
23, No. 2, p . 502, March 1978.

4. Everson, R . C . , E . T. Woodburn, and A. R . M. K i r k , J. CATAL., 2, p . 136

(1978).

5. Yang, C . H. and A . G. Oblad, P r e p r i n t s , D i v . of P e t r . Cheni., Anaheim, C4.,

-
23, No. 2, p. 513, March 1978.

Shah, Y . T . ana A. J . P e r r o t t a , I A EC PROD R ?, D, is, p. 123 ( 1 9 7 6 ) .

Dry, M. E., T. S h i n g l e s , and L . J . E o s h o f f , J . CATAL., 5, p . 99 ( 1 9 7 2 ) .

Atwood, H. E. and C. 0. Eennett, I & EC PROC. DES. DEV., 18,p . 163 (1979)

Anderson, R. B., i n " C a t a l y s i s " , p. 257, V o l . I V , Ed. by P . H. Eininett,

R h e i n h o l d Pub. Co., N . Y . , 1956.

10. C1iei;iical and E n g i n e e r i n g Plews, S e p t . 17, 11. 13, 1 9 7 9 .

11. Denieter, J . J . , Youngblood, A . J., F i e l d , J . H . , and B l e n s t o c k , D . , U. S.

BUR. MI:.ILS REPT. I I V . 7033 ( 1 9 6 7 ) .

12. Haynes, W. P . , B a i r d , i4. J . , Schehl, R . R . and Zarochak, M. F., Preprints,

D i v . P e t r . Chem., ACS, 2, No. 2, p . 559, 1Y78.

13. S a n c i e r , K . M., I s a k s o n , 14. E., Wise, H . , P r e p r i n t s , D i v . of P e t r . Chem.,

ACS, g, No. 2, p. 545, 1978.
14. Schehl, R. R., P i t t s Energy Tech Ctr., p r i v a t e conimunication.

15. K u g l e r , E . L., p a p e r p r e s e n t e d a t t h e ADVANCES I!( CATALYTIC CHEMISTRY.

Snowbird, UT, O c t . 2-5, 1979.

16. H e n r i c i - O l i v e , G., O l i v e , S . , Angem. Chein. I n t . Ed. E n g l . , 15,p . 136,

1976.

114
 TABLE 1

COZ/H20 IWKE AT TWO TEMPERATURES

-
H2/COp xco CO-P 2 0 0

250 C 2.24 .26 .14 ,004

2.25 .34 .25 .01
2.16 .50 .37 .01
5.9 .79 .42 ,016
9.9 .74 .27 .027

300 C 1.2 .60 1.9 ,057

2.a .59 1.1 ,077
5.5 .62 0.6 ,083
3.6 .75 1 .o ,091
6.1 .79 1 .o ,153
7.3 .74 0.6 ,110
9.3 .76 0.45 .11

TA6LE 1 1

ETHYLEIIE/ETHAilE ilAKE AT TWO TEVPERATURES

HZ/CO xco C2H4/C2H6

250 C 1.5 .15 .14

1.2 .21 .13
2.24 .26 .092
2.25 .34 ,076
2.16 .50 ,050
5.9 .79 .020
8.9 .74 ,012

300 C 1.05 .26 .096

1.20 .41 .079
1.20 .60 ,028
2.60 .59 .023
5.50 .62 ,012
9.30 .76 .005
--
TABLE 111

COMPARISOH OF C l FRACTION AT TWO TEMPERATURES

H2/C0 PT(MPa) C i Fraction

T(C) xco
250 .50 2.5 1.47 .31
300 .51 1.7 1.47 .12

250 .55 4.0 2.15 .18

300 .58 3.3 2.02 .10
250 .65 6.7 2.84 .13
300 .76 8.3 2.84 .07

115
FIGURE 1: SCHEMATIC OF EXPERIMEP!TAL EQUIPI.1ENT

FIGURE 2 : CATALYST ASSEMBLY

FLOW

116
 F1GUP.E 3: INDUCTIOtl PEEIOD: CGNVERSlCfl VERSUS TIGE

. . _ _ _ - - _ -- .. /
TOS
\
= 0

.,
/
/
.80 \

/
\
, _. - _ _ c _ c - - -

---- /

TOS = 3 5
.70 /----
I-
0 /
X
V
.60
/
/'
;TOS = 20
.50

.40 1 I I
1 2 3

TIME F R O M S T A R T OF D A I L Y RUN , hr

FIGURE 4: \!EIGHT iRACTION C5' VS. X,-o (250C)

.30

0 H2/CO 2
Ed H 2 / C O = 2.8
+ r J A H 2 / C O = 3.9
u

+
0 A
3
.10

I I I I I I I
.10 .20 .30 .40 .50 .60 .70

xco
117
.-
n
x

-
0
0

0.

0. I I I ! I I I
2 4 6 8 10 12 14

C A R B O N NO. ( P )

FIGURE 6: PREDICTED VS. MEASURED VALUES OF RCO

AL S

0
0@' / h

v
0

t/
15 250 C

@ 300 C

0
n
W
K
n 10 .O

1/ I I I I I
10 15 20 25 30

ME A S U f? E 0 nc o . rn o I P 5 I m 2 - h r

118
 Synthesis Gas Conversion to Gasoline Range Hydrocarbons
over Medium Pore Zeolite Catalysts Containing 3d-Metals and Bimetallics

V. U. S. Rao, R. J. Gormley, H. W. Pennline, L. C. Schneider and R. Obermyer*

Pittsburgh Energy Technology Center

4800 Forbes Avenue
Pittsburgh, PA 15213
and
*Department of Physics
Pennsylvania State University
McKeesport, PA 15132

Introduction

There is much current interest in the conversion of synthesis gas to gasoline range hydro-
carbons using bifunctional zeolite catalysts (1,Z). The medium pore (dia 6A) zeolite
ZSM-5 in combination with Fe was shown to yield a high fraction of aromatics in the
product, resulting in a favorable octane number ( = 9 0 ) . The transition metal (TM)
component catalyzed the hydrogenation of CO while the acid function of the zeolite led
to an aromatic product. Owing to the medium size pores of ZSM-5 there was a fairly
sharp cut-off, in the product distribution near the end of the gasoline range for the
aromatic fraction.

I n order to explore further the role of the TM component and the acidity of the zeolite
on the product composition, experiments were performed i n our laboratory on ZSM-5
impregnated with Fe and Fe-Co, and on Silicalite impregnated with Fe. Silicalite is a
molecular sieve form (3) of Si0
2'
A romparison of the crystallographic studies (4,5) on ZSM-5 and Silicalite, shows that
the two zeolites possess very similar crystal structures. While the SifA1 ratio in
ZSM-5 can be varied from 3 to 03, Silicalite has essentially no Al. Hence, it appears
that Silicalite is the limiting form of ZSM-5 when the A1 concentration is vanishingly
small. Owing to the lack of cations which can be exchanged with protons, Silicalite
has no acidity, while HZSM-5 is a highly acidic zeolite. Our investigations sought
to find the difference in selectivity for synthesis gas conversion by ZSM-5 (Fe) and
Silicalite (Fe) catalysts resulting from the above mentioned difference in acidity.

A further aim of the investigation was to investigate possible difference in selectivity

between ZSM-5 (Fe) and ZSM-5 (Fe-Co) catalysts, resulting from the different 3d-electron
concentration of the M component. Magnetic studies (TMA) were performed to characterize
the TM component and particularly to detect the formation of bimetallic Fe-Co clusters.

Experimental

The zeolites were prepared using methods described in the literature (3,6). The metal
component was introduced by gradually adding the metal nitrate solution to the zeolite
until incipient wetness was reached. The impregnation with the metal nitrate solution
was carried out for an hour under vacuum in order to enable the nitrate solution to
enter the pores o f the zeolite. The material is initially dried with constant stirring
over a boiling water bath, and further dried in air at 110" C for 12 hours. It is then
pelleted to yield tablets 3mm in diameter. I n the case of the Silicalite based catalysts,
about 10% by weight of an amorphous silica such as Ludox AS-40 was added as a binder
before the pelletization step.
119
The c a t a l y s t s w e r e t e s t e d f o r s y n t h e s i s g a s c o n v e r s i o n i n b o t h a f i x e d bed m i c r o r e a c t o r
and a B e r t y ( c o n t i n u o u s f l o w s t i r r e d t a n k ) r e a c t o r (7). The l a t t e r i s shown i n F i g u r e 1.
The c a t a l y s t p e l l e t s were l o a d e d i n t o t h e 2-inch d i a m e t e r CFSTR chamber and r e t a i n e d
by g l a s s wool w i t h a s c r e e n . I m p e l l e r speed was 1240 rpm. E x c e l l e n t bed t e m p e r a t u r e
c o n t r o l was o b t a i n e d by a m o d i f i c a t i o n which i n v o l v e d t h e i n s t a l l a t i o n o f a c o i l i n t h e
head o f t h e r e a c t o r t h r o u g h which a i r c o u l d f l o w f o r f a s t e r h e a t removal.

A s c h e m a t i c diagram o f t h e r e a c t o r s y s t e m i s shown i n F i g u r e 2. Synthesis gas with a

H f C 0 - r a t i o of e i t h e r 2 1 1 o r 111 would p a s s t h r o u g h a c a r b o n t r a p and e n t e r t h e r e a c t o r .
Lgquid and s o l i d h y d r o c a r b o n p r o d u c t s a r e c o l l e c t e d i n a h o t t r a p u s u a l l y m a i n t a i n e d a t
150" C and i n a n i c e t r a p . T h i s s e r i e s of t r a p s a r e a l t e r n a t e d and d r a i n e d p e r i o d i c a l l y .
Product gases a r e metered and then f l a r e d .

The t a b l e t s of t h e z e o l i t e i m p r e g n a t e d w i t h TM were r e d u c e d i n f l o w i n g H a t 2 1 b a r
and L50° C f o r 24 h r s . They were t h e n c a r b i d e d w i t h s y n t h e s i s g a s a t 7 t a r and 250' C
f o r 24-48 h r s t o y i e l d t h e a c t i v e c a t a l y s t . The gas p h a s e p r o d u c t (C -C h y d r o c a r b o n s )
was a n a l y z e d by g a s chromatography. The l i q u i d p r o d u c t w a s s e p a r a t e d l i n ? o p a r a f f i n s ,
o l e f i n s , a r o m a t i c s and o x y g e n a t e s by column chromatography u s i n g FIA d e t e c t i o n .

R e s u l t s and D i s c u s s i o n

(a) I n f l u e n c e of Z e o l i t e A c i d i t y :

The r e s u l t s o b t a i n e d i n t h e B e r t y r e a c t o r on t h e c a t a l y s t s ZSM-5 ( 1 1 . 1 w t % Fe) and

S i l i c a l i t e ( 1 3 . 6 w t % Fe) a r e shown i n T a b l e 1. I t i s a p p a r e n t t h a t a h i g h p e r c e n t a g e of
a r o m a t i c s i s o b t a i n e d from t h e ZSM-5 (11.1% F e ) c a t a l y s t , w h i l e t h e p r o d u c t from t h e
S i l i c a l i t e (13.6% Fe) c a t a l y s t h a s a low a r o m a t i c f r a c t i o n b u t much h i g h e r o l e f i n and oxy-
genate fractions. I t i s t h u s a p p a r e n t t h a t t h e a c i d f u n c t i o n of ZSM-5 b a s e d c a t a l y s t i s
r e s p o n s i b l e f o r t h e c o n v e r s i o n of t h e o l e f i n s and o x y g e n a t e s t o a r o m a t i c s . The a r o m a t i c
f r a c t i o n i m p a r t s a h i g h o c t a n e number t o t h e p r o d u c t .

(b) High O l e f i n Y i e l d s from S i l i c a l i t e Based C a t a l y s t s :

The i n t e r e s t i n g a s p e c t o f t h e p r o d u c t s l a t e s from t h e S i l i c a l i t e b a s e d c a t a l y s t s was t h e

h i g h p e r c e n t a g e of o l e f i n s i n b o t h t h e g a s and l i q u i d p h a s e p r o d u c t s . When promoted
w i t h p o t a s s i u m , t h e Fe c o n t a i n i n g S i l i c a l i t e c a t a l y s t y i e l d e d a l a r g e C2-C4 o l e f i n
f r a c t i o n a s s e e n i n T a b l e 2. The C -C o l e f i n f r a c t i o n from S i l i c a l i t e ( 7 . 8 % F e ,
0.9% K ) i n a f i x e d bed microreactor2is4compared w i t h t h a t from a p r e c i p i t a t e d
Fe-Mn c a t a l y s t of K o l b e l e t a 1 (8), known f o r i t s v e r y h i g h o l e f i n y i e l d . It i s s e e n
t h a t t h e o l e f i n y i e l d s f r o m t h e two c a t a l y s t s a r e q u i t e Comparable. The S i l i c a l i t e
( 7 . 8 % F e , 0.9% K) c a t a l y s t y i e l d s a much h i g h e r C -C o l e f i n f p a r a f f i n r a t i o t h a n t h e
p r e c i p i t a t e d Fe-Mn c a t a l y s t and h e n c e i s o f p o t e n g i a f commercial i n t e r e s t . The mechanism
f o r t h e enhancement o f o l e f i n p r o d u c t i o n on a d d i n g K a s a promocer h a s been d i s c u s s e d by
Dry e t a l . ( 9 ) .

(c) I n f l u e n c e of T r a n s i t i o n M e t a l Component o n P r o d u c t Composition:

The a d d i t i o n o f c o b a l t t o F e c o n t a i r l i n y ZSM-5 c a t a l y s t w a s found t o r e s u l t i n a marked

change i n p r o d u c t c o m p o s i t i o n a s s e e n from t h e B e r t y r e a c t o r s t u d y r e s u l t s i n T a b l e 3 .
I t i s s e e n t h a t t h e i n c o r p o r a t i o n of c o b a l t i n t o t h e c a t a l y s t r e s u l t s i n ( a ) r e d u c t i o n
i n t h e w a s t e f u l s h i f t c o n v e r s i o n a s s e e n from t h e d e c r e a s e +n Cog f" t h e p r o d u c t
( h ) l o w e r i n g o f t h e a r o m a t i c f r a c t i o n t o a b o u t 10% o f t h e C5 f r a c t i o n . However, t h e
Octane number remained a t a r e l a t i v e l y h i g h v a l u e of 81, d e s p i t e t h e d e c r e a s e i n t h e
a r o m a t i c f r a c t i o n . Hence, t h e i m p r e g n a t i o n o f z e o l i t e s w i t h b i m e t a l l i c TM c l u s t e r s
p r o v i d e s a P r o m i s i n g means o f a l t e r i n g t h e e x t e n t of s h i f t c o n v e r s i o n and t h e c o m p o s i t i o n
o f t h e l i q u i d p r o d u c t . Changes i n t h e a r o m a t i c f r a c t i o n w i t h TM component was a n unex-
pected r e s u l t s i n c e a r o m a t i z a t i o n i s normally a s s o c i a t e d w i t h the a c i d i t y of t h e z e o l i t e .
I t i s p o s s i b l e t h a t some of t h e c o b a l t i s a t t a c h e d t o t h e A 1 s i t e s i n t h e z e o l i t e , r e d u c i n g
its acidity. F u r t h e r s t u d i e s on t h i s s u b j e c t a r e n e c e s s a r y .
120
(d) Magnetic Studies:

The magnetic properties of TM impregnated zeolite catalysts have been investigated

between 77K and 923K in applied fields up to 21 kOe. Samples of ZSM-5 (11.1% Fe),
ZSM-5 (5.6% Fe, 4.5% co) and Silicalite (13.6% Fe) were magnetically analyzed after
each of the impregnation, reduction and carburization steps and after use as a
catalyst.

The reduced samples of ZSM-5 (11.1% Fe) and Silicalite (13.6% Fe) indicate that Fe IS in
the metallic state with 86% and 85% reduction, respectively. Thermo-magnetic analysis
(TMA) o f carbided ZSM-5 (11.1% Fe), show it to be in the high Curie point form (10) Of
the Hagg carbide. TMA analysis reveals the used ZSM-5 (11.1% Fe) to be
the hexagonal close packed (hcp) carbide form of Fe2C, and the used Silicalite
(13.6% Fe) to be the high Curie point form of the Hagg carbide.

The TMA of ZSM-5 (5.6% Fe, 4.5% Co) shows that the reduced, carbided, and spent samples
have large magnetic moments (1.94, 2 . 0 4 and 2.61p8per TM atom respectively, at room
temperature) and high Curie points (> 900" C), which cannot be accounted for on the
basis of individual Fe and Co particles. The magnetic data indicate the composition
to be that of a Fe-Co alloy (11). Hence, we conclude that the difference in selectivity
between ZSM-5 (11.1% Fe) and ZSM-5 (5.6% Fe, 4.5% Co) catalysts can be attributed to the
presence of bimetallic TM clusters in the latter, with consequent changes in the
average number of 3d-electrons per TM atom.

(e) TM Cluster Size and Bifunctional Catalysis:

To determine TM particle size in the bifunctional catalysts CO adsorption studies were
performed to determine the TM surface area. These studies showed that the TM clusters
had an average diameter of 100-110 A. Owing t o the limitations connected with CO
adsorption for estimating metal surface areas, the above may be considered to be
approximate values of the TM cluster diameter. Hence, the majority of the TM
clusters must reside outside of the pores of the zeolite. We believe that the
bifunctional catalytic behavior of these catalysts results from high interparticle
diffusivity relative to intracrystalline diffusivity (12).

Conclusions

Our experiments lead to the following conclusions:

(1) Zeolite acidity plays an important role in the formation of aromatics from syn-
thesis gas by bifunctional catalysts as strikingly evidenced in a comparison of the
product slates from ZSM-5 (11.1% Fe) and Silicalite (13.6% Fe).
( 2 ) The transition metal component impregnated into the zeolite plays an important
role in selectivity as seen from the liquid phase products from ZSM-5 (11.1% Fe) and
ZSM-5 (5.6% Fe, 4.5% Co). I n this context, zeolites containing bimetallic clusters
are of special interest.
(3) Silicalite impregnated with Fe and promoted with K has an exceptionally high
selectivity for the production of C2-C4 olefins from synthesis gas.

Acknowledgements

We wish to thank R. R. Schehl and B. D. Blaustein for useful discussions, S. S. Pollack

for x-ray diffraction analyses, M. F. Ferrer for FIA chromatographic studies, A. Elattar
of the University of Pittsburgh for CO adsorption measurements, and W. Picking of
Gulf Research for measuring octane numbers.
121
 T a b l e 1. - Comparison of P r o d u c t s f r o m ZSM-5 (11.1% Fe) and S i l i c a l i t e (13.6% F e )
C a t a l y s t s w i t h H /C0=2, and P=21 b a r .
2
Catalyst ZSM-5 (11.1%Fe) S i l i c a l i t e (13.6% Fe)
Temperature, O C 300 280
CO C o n v e r s i o n , % 68.2 39.4
H Conversion, % 38.7 16.5
2
Spare Velocity (h-l) 1500 1350
P r o d u c t C o m p o s i t i o n (%)
52.0 51.1
3
cHn + oxygenates
19.4
28.6
22.1
26.9
Hydrocarbon a n d Oxygenate C o m p o s i t i o n (%)
CH 54.1 26.5
1.1, 1 5 . 0 2 . 5 , 15.0
:2k,4' :2:6 2.1, 6.3 10.8, 7.2
C3H6' C2H;o 0.0, 4.5 4.8, 4.8
C4+';nd oxygenates 16.9 25.0
5
C o m p o s i t l o n o f C,+ and o x y g e n a t e s (%)
Aromatics 12 4
Olefins 3 41
Saturates 24 33
Oxygenates 1 22
% G a s o l i n e r a n g e (BP <204O C) 75 77
R e s e a r c h o c t a n e No. 96 36

Table 2 . - C o n v e r s i o n o f S y n t h e s i s Gas t o O l e f i n s i n F i x e d Bed R e a c t o r s , U s i n g S i l i c a l i t e

(7.8% F e . 0 . 9 % K) Compared w i t h T h a t U s i n g a P r e c i p i t a t e d Fe-Mn
C a t a l y s t of K o l b e l e t a1 (8).

Catalyst S i l i c a l i t e ( 7 . 8 % F e , 0.9% P r e c i p . Fe-Mn

(our) (Kolbel e t a l )
Pressure (bar) 21 14
T e m p e r a t u r e ("C) 280 290
H /CO R a t i o 0.9 0.8
&ace V e l o c i t y ( h - l ) 1300 353
P r o d u c t C o m p o s i t i o n (CH + Oxygenates) %
CH 8.6 12.1
cfi 8.2 7.6
C2H4 0.4 4.9
C2H6 19.3 17.3
C3H6 <0.2 2.1
C3H8 8.6 15.2
C4H8 <0.2 3.1
c4-Eo O l e f i n s 36.1 40.1
c2-c4
2 4 Paraffins <0.8 10.1
C,+ a n d o x y g e n a t e s 55.1 47.8
c;-c4 Olefins
>45.1 4.0
C -C P a r a f f i n s
2 4

122
Table 3 . - Product Compositions from the Catalysts ZSM-5 (11.1% Fe) and ZSM-5 ( 5 . 6 % Fe,
4 . 5 % Co), in a Berty Reactor, Showing the Influence of cobalt addition to the Catalyst.
Process Condition: H2/C0 = 2 , P = 2 1 Bar and GHSV = 1000 hr-l

Catalyst ZSM-5 (11.1% Fe) ZSM-5 ( 5 . 6 % Fe, 4 . 5 % Co)

Temperature 300 280
CO Conversion, % 68.2 37.8
H Conversion, X 38.7 41.3
S$ace Velocity 1500 1400
Product Composition ( X )

3
~ i +; Oxygenates
~
52.0
19.4
28.6
9.8
51.8
38.4
Hydrocarbon and Oxygenate Composition (%)
C -C hydrocarbons 83.1 74.3
C1+ 2nd Oxygenates 16.9 25.7
5
Composition of C,+ and Oxygenates (%)
Aromatics 72 10
Olefins 3 46
Saturates 24 37
Oxygenates 1 7
X Gasoline range (BP 204' C) 75 94
Research octane No. 96 81

123
 References

1. C. D . Chang, W . H. Lang and A. J. S i l v e s t r i , J. C a t a l . 56, 268 (1979).

2. P. D. C a e s a r , J. A. Brennan, W . E. Garwood and J. C i r i c , 3. C a t a l . 56, 274 ( 1 9 7 9 ) .

3. R. W . C r o s e and E. M. F l a n i g e n , U. S . P a t e n t 4 , 0 6 1 , 7 2 4 (1977).

4. G. T. K o k o t a i l o , S. L. Lawton, D. H. Olson and W . M. Meier, N a t u r e 272, 437 ( 1 9 7 8 ) .

5. E. M. F l a n i g e n , J. M. B e n n e t t , R. W . Grose, J. P. Cohen, R. L. P a t t o n , R. M. K i r c h n e r
and J. W . Smith, N a t u r e 271, 437 ( 1 9 7 8 ) .

6. R . J. Argauer and G . R. L a n d o t t , U. S. P a t e n t 3,702,886 ( 1 9 7 2 ) .

7. J. M. B e r t y , Chem. Engr. P r o g . z,
68 (1974).

8. H. K o l b e l , M. R a l e k and K. D . T i l l m e t z , P r o c . 1 3 t h I n t e r s o c . Energy Conv. Eng.

Conf., S o c i e t y o f Automot. E n g i n e e r s ( 1 9 7 8 ) , p . 482.

9. M. E. Dry, T. S h i n g l e s , L . J. Boshoff and G . J. O o s t h u i z e n , J. Catal. 2, 1 9 0 (1969).

10. K . M. S a n c i e r , W. E. I s a k s o n and H. Wise, P r e p r i n t s , Div. of P e t r o l e u m C h e m i s t r y ,

ACS, 23 ( 2 ) . 545 ( 1 9 7 8 ) .

11. R . M. B o z o r t h , "Ferromagnetism", Van N o s t r a n d , New York, 1 9 5 1 , p p . 190-209.

1 2 . P. B. Weisz, Adv. C a t a l . 13, 1 3 7 (19G2).

124
 Bed thermocouple

F i g u r e 1. - B e r t y R e a c t o r (CFSTR)

125
h
0
U
U
m
p:

N
THE HYD-ION OF CARBON bONOXIDE OVER UCJSUPPORTED I I O N 4 1 A N G F N E S E CATALYSTS FO3
THE PR~DUCTION OF Low-i.DLECLLAR W EI OLEFINS. Y. S. T d , A. G. Oblad and F. V.
m
liarson, Departrrwt of F u e l s Engineering, 320 W. C. Br-ng Building, U n i v e r s i t y
of Utah, Salt Lake City, Utah 84112.

The h y d r o g e n a t i o n of carbon monoxide f o r t h e p r o d u c t i o n o f low m o l e c u l a r w e i g h t (C -

C o l e f i n s has been i n v e s t i g a t e d o v e r unsupported iron-manganese c a t a l y s t s . A segies
Of f i f t e e n c a t a l y s t s o f d i f f e r e n t iron/manganese r a t i o were prepared and e v a l u a t e d .

The s c r e e n i n g t e s t s were conducted i n a f i x e d - b e d , bench-scale r e a c t o r . The s t a n d a r d

c a t a l y s t e v a l u a t i o n co d i t i o n s were 473-523 K, 500 p s i g , 2/1 H /CO r a t i o and a gas h o u r l y
space v e l o c i t y 1.08 cmgg-ls-l. The most p r o m i s i n g c a t a l y s t wi?h r e g a r d t o t h e C2-C4
hydrocarbon y i e l d was composed o f 2 . 2 p a r t s o f manganese p e r 100 p a r t s o f i r o n .

Four o f t h e c a t a l y s t s , Mn/Fe=2.2, Mn/Fe=8.4, Mn/Fe=63 and Mn/Fe=278 were s e l e c t e d

f o r an extended process v a r i a b l e i n v e s t i g a t i o n . The o l e f i n y i e l d i n c r e a s e d w i t h i n -
c r e a s i n g r e a c t i o n temperatures, w i t h decreasing space v e l o c i t y and w i t h d e c r e a s i n g H2/C0
r a t i o . The dependence o f t h e o l e f i n y i e l d on r e a c t o r p r e s s u r e r e p o r t e d i n t h e l i t e r a t u r e
was n o t observed i n t h i s i n v e s t i g a t i o n . The a c t i v a t i o n energy i n t h e temperature r a n g e
473-523 K was 20-30 k c a l mol-1.

127
 A MODEL FOR THE ISOTHERMAL PLASTOMETRIC BEHAVIOR OF COALS

W i l l i a m G. L l o y d , Henry E. F r a n c i s , Morgan R. Yewell, Jr.

I n s t i t u t e f o r Mining and M i n e r a l s R e s e a r c h , U n i v e r s i t y of Kentucky,

P. 0. Box 13015, L e x i n g t o n , KY 40583

Raymond 0. Kushida and Vega D. Sankur

J e t P r o p u l s i o n L a b o r a t o r y , C a l i f o r n i a I n s t i t u t e of Technology
P a s a d e n a , CA 91103

Introduction

The p l a s t i c i t y of b i t u m i n o u s c o a l s i n t h e r a n g e 350-5OO0C i s of c r i t i c a l
i m p o r t a n c e i n thermomechanical f l u i d i z a t i o n s u c h a s i s r e q u i r e d f o r c o a l pump-
i n g by h e a t e d s c r e w s (1-3) and i n h y d r o g e n o l y s i s i n t h e a b s e n c e of added s o l v e n t
(4,s). The f a c t t h a t t h e optimum r e a c t i o n t e m p e r a t u r e s f o r t h r e e major c u r r e n t
l i q u e f a c t i o n t e c h n o l o g i e s a r e n e a r l y i d e n t i c a l ( 6 ) and a r e c l o s e t o t h e f l u i d i t y
maxima f o r many p l a s t i c c o a l s s u g g e s t s t h a t t h e p r o c e s s e s comprising c o a l "melt-
i n g " are c r i t i c a l l y i m p o r t a n t t o h y d r o l i q u e f a c t i o n . More g e n e r a l l y , c o a l p l a s -
t i c i t y i s o b v i o u s l y i n v o l v e d i n c a k i n g problems (7-10).

The most w i d e l y u s e d method of measuring c o a l p l a s t i c i t y w a s developed by

G i e s e l e r (11). With m i n o r m o d i f i c a t i o n s t h i s r e m a i n s a s t a n d a r d p r o c e d u r e ( 1 2 ) ;
i t s r e l a t i o n s h i p t o o t h e r measurements h a s been d i s c u s s e d e l s e w h e r e ( 1 3 ) . T h i s
method measures t h e r e s i s t a n c e of a mass of well-packed p u l v e r i z e d c o a l t o t h e
r o t a t i o n o f a rabble-arm s t i r r e r which i s d r i v e n t h r o u g h a c o n s t a n t - t o r q u e c l u t c h .
A t low t e m p e r a t u r e s t h e s o l i d mass c o m p l e t e l y i m m o b i l i z e s t h e s t i r r e r s h a f t . In
t h e s t a n d a r d G i e s e l e r p r o c e d u r e t h e c o a l i s h e a t e d a t a uniform r a t e of 3"C/min.
A s the coal begins t o s o f t e n -- t y p i c a l l y a t a b o u t 390'C -- t h e s t i r r e r s h a f t
commences t o t u r n s l o w l y . A s t e m p e r a t u r e i n c r e a s e s t h e c o a l becomes more f l u i d
and t h e s h a f t t u r n s more r a p i d l y , e v e n t u a l l y a c h i e v i n g a maximum r a t e . The c o a l
m e l t -- a c t u a l l y a h e t e r o g e n e o u s m i x t u r e of s o l i d s , m o l t e n p h a s e and gaseous
p y r o l y z a t e -- t h e n u n d e r g o e s a t h i c k e n i n g o r "coking"; t h e s t i r r e r s h a f t t u r n s
p r o g r e s s i v e l y more s l o w l y , and e v e n t u a l l y s t o p s . Gieseler d a t a a r e r e c o r d e d i n
u n i t s of d i a l d i v i s i o n s per min (ddpm), where 100 ddpm = 1 s h a f t r o t a t i o n p e r min.
For t h r e e b i t u m i n o u s c o a l s of v a r y i n g p l a s t i c i t y t h e s t a n d a r d G i e s e l e r d a t a a r e
shown i n Table 1.

The I s o t h e r m a l bfodel

It i s o f t e n u s e f u l t o s t u d y phenomena under i s o t h e r m a l c o n d i t i o n s . Gieseler

p l a s t o m e t r y l e n d s i t s e l f t o such s t u d i e s , s i n c e sample warmup t i m e i n t h e s t a n d a r d
c r u c i b l e (2-3 min.) i s s h o r t i n comparison w i t h t h e u s u a l m e l t i n g / c o k i n g time
s c a l e (20-120 min.). I s o t h e r m a l G i e s e l e r p l a s t o m e t r y h a s been e x p l o r e d by F i t z -
g e r a l d (14,15) and by Van K r e v e l e n and coworkers ( 1 6 , 1 7 ) . A p l o t of log(ddpm)
a g a i n s t time shows a l o n g l i n e a r coking r e g i o n ( 1 4 , 1 5 ) .

F i g u r e 1 (open c i r c l e s ) shows t h e i s o t h e r m a l p l a s t o m e t r i c c u r v e s a t 410-2°C

o b t a i n e d with t h e t h r e e c o a l s d e s c r i b e d i n T a b l e 1. Both t h e maximum f l u i d i t i e s
128
and t h e p e r i o d s of f l u i d i t y are s e e n t o v a r y s u b s t a n t i a l l y among t h e s e c o a l s .

The l i n e a r i t y of t h e coking s l o p e s h a s been i n t e r p r e t e d t o imply a sequence

o f f i r s t - o r d e r r e a c t i o n s (14-17):

c + 11 k (i n i t ) ( f i r s t - o r d e r melting) (1)
M + S k(coke) ( f i r s t - o r d e r coking) (2)

where C, M and S r e p r e s e n t t h e m e l t a b l e p o r t i o n of t h e o r i g i n a l c o a l , t h e f r a c -
t i o n which i s molten ( m e t a p l a s t ) , and t h e f r a c t i o n which i s r e s o l i d i f i e d (coked).
T h i s scheme g i v e s rise t o t h e r a t e l a w :

d[Ml/dt = ki[C] - kc[M] (3)

There are two problems w i t h t h i s scheme. F i r s t , i t does n o t g e n e r a t e model

c u r v e s which resemble observed c u r v e s . S p e c i f i c a l l y , i t p r e d i c t s t h e r a t e of
i n c r e a s e of f l u i d i t y during t h e s o f t e n i n g process t o d e c e l e r a t e progressively,
w h i l e i n f a c t t h i s i n c r e a s e i s e x p o n e n t i a l w i t h time over most of t h e m e l t i n g
period. Second, t h i s scheme s p e c i f i c a l l y assumes t h a t Gieseler f l u i d i t y i s a
l i n e a r measure o f t h e molten f r a c t i o n o r m e t a p l a s t ; b u t t h a t assumption i s m i s -
t a k e n , as w e w i l l show.

For t h e purpose of more c l o s e l y modeling t h e a c t u a l i s o t h e r m a l c u r v e s we

propose a second m e l t i n g p r o c e s s , such t h a t t h e r a t e of i n c r e a s e of f l u i d i t y i s
dependent upon t h e c o n c e n t r a t i o n s o f b o t h m e t a p l a s t and unmelted f r a c t i o n :

C + M -+ 2 M k (me1t ) (4)

The r a t e l a w now a c q u i r e s a t h i r d term:

dF/dt = ki[C] + km[C][M] - kc[Ml (5)

(We use F f o r f l u i d i t y , r a t h e r t h a n [MI f o r m e t a p l a s t , on t h e l e f t - h a n d s i d e ) .

The v i r t u e of Equation 5 i s t h a t , f o r most i s o t h e r m a l r u n s , i t c a n p r o v i d e a
f a i r l y good f i t t o t h e e x p e r i m e n t a l d a t a , and t h e r e f o r e can d e f i n e t h e e x p e r i -
mental c u r v e s i n terms of n u m e r i c a l c o n s t a n t s a s s o c i a t e d w i t h t h e m e l t i n g and
coking p r o c e s s e s . The s o l i d p o i n t s i n F i g u r e 1 a r e v a l u e s g e n e r a t e d b y t h e Equa-
t i o n 5 model, u s i n g t h e v a l u e s g i v e n i n T a b l e 2. It is a c h a r a c t e r i s t i c o f t h i s
model t h a t t h e e x p e r i m e n t a l p o i n t s i n t h e v i c i n i t y of maximum f l u i d i t y t e n d t o
b e h i g h e r t h a n t h o s e g e n e r a t e d by t h e model. T h i s may r e f l e c t f o r m a t i o n o f g a s
b u b b l e s , which l e a d t o anomalously h i g h e x p e r i m e n t a l r e a d i n g s .

In a p p l y i n g t h i s model, t h e l e a s t - s q u a r e s m e l t i n g and coking s l o p e s are

c a l c u l a t e d from t h e e x p e r i m e n t a l d a t a ; w e use a l l d a t a between 1 ddpm and one
f o u r t h t h e maximum observed f l u i d i t y . The e x t r a p o l a t e d maximum f l u i d i t y (emf)
and t h e t i m e of maximum f l u i d i t y a r e t a k e n from t h e i n t e r s e c t i o n o f t h e s e s l o p e s .

From t h e s e d e t e r m i n a t i o n s , approximate v a l u e s f o r t h e m o d e l c o n s t a n t s can

b e e s t i m a t e d e m p i r i c a l l y from t h e c u b i c e q u a t i o n s :

129
 -m(melt)
= -0.3179 + .71507 x R - .15991 x R2 + .012348 x R3
k (me1t )

-m(coke)
= -0.6934 + 1.1504 x R - .26779 x R2 + .020826 x R3 (7)
k(coke)

P , n [ k ( i n i t ) ] = -16.127 + 2.8478 x P - .25098 x P2 + .005726 x P3 (8)

where m(me1t) and m(coke) d e n o t e t h e m e l t i n g and c o k i n g s l o p e s , R = m ( m e l t ) /

m(coke), and P = [ ( m ( m e l t ) + m(coke)) x t(max f l u ) ] . These e q u a t i o n s g i v e f a i r l y
good f i t s when k(me1t) is i n t h e r a n g e 0.5 t o 4 min.-l and kccoke) is i n t h e range
0.2 to 1.5 min.-l. T o r e l a t e t h e c o n c e p t u a l molten f r a c t i o n [MI t o t h e o b s e r v e d
ddpm, t h e emf from a model c u r v e i s compared w i t h t h a t from t h e e x p e r i m e n t a l curve.
F o r example, Ohio 1/9 seam c o a l a t 411a h a s an e x p e r i m e n t a l emf of 81.3 ddpm, and
a c a l c u l a t e d emf ( u s i n g t h e k v a l u e s of T a b l e 2 ) of [MI = 0.683. When each datum
i n t h e model c u r v e i s m u l t i p l i e d by t h e f a c t o r 81.3/0.683, t h e model f l u i d i t i e s
a r e c o n v e r t e d t o u n i t s of ddpm. [ D e t a i l e d p r o c e d u r e s and programs f o r t h e s e
e s t i m a t e s a r e a v a i l a b l e from t h e a u t h o r s . ]

E f f e c t of Temperature

I s o t h e r m a l c u r v e s w e r e o b t a i n e d upon Kentucky 811 seam c o a l a t f i v e a d d i -

t i o n a l t e m p e r a t u r e s , i n t h e r a n g e 400-460°C. Values of t h e model c o n s t a n t s a r e
g i v e n i n T a b l e 3. An A r r h e n i u s p l o t of t h e model c o n s t a n t s k(me1t) and k ( c o k e )
is shown i n F i g u r e 2. F o r t h i s c o a l t h e v a l u e of t h e a p p a r e n t E, f o r k(me1t)
( b e s t 5 of 6 d a t a ) i s 173 f 13 k J ; t h a t f o r kccoke) ( a l s o b e s t 5 of 6 ) is 228 t.
6 kJ. V i s c o s i t i e s commonly show an analogous " a c t i v a t i o n e n e r g y of v i s c o s i t y "
(18,191. The a p p a r e n t Ea of maximum f l u i d i t y i s a p p r o x i m a t e l y 600 k J , h i g h when
compared w i t h t h o s e f o r a s p h a l t (120-150 k J ) and g l a s s (390-400 k J ) (20,211.

When t h e t e m p e r a t u r e d e p e n d e n c i e s f o r t h e p a r a m e t e r s of t h i s model have been

e s t i m a t e d from t h e d a t a o f Table 3, i s o t h e r m a l c u r v e s may b e c a l c u l a t e d f o r any
i n t e r p o l a t e d t e m p e r a t u r e , o r f o r any e x t r a p o l a t e d t e m p e r a t u r e c l o s e t o t h e r a n g e
of e x p e r i m e n t a l d a t a . F i g u r e 3 shows a f a m i l y of f l u i d i t y e n v e l o p e s f o r t h e
Kentucky 811 seam c o a l , b a s e d upon d a t a c a l c u l a t e d f o r t h e r a n g e 392-468'C. Each
c u r v e i s an " i s o f l u i d i t y " e n v e l o p e , open a t t h e t o p . F i g u r e 3 i s r e a d a l o n g h o r i -
z o n t a l ( i s o t h e r m a l ) l i n e s . A t 430" t h i s c o a l e x h i b i t s a p l a s t i c p e r i o d ( f l u i d i t y
g r e a t e r t h a n 1 ddpm) from 2 t o 30 min., and h a s a f l u i d i t y e x c e e d i n g 100 ddpm from
5 t o 20 min. T h i s p r o j e c t i o n , which w i l l a f f o r d markedly d i f f e r e n t e n v e l o p e s f o r
d i f f e r e n t c o a l s , may f i n d use i n a p p l i c a t i o n s i n which t h e p l a s t i c p r o p e r t i e s of
b i t u m i n o u s c o a l s are i m p o r t a n t .

Discussion

The o r g a n i c s t r u c t u r e s of c o a l s a r e numerous and v a r i e d . Bonds which t h e r m a l l y

c l e a v e a t u s e f u l r a t e s a t 390-400°C ( d i s s o c i a t i o n e n e r g i e s o f 210-230 k J ) a r e n o t
t h e same a s t h o s e c l e a v e d a t 460" (240-260 k J ) . A m a j o r r e a s o n f o r i s o t h e r m a l
measurements i s t o c o n t r o l t h i s v a r i a b l e .

G i e s e l e r f l u i d i t y c a n be r e l a t e d t o v i s c o s i t y u n i t s by c a l i b r a t i n g w i t h
s t a n d a r d f l u i d s . Measurements w i t h t h e p l a s t o m e t e r u s e d i n t h i s s t u d y and w i t h

130
a p p r o p r i a t e s t a n d a r d s (22) i n t h e range 500 - 10,000 p o i s e y i e l d a l i n e a r c a l i -
bration:

Iln(p0is.e) = 16.2789 - 0.96787 9.n (ddpm) (9)

w i t h a c o r r e l a t i o n c o e f f i c i e n t of .9997. A c t u a l c o a l m e l t s are heterogeneous

(7,161, p s e u d o p l a s t i c ( 2 3 ) , and v i s c o e l a s t i c i n t h e i r l a t e r coking s t a g e s ( 2 4 ) .
I t i s n e v e r t h e l e s s u s e f u l t o i n t e r p r e t G i e s e l e r f l u i d i t i e s a s e s t i m a t e s of t r u e
viscosities.

Nicodemo and N i c o l a i s ( 2 5 ) and Fedors ( 2 6 ) have shown t h e v i s c o s i t y of

Newtonian s u s p e n s i o n s of s o l i d s t o conform t o t h e e x p r e s s i o n :

where n , no, and 4 are t h e s u s p e n s i o n v i s c o s i t y , s o l v e n t v i s c o s i t y , and s o l i d s

f r a c t i o n . Data o b t a i n e d by Lee (27) show t h e l o g a r i t h m of t h e maximum f l u i d i t y
of c o a l b l e n d s t o v a r y l i n e a r l y w i t h composition. These o b s e r v a t i o n s a r e t e l l i n g
us t h e same t h i n g : t h a t t h e l o g a r i t h m o f f l u i d i t y , n o t f l u i d i t y i t s e l f , i s a
d i r e c t measure of t h e molten f r a c t i o n . I f w e assume t h a t a f l u i d i t y of 1 ddpm
corresponds t o t h e maximum s o l i d f r a c t i o n Omax, we can p r o j e c t t h e r e l a t i o n s h i p :

!Ln(F) = &n(F").[1 tJ
-- 1 (11)
'max

To use Equation 11 we need e s t i m a t e s o f tJmX and of t h e f l u i d i t y of p u r e

m e t a p l a s t , FO. The maximum s o l i d f r a c t i o n i n a random d i s p e r s i o n of monodisperse
s p h e r e s is 0.63 (28,29). T h i s f r a c t i o n is h i g h e r f o r p o l y d i s p e r s e s p h e r e s ( 3 0 )
and f o r some s i z e d i s t r i b u t i o n s may b e as h i g h as 0.9 (31). For c o a l m e l t s w e
w i l l assume a v a l u e of $max of 0.80. I f t h e e x t r a p o l a t e d maximum f l u i d i t y of t h e
P i t t s b u r g h 118 seam sample a t 412" (1.0 x lo6 ddpm) i s t a k e n as a rough e s t i m a t e
of F a , we can e s t i m a t e s o l i d f r a c t i o n s i n o t h e r c o a l s from f l u i d i t i e s a t t h i s
temperature. F l u i d i t i e s of 10, 100, 1,000 and 10,000 ddpm i n d i c a t e s o l i d f r a c -
t i o n s of approximately .67, .53, .40 and .27. The minimum v a l u e s of @ f o r Ohio 119
and Kentucky 1\11 samples i n Table 2 are approximately 0.55 and 0.41.

The l i n e a r i t y of l o g ( F ) w i t h @ h a s m e c h a n i s t i c i m p l i c a t i o n s as w e l l . The
left-hand of Equation 3 i s more a c c u r a t e l y e x p r e s s e d as d Rn[M]/dt. The c u r v e s
of F i g u r e 1 show l i n e a r i n c r e a s e s of m e t a p l a s t w i t h t i m e i n t h e e a r l y s t a g e s ,
and l i n e a r d e c r e a s e s o f m e t a p l a s t w i t h t i m e ( z e r o t l t o r d e r k i n e t i c s ) i n t h e l a t e r
coking s t a g e s .

E x t r u s i o n pumping of c o a l s i n t h e p l a s t i c s t a t e e n t a i l s s u b s t a n t i a l l y
i s o t h e r m a l o p e r a t i o n s f o r r e s i d e n c e times o f a few minutes i n t h e screw (1-3).
S e v e r a l c o a l s , i n c l u d i n g t h o s e of t h e p r e s e n t s t u d y , have been e x t r u d e d w i t h no
d i f f i c u l t y i n JPL's 1.5-in. c o a l pump. Two c o a l s which showed v e r y l i t t l e p l a s -
t i c i t y ( l e s s t h a n 2 ddpm) were n o t e x t r u d a b l e ( 3 ) . The i s o t h e r m a l p l a s t o m e t r y
p r o f i l e s may prove t o b e a u s e f u l t o o l i n p r e d i c t i n g b e h a v i o r i n c o a l pumps.
Recent e v i d e n c e of t h e s u b s t a n t i a l e f f e c t of p r e s s u r e upon observed p l a s t i c i t y
(10) i n d i c a t e s t h a t t h i s v a r i a b l e should be c o n s i d e r e d i n f u t u r e work.

131
Acknowledgments

C h r i s t o p h e r England ( J e t P r o p u l s i o n L a b o r a t o r y ) f i r s t s u g g e s t e d t h i s
s t u d y . This work was performed f o r t h e c o a l pump development p r o j e c t , J e t
P r o p u l s i o n Laboratory, C a l i f o r n i a I n s t i t u t e of Technology, under C o n t r a c t no.
954920. The c o a l pump p r o j e c t is s u p p o r t e d by t h e Department of Energy through
a n agreement w i t h t h e N a t i o n a l A e r o n a u t i c s and Space A d m i n i s t r a t i o n .

References

P. R. Ryason and C. England, F u e l , 57, 241 (1978).

V. Kevorkian and F. J. Cumings, U. S. P a t e n t 4,106,997 (1978).

W. J. Schatz, E. G. C a r p e n t e r , C. S. Daksla, C. England, S. P. F e i n s t e i n ,

R. 0. Kushida, D. W. Lewis, W. G. Lloyd and V. D. Sankur, "Coal Pump
Development -
Phase I F e a s i b i l i t y Report", JPL 5030-235, J e t P r o p u l s i o n
Laboratory, C a l i f o r n i a I n s t i t u t e of Technology, Pasadena, September 1978.

H. E. Mehesch, E r d o e l , Kohle, Erdgas, Petrochem., I,

323 (1978).

Y. S a t o , K. lmuta and T. Yamakawa, F u e l , 58, 322 (1979).

B. Gates, Chemtech, 1979, 97.

D. W. Van Krevelen, "Coal", E l s e v i e r P u b l i s h i n g Co., Amsterdam, 1961,
pp 263ff.

R. Loison, A. P e y t a v y , A. F. Boyer and R. G r i l l o t , i n H. H. Lowry, e d . ,

"Chemistry o f Coal U t i l i z a t i o n " , supplementary v o l . , John Wiley & Sons,
New York, 1963, pp 1 7 7 f f .

S. V. Sobolev and E. M. T a i t s , Khim P e r e r a b . Topl., 2, 68 (1974).

M. Kaiho and Y. Toda, F u e l , 58, 397 (1979).

K. G i e s e l e r , Gluckauf, 2, 1 7 8 (1934).

ASTM Method D 2639-74, Amer. SOC. f o r T e s t i n g and M a t e r i a l s , P h i l a d e l p h i a ,

PA, 1974.

R. Loison, e t a l . , r e f . ( 8 ) , pp 152-69.

D. F i t z g e r a l d , Trans. Faraday SOC., 52, 362 (1956).

D. F i t z g e r a l d , F u e l , 35, 178 (1956).

D. W. Van Krevelen, F. J. Huntjens and H. N. M. Dormans, M.,462 (1956).

H. A . G. Chermin and D. W. Van Krevelen, g.,

2,85 (1957).

132
 E. N. da C. Andrade, Nature, 125, 309 (1930); E. N. d a C. Andrade,
" V i s c o s i t y and P l a s t i c i t y " , Chemical P u b l i s h i n g Co., I n c . , New York,
NY, 1951.

(19) S. G l a s s t o n e , K. J. L a i d l e r and H. E y r i n g , "The Theory of Rate P r o c e s s e s " ,

McGraw-Hill Book Co., I n c . , New York, 1941, pp 480ff.

P. B. Macedo and A. N a p o l i t a n o , J. Chem. Phys., 2, 1887 (1968).

H. E. Schweyer and R. W. Lodge, Ind. Eng. Chem., Prod. R e s . Develop.,

-
13, 202 (1974).

Cannon Instrument Co., S t a t e C o l l e g e , PA 16801.

P. L. Waters, F u e l , 3, 3 (1962).

D. Fitzgerald, H.,
36, 389 (1957).

L. Nicodemo and L. N i c o l a i s , Polymer, 15,589 (1974).

R. F. Fedors, E.,
16,305 (1975).

H. C. Lee ( K a i s e r S t e e l Corp.), p r i v a t e communication.

6 . D. S c o t t , Nature, 188,908 (1960).

R. F. Fedors, J. C o l l o i d I n t e r f a c e Sci., 46, 545 (1974).

R. F. Fedors, Polymer, 0,
225 (1979).

S. F e i n s t e i n ( J e t P r o p u l s i o n L a b o r a t o r y ) , p r i v a t e communication.

133
 Table 1

P r o p e r t i e s of T h r e e B i t u m i n o u s Coals

Seam Ohio 89 Kentucky 111 P i t t s b u r g h 88

source Noble Co. W e b s t e r Co. (from M E T C )
Proximate:
moisture 2.15% 1.97% 0.79%
ash 18.87 8.34 8.65
vol. matter 39.40 41.19 40.85
fixed carbon 39.58 48.50 49.71
Ultimate:'
carbon 79.41 82.21 84.83
hydrogen 5.30 5.43 5.49
nitrogen 1.13 1.36 1.44
sulfur 5.38 3.52 2.92
oxygen 8.78 7.48 5.33
Heating value' 14,010 B t u / l b 14,770 B t u / l b 15,290 B t u / l b
Free swelling index 3 7 7%
Petrographic analysis'
exinoids 2.1% 5.1% 4.0%
vitrinoids 70.1 76.3 75.3
other reactives 1.9 1.2 0.9
i n e r t macerals 12.9 11.0 13.7
ASTM G i e s e l e r p l a s t o m e t r y
softening T 398°C 392'C 372°C
coking T 462" 474O 485"
max f l u T 435" 435O (414-459")
max f l u i d i t y 114 ddpm 6240 ddpm >>25000 ddpm
________--__________-_--_-_---------_
As r e c e i v e d . Moisture- and a s h - f r e e b a s i s . By d i f f e r e n c e .

134
 I0 5 I I I I I I

..

I o4
0
8.
0.0
.O

'8
'0
'0
? * c
8

IO

Time, m i n u t e s
F i o u r e 1. I s o t h e r m a l n l a s t o m e t r i c c u r v e s of t h r e e b i t u m i n o u s c o a l s .
A - Ohio F9 seam (Noble Co.) a t 411OC. B - Kentucky b l l seam ( I l e b s t e r Co.)
a t 410°C. -
C P i t t s b u r K h h3 S e a n ( f r o m ::ETC) a t 412°C. 07en c i r c l e s a r e
e x p e r i m e n t a l d a t a ; s o l i d n o i n t s are c a l c u l a t e d by t h e t h r e e - T a r a m e t e r model
( v a l u e s g i v e n i n T a b l e 2).
1 ;5

Figure 1
 Table 2
C h a r a c t e r i s t i c s of Three I s o t h s r m a l P l a s t i c Curves a t 410-412°C
Ohio #9 K e n t u c k y #11 Pittsburgh #8
411°C 410°C 412’C
Melting slope 0.425 0.621 1.084
Coking s l o p e -0.216 -0.151 -0.125
Maximum f l u i d i t y ,
6
ddpm’ 81 896 1.0 x 10
T i m e o f maximum
fluidity ’ 14.34 15.42 15.75
Calculated values :
‘k ( i n i t ) 6.0 4.3 3.4 x
k(me1t) 0.77 0.79 1.24
k (coke) 0.35 0.16 0.125

’ By e x t r a p o l a t i o n o f m e l t i n g a n d c o k i n g s l o p e s .
Using t h e t h r e e - p a r a m e t e r model d e s c r i b e d i n t e x t . Dimensions of
k ( i n i t ) and k ( c o k e ) a r e m i n - l ; k ( m e 1 t ) i s m i n - l mass f r a c t i o n - I .

Table 3
E f f e c t of T e m p e r a t u r e upon the I s o t h e r m a l P l a s t i c C u r v e s o f K e n t u c k y
811 Seam C o a l (40O-46O0C)

Temperature,’C -
400. 410. 425.5 440. 449.9 460.
Melting slope 0.172 0.621 1.35 1.60 2.57 5.3
Coking s l o p e -0.069 -0.151 -0.325 -0.679 -1.11 -1.56
Maximum f l u i d i t y ,
ddpm’ 44 896 2.58E4 3.34E4 8.89E4 2.21E6
T i m e o f maximum
fluidity’, min. 25.82 15.42 11.14 8.12 6.30 4.13
Calculated values : *
k(init) 1.2E-3 4.33-5 1.9E-6 3.OE-6 6.5E-7 4.3E-7
k(me1t) 0.26 0.79 1.74 2.49 4.05 7.1
k(coke) 0.083 0.158 0.339 0.848 1.40 1.66

’ By e x t r a p o l a t i o n of m e l t i n g a n d c o k i n g s l o p e s .
* S e e T a b l e 2 , f o o t n o t e 2.

136
 5

2
h
m

2
e
'
.6
505
I4
VI
v

02

01

05
I36 I40 I44 I48
IO~/OK
F i n u r e 2. A r r h e n i u s d e q e n d e n c y o f t h e model c o n s t a n t s k ( n e 1 t )
( c i r c l e s ) and k ( c o k e ) ( d i a m o n d s ) f o r Kentucky 811 seam coal

b\
480

460
u

440
a
U
m

E' 420
a,

k C
D E
400
I I I I I
0 IO 20 30 40 50 60 70
Time, m i n u t e s \
F i g u r e 3. I s o t h e r m a l f l u i d i t y e n v e l o n e s f o r Kentucky #ll seam c o a l
A - - -
l o 4 ddpm. B lo3 ddpm. C 10' ddqm. D 1 0 dd?n. E 1 d d y - -
137
PITCH RESIDUES FKON UPGRADING OF BITUMEN ANI) HEAVY OILS AS ADDITIVES I N COKEMAKIWG:
INFLUENCE OF PITCH PROPERTIES

K . B e l i n k o , L.A. C i a v a g l i a , B.N. Nandi a n d J . M . Denis,

Energy Research L a b o r a t o r i e s
Canada Centre f o r M i n e r a l and Energy Technology,
Department of Energy, Mines and P e s o u r c e s ,
c / o 555 Booth S t r e e t , Ottawa, O n t a r i o K 1 A O G 1

INTRODUCTION

Impending s h o r t a g e s of good c o k i n g c o a l s t h r o u g h o u t t h e world h a v e

prompted a s e r i e s o f i n v e s t i g a t i o n s a t CANMET (Canada C e n t r e f o r M i n e r a l a n d Energy
Technology) i n t o t h e u t i l i z a t i o n o f w e s t e r n Canadian m a r g i n a l c o k i n g c o a l s i n t h e
p r o d u c t i o n of m e t a l l u r g i c a l g r a d e c o k e . One p o s s i b l e way t o do t h i s i s t o add
r e s i J u a l p i t c h from thermal h y d r o c r a r k i n g of b i t u m e n and heavy o i l s t o s u c h c o a l s
( 1 ) . T h i s p i t c h h a s been found t o b e an e x c e l l e n t a d d i t i v e f o r u p - g r a d i n g low
f l u i d , low v o l a t i l e , i n e r t - m a c e r a l r i c h c o a l s . The p i t c h a c t s a s a f l u i d i t y -
e n h a n c i n g a g e n t , and by i n t e r a c t i n g w i t h t h e v i t r i n i t e o f t h e c o a l , augments t h e
s u p p l y o f r e a c t i v e c a r b o n n e c e s s a r y f o r b o n d i n g t o g e t h e r of i n e r t m a c e r a l s .

The p u r p o s e of t h i s p u b l i c a t i o n is t o a d d f u r t h e r i n s i g h t i n t o t h e r o l e
of p i t c h i n c a r b o n i z a t i o n o f c o a l / p i t c h b l e n d s . P i t c h e s d e r i v e d from t h e r m a l
h y d r o c r a c k i n g o f bitumen a t d i f f e r e n t d e g r e e s of s e v e r i t i e s were u t i l i z e d f o r t h i s
p u r p o s e . T h i s p r o v i d e d a means o f a s s r s s i n g t h e p r o p e r t i e s of t h e p i t c h e s i n t h e
carbonization process without changing the basic chemical nature of the parent
material.

EXPERIMENTAL

The p r o p e r t i e s o f t h e p i t c h e s d e r i v e d from t h e r m a l h y d r o c r a c k i n g o f
A t h a b a s c a bitumen u n d e r v a r i o u s o p e r a t i n g c o n d i t i o n s a r e g i v e n i n T a b l e 1. These
four p i t c h e s were p r o d u c e d u n d e r d i f f e r e n t d e g r e e s of s e v e r i t y d u r i n g t h e p r o c e s s
A b e i n g c h a r a c t e r i s t i c of p i t c h o b t a i n e d under r e l a t i v e l y mild c o n d i t i o n s and D,
o f p i t c h o b t a i n e d a t h i g h s e v e r i t i e s . A r r l a t i o n was found t o e x i s t betwcen t h e
d e g r e e o f s e v e r i t y d u r i n g h y d r o c r a c k i n g and t h e v a r i o u s p r o p e r t i e s l i s t e d i n
T a h l e 1 ( e . g . CCR, a r o m a t i c i t y , s o f t e n i n g p o i n t ) .

TABLE 1

P h y s i c a l and Chemical P r o p e r t i e s o f P i t c h e s

- tch ___
-
A -
B C -
D
Vola t i l e matter % 73.1 64.8 53.5 44.6
Ash % 1.8 2.3 3.2 5.8
Softening temperature OC 50 95 105 135
Conradson c a r b o n r e s i d u e % 34.7 42.2 50.7 64.6
Specific gravity 1.10 1.12 1.16 1.24
Benzene-insolubles* 2.6 4.2 11.6 20.6
Asphaltenes % 37.2 44.6 48.1 55.2
H/C 1.32 1.15 1.09 0.94
Sulphur % 5.58 5.6: 6.33 4.85
Aromaticity** % 38.2 49.4 56.3 69.8
-- -_
* Ash-free b a s i s , ** 1%NMR a n a l y s i s
138
 The c o a l u s e d was a w e s t e r n C a n a d i a n , low f l u i d , h i g h r a n k b i t u m i n o u s
c o a l having a r e l a t i v e l y high c o n c e n t r a t i o n o f i n e r t macerals. Proximate, u l t i m a t e
a n d P e t r o g r a p h i c a n a l y s e s of t h i s c o a l a r e g i v e n i n T a b l e 2 .

TABLE 2

P r o p e r t i e s o f t h e Coal

Proximate Analysis (dry basis)

Ash % 9.8
Volatile matter % 21.2
F i x e d Carbon % 69.0
Ultimate Analysis
Carbon % 78.9
Hydrogen % 4.3
Sulphur % 0.8
Nitrogen % 1.3
Oxygen (by d i f f . ) % 4.9
Ash % 9.8
Petrographic Analysis
V it r i n i t e vol. % 51.8
Semi-f u s i n i t e vol. % 34.2
F u s i n i te vol. % 11.2
Micrini t e vol. % 2.6
Exinite vol. % 0.2

Mean r e f l e c t a n c e i n o i l , 1.17
RO

C o a l f p i t c h b l e n d s w i t h v a r y i n g p i t c h c o n c e n t r a t i o n s were p r e p a r e d and
t h e i r f l u i d i t i e s d e t e r m i n e d by means of a G i e s e l e r p l a s t o m e t e r . The f l u i d i t i e s of
t h e v a r i o u s blends a r e r e p o r t e d i n Table 3. A v a l u e r e p r e s e n t i n g t h e c o n c e n t r a t i o n
of p i t c h which c a n p o t e n t i a l l y i n t e r a c t w i t h t h e c o a l d u r i n g c a r b o n i z a t i o n , Cp, i s
a l s o g i v e n i n T a b l e 3. Cp was c a l c u l a t e d on t h e f o l l o w i n g b a s i s :

where CCR i s t h e Conradson c a r b o n r e s i d u e (2) a n d a p p r o x i m a t e s t h e c o n t r i b u t i o n of

c a r b o n a c e o u s m a t e r i a l made by t h e p i t c h t o t h e b l e n d d u r i n g c a r b o n i z a t i o n .

The v a r i o u s c o a l l p i t c h b l e n d s w e r e c a r b o n i z e d u s i n g a c a n i s t e r c o k i n g
t e c h n i q u d e v e l o p e d a t CANMET ( 3 ) . The b l e n d s were p a c k e d t o a b u l k d e n s i t y o f
5 .
8 0 1 kg/m i n t o p e r f o r a t e d t i n p l a t e c a n i s t e r s 2 9 . 3 cm l o n g and 1 . 6 cm i n d i a m e t e r .
Twenty c a n s , e a c h c o n t a i n i n g a d i f f e r e n t b l e n d were s i d e - c h a r g e d i n t o CANMET'S
250-kg moveable w a l l c o k e o v e n .

The r e l a t i v e s t r e n g t h s of t h e c o k e s p r o d u c e d f r o m t h e c a n i s t e r t e s t were
d e t e r m i n e d by a small s a m p l e t u m b l e r t e s t d e v e l o p e d by B i t u m i n o u s Coal R e s e a r c h
(BCR) ( 4 ) and a r e r e p o r t e d i n T a b l e 3 . T h e s e s t r e n g t h i n d i c e s are a m e a s u r e o f
s i z e r e d u c t i o n i n tumbled c o k e p a r t i c l e s and t h e r e f o r e a large index corresponds
t o a weak c o k e .

O p t i c a l e x a m i n a t i o n s of t h e v a r i o u s c o k e s w e r e made w i t h a L e i t z r e f l e c -
t e d l i g h t m i c r o s c o p e u s i n g an o i l immersion l e n s . The m i c r o g r a p h s w e r e t a k e n a t
6OOX m a g n i f i c a t i o n u s i n g p a r t i a l l y c r o s s e d n i c o l s .
139
 TABLE 3

C a r b o n i z a t i o n D a t a f o r Coal P i t c h B l e n d s

__ __ __
-
0
__
__
Conc trat:
5 8
~
itch
__
10
__
n Blend w t %
'x-pi-
Pitch A
contribution o f carbon % N i l 1.5 2.4 3.1
f r o m p i t c h . Cp
F l u i d i t y of b l e n d ddlmin N i l 1.9 6.1 6.4
BCR* s t r e n g t h i n d e x N/A** 49.0 36.4 38.2
Pitch B
Contribution of carhon % Ni1 2.1 3.3 4.1
from p i t c h , Cp
F l u i d i t y of blend ddlmin Ni1 1.5 5.7 7.1
BCR* s t r e n g t h i n d e x N/A** 53.8 35.3 34.5
Pitch C
Contribution of carbon
from p i t c h , C
% Nil 2.6 4.1 5.0 7.1 I 8.2

F l u i d i t y of blegd ddlmin Ni1 1.1 5.0 13.0 370 400

BCR* s t r e n g t h i n d e x N/A** 52.7 36.7 36.9 39.0 40.3
Pitch D
Contribution of carbon % N i l 3.3 5.2 6.5 9.1 10.4
f r o m p i t c h , Cp
F l u i d i t y of b l e n d ddlmin N i l 1.0 4 .o 6.8
BCR* s t r e n g t h i n d e x MIA** 57.8 53.1 35.1

* B i t u m i n o u s C o a l K e s e a r r h I n c . , P i t t s b u r g h , P.A.
** A n o n - a g g l o m e r a t e d c h a r was p r o d u c e d

RESULTS AND DISCUSSION

A photograph showing t w o r e p r e s e n t a t i v e cokes from t h e c a n i s t e r t e s t is

shown i n F i g . 1. The c o k e shown a t t h e t o p was p r o d u c e d f r o m c o a l w i t h n o p i t c h
a d d i t i v e a n d was p o o r l y a g g l o m e r a t e d . The c o k e a t t h e b o t t o m was a g g l o m e r a t e d and
h a r d a n d was t y p i c a l o f c o k e s produced f r o m c o a l l p i t c h b l e n d s . The f o r m e r c o k e
c o u l d n o t b e e v a l u a t e d by t h e BCR t u m b l e r t e s t b e c a u s e of i t s n o n - a g g l o m e r a t e d
c h a r a c t e r . The s t r e n g t h i n d i c e s of t h e c o k e s p r o d u c e d from c o a l l p i t c h b l e n d s a r e
given i n Tahle 3 .

The s t r e n g t h s o f t h e c o k e s p r o d u c e d from b l e n d s c o n t a i n i n g p i t c h A a n d
p i t c h B were n o t f o u n d t o v a r y s i g n i f i c a n t l y f o r p i t c h c o n c e n t r a t i o n s a b o v e 5 % . On
t h e o t h e r h a n d . a d d i t i o n s of more t h a n 10% p i t r h i n r o a l l p i t r h C a n d c o a l l p i t c h I)
b l e n d s were f o u n d t o b e d e t r i m e n t a l t o c o k e s t r c n g t h . Thr i n f l u e n c e o f ? i t c t l
c o n c e n t r a t i o n on c o k e s t r e n g t h was t h e r e f o r e more p r o n o u n c e d f o r p i t c h o b t a i n e d
from h i g h s e v e r i t y t h e r m a l h y d r o c r a c k i n g r u n s . I t would h e d i f f i c u l t t o p r e d i c t
a n e x a c t optimum p i t c h c o n c e n t r a t i o n h a s c d s o l e l y o n t h e r e s u l t s r e p o r t e d i n
Table 4 f o r m a l l p i t c h D blends.

C n a l l p i t c h h l c n d s h a v i n g Cp v a l u p s i n e x c s s s o f a b o u t 7 % p r o d u c e d cokes
of p r o g r r s s i v e l y weaker s t r p n g r h s . The Conradson c a r h o n r e s i d u c ( C C R ) c o n t e n t s o f
p i t c h e s A a n d H w e r e s u f f i c i p n t l y l o w t o p e r m i t a d d i t i o n s o f up t o 1hX p i t c h t o t h e
C o a l w i t h o t i t C P valut2s o f t h e h l e n d e x c e d i n g 77,. T h i s Would a c c o u n t f o r t h e l a c k
o f a minimum i n IlCR s t r e n g t h i n d e x f n r c o k e s p r o d u c e d from b l e n d s c o n t a i n i n g p i t c h

140
A and p i t c h B w i t h i n t h e c o n c e n t r a t i o n r a n g e i n v e s t i g a t e d .

F l u i d i t y d a t a f o r t h e v a r i o u s b l e n d s a r e summarized i n T a b l e 3. A
mlrked i n c r e a s e i n t h e f l u i d i t y o f t h e b l e n d s w a s o b s e r v e d f o r p i t c h c o n c e n t r a t i o n s
g r e a t e r t h a n LO%. The i n c r e a s e i n f l u i d i t y w a s g e n e r a l l y f o u n d t o b e more p r o -
nounced f o r p i t c h o b t a i n e d f r o m h i g h s e v e r i t y t h e r m a l h y d r o c r a c k i n g r u n s . This
p e r h a p s s u g g e s t s t h a t t h e r e i s a b e t t e r i n t e r a c t i o n between p i t c h and t h e v i t r i n i t e
o f t h e c o a l i n c a s e s where t h e p i t c h was t r e a t e d u n d e r more s e v e r e c o n d i t i o n s
during thermal hydrocracking. I t is e v i d e n t f r o m T a b l e 1 t h a t p i t c h a r o m a t i c i t y
is d i r e c t l y r e l a t e d t o t h e d e g r e e of s e v e r i t y d u r i n g t h e r m a l h y d r o c r a c k i n g . The
i n t e r a c t i o n between t h e p i t c h and t h e v i t r i n i t e may t h e r e f o r e b e r e l a t e d t o t h e
a r o m a t i c i t y of t h e p i t c h :

Based on some of t h e a r g u m e n t s p r e s e n t e d a b o v e , t h e f o l l o w i n g r e l a t i o n -
s h i p was found t o b e c o n s i s t e n t w i t h t h e d a t a i n T a b l e 3:

0.97
BCR s t r e n g t h i n d e x = 26.47 + 1 . 7 5 Cp e x p *-A3,2F, 1.5 5 CP 5 1 0 . 4 2)

Where Cp i s d e f i n e d a c c o r d i n g t o E q u a t i o n l ) , A i s t h e a r o m a t i c i t y o f p i t c h d e t e r -
mined by l 3 C NMR and F i s t h e f l u i d i t y o f t h e c o a l / p i t c h b l e n d . E q u a t i o n 2) i s
p l o t t e d i n F i g . 2 and w a s f o u n d t o h a v e a c o e f f i c i e n t o f c o r r e l a t i o n o f 0.89.

A c c o r d i n g t o E q u a t i o n 2 ) , t h e BCR s t r e n g t h i n d e x of a coke p r o d u c e d from

a c o a l / p i t c h b l e n d i s n o t o n l y d e p e n d e n t on t h e v a l u e of Cp, b u t a l s o on t h e
f l u i d i t y of t h e b l e n d . Low v a l u e s o f Cp i n t h e b l e n d a p p e a r t o b e d e s i r a b l e i n
a c h i e v i n g good coke s t r e n g t h p r o v i d e d t h e f l u i d i t y o f t h e b l e n d i s s u f f i c i e n t l y
h i g h t o make t h e e x p o n e n t i a l term in t h e e q u a t i o n a p p r o a c h u n i t y . Once t h e expon-
e n t i a l t e r m h a s a p p r o a c h e d u n i t y , a d d i t i o n a l i n c r e a s e s i n Cp may o n l y c o n t r i b u t e t o
a d e t e r i o r a t i o n i n coke s t r e n g t h . The i n t e r - r e l a t i o n s h i p between Cp a n d f l u i d i t y
b o r n e o u t by E q u a t i o n 2) e m p h a s i z e s t h e n e e d f o r c o n t r o l l e d f l u i d i t y i n e n s u r i n g a
u n i f o r m and e f f i c i e n t d i s t r i b u t i o n o f t h e b i n d i n g material t h r o u g h o u t t h e c o a l
during carbonization. T h i s i s d e m o n s t r a t e d , f o r i n s t a n c e , i n t h e c a s e of 5%
a d d i t i o n o f p i t c h D t o t h e c o a l , T a b l e 3. Although t h e Cp v a l u e was r e l a t i v e l y
h i g h , low f l u i d i t y p r e v e n t e d p r o p e r d i s t r i b u t i o n of t h e b i n d i n g material in t h e
c o a l during carbonization; c o n s e q u e n t l y , a weak coke w a s p r o d u c e d .

I n o r d e r t o c o n f i r m t h i s dependence on f l u i d i t y , a series o f m i c r o s c o p i c
e x a m i n a t i o n s w a s made on t h e c o k e s p r o d u c e d from t h e c a n i s t e r t e s t . The c o k e pro-
duced from t h e c o a l w i t h no p i t c h a d d i t i v e was found t o b e p o o r l y bonded. Inert
m a c e r a l s were s e g r e g a t e d w i t h i n t h e c o k e s t r u c t u r e w i t h l i t t l e or no b i n d i n g
m a t e r i a l s u r r o u n d i n g them ( F i g . 3). C o a l / p i t c h b l e n d s p r o d u c e d c o k e s o f v a r y i n g
q u a l i t i e s d e p e n d i n g on v a l u e s of Cp and f l u i d i t y . T h r e e s p e c i f i c c a s e s w e r e chosen
t o d e m o n s t r a t e t h i s dependence: ( i ) c o a l + 5% p i t c h D, ( i i ) c o a l + 10%p i t c h D and
( i i i ) c o a l + 1 6 % p i t c h D.

In case ( i ) , coal + 5% p i t c h D, some d e g r e e of b o n d i n g was o b s e r v e d

between i n e r t m a c e r a l s , b u t t h e b o n d i n g was g e n e r a l l y d i s c o n t i n u o u s a n d s p o r a d i c .
T h i s i s e x e m p l i f i e d f o r i n s t a n c e i n F i g . 4 . It i s n o t e w o r t h y t h a t f o r b l e n d s
h a v i n g s i m i l a r Cp v a l u e s b u t h i g h e r f l u i d i t i e s , e . g . c o a l + 1 0 % p i t c h A, b o n d i n g
was found t o b e c o n s i d e r a b l y more u n i f o r m t h a n t h a t shown i n F i g . 4. The d i f f e r -
ence i n bonding can t h e r e f o r e b e a t t r i b u t e d t o t h e f l u i d i t y of t h e r e s p e c t i v e
blends.

The coke p r o d u c e d from c a s e ( i i ) , c o a l + 10% p i t c h D, w a s f o u n d t o

e x h i b i t e x c e l l e n t b o n d i n g . The b i n d i n g m a t e r i a l w a s u n i f o r m l y a n d c o n t i n u o u s l y
d i s t r i b u t e d t h r o u g h o u t t h e c o k e and t h e i n e r t m a c e r a l s were embedded w i t h i n t h e
coke matrix, F i g . 5. These o b s e r v a t i o n s w e r e c o n s i s t e n t w i t h t h e r e l a t i v e l y good
BCR s t r e n g t h i n d e x o b t a i n e d f o r t h i s coke.
141
 The d e t e r i o r a t i o n i n coke s t r e n g t h o b s e r v e d f o r c a s e ( i i i ) , c o a l +
16%
p i t c h D, was a t t r i b u t e d t o t h e development of m i c r o - c r a c k s w i t h i n t h e c o k e s t r u c -
t u r e , Fig. 6 . The mechanism by which t h e s e c r a c k s form i s n o t w e l l u n d e r s t o o d ,
b u t c o u l d p e r h a p s r e s u l t f r o m a n e x c e s s of b i n d i n g m a t e r i a l between t h e i n e r t
m a c e r a l s of t h e c o a l , t h e r e b y w e a k e n i n g t h e o v e r a l l s t r u c t u r e .

From t h e t h r e e c a s e s c o n s i d e r e d , i t i s e v i d e n t t h a t coke s t r e n g t h c a n b e
c o r r e l a t e d t o t h e m i c . r o - s t r u c t u r e o f t h e c o k e s . The c o k e q u a l i t y a p p e a r s to b e a
c o m p l e x f u n c t i o n of t h e amount of p i t c h a d d e d , t h e p h y s i c o - c h e m i c a l p r o p e r t i e s of
t h e p i t c h and t h e f l u i d i t y of t h e c o a l / p i t c h b l e n d .

It should be emphasized t h a t t h e arguments p r e s e n t e d i n t h i s paper apply

s p e c i f i c a l l y t o i n e r t - m a c e r a l r i c h , low f l u i d , h i g h r a n k c o a l s . E q u a t i o n 2 ) h a s
s o f a r only h e e n t e s t e d f o r t h i s p a r t i c u l a r t y p e of c o a l . I t i s p o s s i b l e t h a t
o t h e r c o a l s may y i e l d r e s u l t s t h a t do n o t c o n f o r m e x a c t l y t o t h i s e q u a t i o n . For
i n s t a n c e , t h e c o a l u s e d i n t h i s work had no i n h e r e n t f l u i d i t y , and c o n s e q u e n t l y a
t e r m f o r t h e f l u i d i t y o f t h e c o a l i t s e l f d o e s n o t a p p e a r i n t h e e q u a t i o n . However
Equation 2) does d e m o n s t r a t e t h e s t r o n g i n t e r - r e l a t i o n s h i p between t h e c o n t r i b u t i o n
of b i n d i n g m a t e r i a l made by t h e p i t c h and t h e f l u i d i t y of t h e b l e n d .

CONCLUSIONS

High r a n k c o a l s f r o m w e s t e r n Canada which are r i c h i n i n e r t m a c e r a l s ,

g e n e r a l l y r e q u i r e a p i t c h a d d i t i v e t o produce m e t a l l u r g i c a l g r a d e coke. P i t c h
c o n c e n t r a t i o n i n t h e c o a l l p i t c h b l e n d d i c t a t e s b o t h t h e amount of b i n d i n g m a t e r i a l
made a v a i l a h l e t n t h e c o a l a n d t h e f l u i d i t y of t h e b l e n d . Both t h e s e p a r a m e t e r s
depend on t h e p h y s i c o - c h e m i c a l p r o p e r t i e s o f t h e p i t c h a n d on t h e e x t e n t of i n t e r -
a c t i o n between t h e p i t c h a n d t h e c o a l .

I n o r d e r t o p r o d u c e good q u a l i t y c o k e f r o m a c o a l / p i t c h b l e n d , t h e b l e n d
must p o s s e s s s u f f i c i e n t f l u i d i t y t o e n s u r e a u n i f o r m and c o n t i n u o u s d i s t r i b u t i o n
of binding m a t e r i a l throughout t h e c o a l . I n e r t m a c e r a l s of t h e c a 1 must b e
9 .
a d e q u a t e l y w e t t e d and bonded t o g e t h e r . Optimum c o k e s t r e n g t h i s a c h i e v e d when
p i t c h i s added i n s u F f i c i e n t amount t o g e n e r a t e a c o n t r o l l e d f l u i d i t y w i t h enough
b i n d i n g m a t e r i a l t o a g g l o m e r a t e t h e coke. I f added i n l a r g e a m o u n t s , t h e p i t c h can
h a v e d e l e t e r i o u s e f f e c t s on t h e r e s u l t a n t c o k e . The r e a s o n why too much p i t c h
weakens the s t r u c t u r e i s n o t w e l l u n d e r s t o o d , b u t a p p e a r s t o be r e l a t e d t o t h e
development o f m i c r o c r a c k s w i t h i n t h e coke m a t r i x .

ACKNOWLEDGEMENTS

The a u t h o r s w i s h t o t h a n k B . H . M o f f a t t a n d S.E. Nixon f o r t h e i r t e c h n i c a l

a s s i s t a n c e d u r i n g t h e c o u r s e of t h i s work. Thanks a r e a l s o due t o W . G a r d i n e r and
h i s s t a f f f o r t h e i r a s s i s t a n c e i n carrying nut carbonization t e s t s .

REFERENCES

1. Bclinko. K . . C i a v a g l i a , L . A . and Nandi. B.N. "Energy f o r i n d u s t r y " , Ed.

P . W . O'Callaghan; Pergamon P r e s s , (London); pp. 79-89 ( 1 9 7 8 ) .

I. American S o c i e t y for T e s t i n g a n d M a t e r i a l s : P a r t 2 3 , D-189 (1975).

3. Montgomery, D.S. and N a n d i , R . N . F u e l s R e s e a r c h C e n t r e D i v i s i o n a l R e p o r t 731

11; Department o f E n e r g y , Mines and R e s o u r c e s , O t t a w a , Canada (1'973).

4. Elosrs, R . C . Ri tllminous Coal R e s e a r c h I n c . , Elonroeville, Pennsylvania;

['e r s o n a 1 Commun i c11t i o n .
14 2
 NO ADDITIVE

COAL -k 10% PITCH D

4 cm

FIGURE 1: High Temperature Cokes Produced From Canister T e s t s

60
0.9r
BINDING INDEX = C P e x p [ F F ]

/
55
W
P
5 50

40

I
3
BINDING INDEX, PER CENT
FIGURE 2 : Relative Strength Indices for Various Coal/Pitch Blends
143
FLGUKE 3 : O p t i c a l Micrograph o f Coke
Proauced from Coal With No
Additive Showing Poor bonding
Between Fused V i t r i n l t e (FV)
and Oxidizcd V i t r i n i t e (OV)
FIGURE 5 : O p t i c a l Micrograph of Coke
Produced from Coal+ 10% P i t c h
D Showing E x c e l l e n t Bonding
of F u s i n i t i c S t r u c t u r e ( F )
by Fused Mass (FM)
144
FIGURE 4 : O p t i c a l Micrograph of Coke
Produced trom Coal + 5% P i t c h
D .Showing Discontinuous Bonding
of Fused Mass (FPI) With F u s i n i -
t i c S t r u c t u r e (F)
FIGURE h : O p t i c a l Micrograph of Coke
Produced From Loa1 + 167, P i t c h
D Showing Development o f Micro-
c r a c k s Within Fused Mass (FM)
 SYIVXETIC FUELS - PITFALLS AND PROMISE. Fred Schulman. Energy Systems
Technology C o r p . , 927-15th S t . , N . W . , Washington, D.C. 2000.5
T e c h n i c a l p r o c e s s improvements and p o l i c y r e s t r a i n t s o n OPEC's a b i l i t y
t o i n c r e a s e o i l p r i c e s a t w i l l a r e two e s s e n t i a l components o f a v i a b l e
s y n t h e t i c f u e l s i n d u s t r y . One w i t h o u t t h e o t h e r s p e l l s f r u s t r a t i o n and
f a i l u r e . The Arab o i l embargo o f 1973-74 and t h e s u b s e q u e n t f i v e - f o l d
i n c r e a s e i n p e t r o l e u m p r i c e s l e d t o m u l t i b i l l i o n d o l l a r programs t o de-
velop s y n t h e t i c f u e l s . E x p e c t a t i o n s o f a g r e a t new s y n t h e t i c f u e l s i n -
d u s t r y were u n f u l f i l l e d as p r i c e s 2nd c o s t s r o s e toward t h e i r e q u i v a l e n t -
v a l u s - t o - o i l . Cost d i f f e r e n t i a l s i n f a v o r o f imported o i l c o n t i n u e t o
i n c r h a s e y e a r by y e a r d e s p i t e many chemical and e n g i n e e r i n g i n n o v a t i o n s .
F o r example, e s t i m a t e d c o s t s o f p r o d u c i n g s h a l e o i l r o s e from $7 p e r b b l
i n 1973 t o $3O/bbl t o d a y . When t n e OPEC c a r t e l r a i s e d o i l p r i c e s a n o t h e r
Sk$ l a s t J u n e , it became even more i m p o r t a n t t o e n c o u r a g e d o m e s t i c o i l
s r o d u c t i o n and t o d e v e l o p energy a l t e r n a t i v e s . OPEC's new p r i c e s w i l l
f o r c e t h e b a s e p r i c e o f s y n t h e t i c f u e l s t o r i s e t o $46-50 by 1983.
i i s i n g f e e d s t o c k c o s t s i m p e r i l t h e domestic p e t r o c h e m i c a l i n d u s t r y and
?ndanger c h e m i c a l e x p o r t s . T h i s p a p e r d e t a i l s some o f t h e s e problems and
s u g g e s t s a number o f energy p o l i c y a c t i o n s aimed a t e s t a b l i s h m e n t o f t h e
i o n e s t i c f u e l s i n d u s t r y o n a sound b a s i s .

145
 Development o f a S i m u l a t e d C a t a l y s t Aging T e c h n i q u e

J.F. K r i z a n d M. T e r n a n

Energy R e s e a r c h L a b o l - a t o r i e s
Canada C e n t r e f o r M i n e r a l and Energy Technology
D e p a r t m e n t of Energy, Mines and R e s o u r c e s Canada
O t t a w a , Canada
K1A O G 1

INTRODUCTTON

Under h y d r o c r a c k i n g c o n d i t i o n s , heavy o i l s p r o d u c e d e p o s i t s t h a t
a c c u m u l a t e on t h e c a t a l y s t s u r f a c e . By p o i s o n i n g and by h i n d e r i n g a c c e s s i b i l i t y
of t h e a c t i v e s i t e s , t h e s e d e p o s i t s c a u s e f o u l i n g of t h e c a t a l y s t . M a t e r i a l
that i s so d e p o s i t e d i s e i t h e r o r i g i n a l l y p r e s e n t i n t h e f e e d , s u c h a s heavy
m e t a l s and m i n e r a l s , or i s formed d u r i n g h y d r o c r a c k i n g . s u c h a s c o k e . Not a l l
d e p o s i t s d e a c t i v a t e t h e s u r f a c e a t t h e same r a t e . I t was e s t a b l i s h e d by r e p e a t e d
r e g e n e r a t i o n t h a t r a p i d f o u l i n g under t y p i c a l bitumen hydrocracking c o n d i t i o n s
i s c a u s e d p r i m a r i l y by c o k e f o r m a t i o n ( 1 ) . To o b t a i n a l o n g e r - l a s t i n g formu-
l a t i o n , c a t a l y s t d e v e l o p m e n t s h o u l d t h e r e f o r e f o c u s o n t y p e s t h a t resist c o k e
formation. Such a n e f f o r t would i n v o l v e a s y s t e m a t i c a p p r o a c h t o c a t a l y s t
p r o d u c t i o n b a s e d on i n f o r m a t i o n o b t a i n e d i n a g i n g t e s t s .

To d e t e r m i n e t h e t r u e a g i n g c l i a r a c t e r i s l i c s , a c t u a l p r o c e s s i n g cond-
i t i o n s m u s t b e m a i n t a i n e d b e c a u s e t h e y a f f e c t p r o d u c t f o r m a t i o n and t h e r e b y
a l s o t h e p r o c e s s of d e a c t i v a t i o n . However, a s e r i o u s d i s a d v a n t a g e o f a g i n g
t e s t s u n d e r a c t u a l p r o c e s s i n g c o n d i t i o n s i s t h a t t h e y a r e s l o w and t h u s consume
a g r e a t d e a l of t i m e and manpower. The t i m e i n v o l v e d becomes c r i t i c a l i f a g i n g
c h a r a c t e r i s t i c s a r e r e q u i r e d f o r a l a r g e number of c a t a l y s t s . I t is t h e p u r p o s e
of t h i s r e p o r t t o d e s c r i b e a t e c h n i q u e t h a t s i m u l a t e s c a t a l y s t a g i n g and pro-
v i d e s p r e l i m i n a r y i n f o r m a t i o n i n a much s h o r t e r t i m e .

EXPERIMENTAL EQUIPMENT AND MATERIALS

A b e n c h - s c a l e f i x e d - b e d r e a c t i o n s y s t e m was u s e d , i n which t h e
b i t u m e n mixed w i t h h y d r o g e n flowed up t h r o u g h t h e c a t a l y s t bed c o n t i n o u s l y .
L i q u i d and v a p o u r were s e p a r a t e d in r e c e i v e r v e s s e l s . The e q u i p m e n t was
p r e v i o u s l y d e s c r i b e d i n d e t a i l ( 2 ) b u t t h e f o l l o w i n g m o d i f i c a t i o n s w e r e made
t o accommodate t h e p a r t i c u l a r r e q u i r e m e n t s of t h e p r e s e n t s t u d y ( 3 ) :

1. Bitumen was s t o r e d i n a h e a t e d h o p p e r from which i t c o u l d b e f e d t h r o u g h

t a p s i n t o t w o 1000-mL b u r e t t e s i n a h e a t e d p l a s t i c c a b i n e t . With a l i g h t
positioned behind t h e c a b i n e t a n d , t h e i n s i d e of t h e c a b i n e t heated t o
a b o u t 75OC, i t w a s p o s s i b l e t o m o n i t o r t h e f e e d l e v e l i n t h e b u r e t t e s .
A M i l t o n Roy " C o n s t a m c t r i c " p u m p , model numbcr 'TCP 4 3 - 4 3 TJ. was u s e d t o
f e e d t h e b i t u m e n t h r o u g h h e a t e d l i n e s i n t o tlic r e a c t o r . A p r e s s u r e gauge
w a s p l a c e d a t t h e pump o u t l e t t o m o n i t o r p r e s s u r e a t t h e pump h e a d .

2. TO r e d u c e t h e r e a c t o r volume, a s t a i n l e s s steel i n s e r t w a s machined t o f i t

i t , r e d u c i n g t h e i n s i d e d i a m e t e r t o 1 . 2 7 cm from 2 . 5 4 cm b u t m a i n t a i n i n g
l e n g t h a t 30.5 c m .
146
 The c a t a l y s t s e l e c t e d f o r c o m p a r a t i v e r u n s was a c o m m e r c i a l t y p e
Harshaw 0603T w i t h 3 w t Z COO and 1 2 w t % MOO s u p p o r t e d o n a l u m i n a . i n t h e
form o f c y l i n d r i c a l 3.2-mm p e l l e t s . About 1 5 8 g o f t h i s c a t a l y s t r e p r e s e n t e d
a f u l l r e a c t o r l o a d b u t o n l y a b o u t 30 g c o u l d be l o a d e d w i t h t h e i n s e r t . The
r a t e o f a g i n g w a s e v a l u a t e d u s i n g A t h a s b a s c a bitumen o b t a i n e d from G r e a t
Canadian O i l S a n d s L i m i t e d a t F o r t McMurray, A l b e r t a . P r o p e r t i e s of t h e feed-
s t o c k are l i s t e d i n T a b l e 1.

TABLE I

P r o p c r t ies of htliah;isca Uitumcn

Specific gravity 1.009 (15/15OC) Benzene i n s o l u b l e s 0.72 wt%

Sulphur 4.48 w t X Carbon 86.36 wt%
Ash 0.59 w t % Hydrogen 10.52 wt%
Conradson Carbon Kesidue 13.3 wtZ Nitrogen 0.45 wt%
Pentane i n s o l u h l e s 15.5 wtZ l ' i t c h (525OC+) 51.5 wt9.

OPERATING CONDITIONS

The c o n d i t i o n s t h a t a f f e c t c a t a l y s t d e a c t i v a t i o n i n a c o n t i n u o u s
f l o w s y s t e m a r e t e m p e r a t u r e , hydrogen p r e s s u r e , h y d r o g e n f l o w r a t e a n d l i q u i d
space velocity. The h y d r o c r a c k i n g p r o c e s s c o n s i s t s of a number of complex
r e a c t i o n s t e p s , i n i t i a l l y i n v o l v i n g v a r i o u s c o n s t i t u e n t s of bitumen. C a t a l y t i c
p r o c e s s e s on a c t i v e s u r f a c e s i t e s p a r t i c i p a t e i n some o f t h e r e a c t i o n steps.

Although i t would be d i f f i c u l t , b e c a u s e of c o m p l e x i t y o f t h e react-

i o n s , t o p r e d i c t a c c u r a t e l y t h c Lmpact of c h a n g e s of any p r o c e s s i n g c o n d i t i o n .
some o v e r a l l e f f e c t s c a n be d e r i v e d f r o m t h e f u n d a m e n t a l s o f r e a c t i o n k i n e t i c s .
The r a t e of i n d i v i d u a l r e a c t i o n s t e p s v a r i e s w i t h t e m p e r a t u r e a n d c o n c e n t r a t i o n
of r e a c t a n t s . C r a c k i n g r e a c t i o n s a r e e n d o t h e r m i c and a c c e l e r a t e w i t h i n c r e a s -
i n g temperature, whereas hydrogenation r e a c t i o n s a c c e l e r a t e w i t h i n c r e a s i n g
hydrogen p r e s s u r e . Coke [ o r m a t i o n d e p e n d s o n t h e r a t e s of c r a c k i n g and d e h y d r o -
g e n a t i o n , f o l l o w e d by p o l y m e r i z a t i o n . T h e r e f o r e c o k e f o r m a t i o n accelerates w i t h
i n c r e a s i n g temperature and d e c r e a s i n g hydrogen p r e s s u r e .

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

series o f s c r e e n i n g e x p e r i m e n t s t o i n v e s t i g a t e t h e e f f e c t o f v a r i a t i o n s i n
s p a c e v e l o c i t y and t e m p e r a t u r e . The e f f e c t o f h y d r o g e n p r e s s u r e on c a t a l y s t
aging w a s s t u d i e d p r e v i o u s l y u s i n g a d i f f e r e n t experimental system ( 4 ) . I n
t h e p r e s e n t s t u d y , t h e h y d r o g e n p r e s s u r e was m a i n t a i n e d c o n s t a n t a t 1 3 . 9 MPa
f o r a l l t e s t s , which is w i t h i n t h e p r a c t i c a l r a n g e f o r h y d r o c r a c k i n g . A sat-
i s f a c t o r y e f f e c t c o u l d n o t h a v e b e e n a c h i e v e d by v a r y i n g o n l y s p a c e v e l o c i t y ;
a n i n c r e a s e i n t e m p e r a t u r e w a s a l s o n e c e s s a r y t o r e d u c e a g i n g time s u f f i c i e n t l y .
A f t e r some p r e l i m i n a r y e x p e r i m e n t a t i o n , o p t i m y d e a c t i v a t i o n c o n d i t i o n s w e r e
found t o p r e v a i l w i t h a s p a c e v e l o c i t y o f 5 h and a t a t e m p e r a t u r e o f 495OC.
The f o l l o w i n g s e r i e s of tests u n d e r d i f f e r e n t o p e r a t i n g c o n d i t i o n s
a r e documented i n t h e p r e s e n t r e p o r t :

Series 1

T r u e o r b a s e d e a c t i v a t i o n t a t ' s w e r e measured a t 45OoC and a t a l i q u i d volumet-

r i c s p a c e v e l o c i t y o f 1 h- b a s e d o n t h c r e a c t o r v o ume packed w i t h t h e c a t a l y s t
p e l l e t s . The c o r r e s p o n d i n g f e e d r a t e was 152 mL h
-i as no i n s r t was p l a c e d i n
t h e r e a c t o r . The h y d r o g e n f l o w r a t e w a s m a i n t a i n e d a t 35.6 cm's-l a t STP. T h i s
t e s t is r e f e r r e d t o a s t r u e a g i n g a n d was r u n c o n t i n u o u s l y f o r 5 6 h o u r s , and
t h e n p e r i o d i c a l l y i n f i v e - t o e i g h t - h o u r i n t e r v a l s , t o t a l l i n g a b o u t 200 h o u r s
i n a l l . A n a l y s e s were p e r f o r m e d on s a m p l e s o f t h e l i q u i d p r o d u c t a c c u m u l a t e d
i n two t o f i v e hour's o f o p e r a t i o n .
147
Series 2

High s p a c e v e l o c i t y tests were p e r f o r m e d u n d e r t h e same c o n d i t i o n s a s f o r t r u e

a g i n g - 1 3 . 9 m a , 450°C. and w i t h o u t i n s e r t - e x c e p t f o r a d i f f e r e n t a r r a n g e m e n t
of s p a c e v e l o c i t i e s . C a t a l y s t a g i n g w a s c a r r i e d o t i n two 12-hour p e r i o d s
-Y
d u r i n 5 YPich s p a c e v e l o c i t y w.ib m a i n t a i n e d :it 5 Ii , and t h e h y d r o g e n f l o w a t
95 c m s a t STP. The l e v e l of n c t i v i t y . i n i t i a l l y anf a f t e r e a c h 12-hour p e r i o d
was d e t r m ' n e d by c h a n g i n g t h e s p a c e v e l o c i t y t o 1 h- , t h e h y d r o g e n f l o w t o
35.6 c>s-* a t STP f o r two h o u r s a n d a n a l y z i n g t h c l i q u i d s a m p l e t h a t a c c u m u l a t e d
d u r i n g t h e s e two h o u r s .

Scrics 3

S i m u l a t e d d e a c t i v a t i o n r a t e s were measured a t h i g h t e m p e r a t u r e a n d h i g h s p a c e
velocitl. T h i s t e s t was r u n a t 495OC and a l i q u i d v o l u m e t r i c s p a c e v e l o c i t y
of 5 h . Thy i n s e r t w a s p l a c e d i n t h e r e a c t o r and t h e c o r r e s p o n d i n g f e d r a t e
was 181 mL.h . The hydrogen f l o w r a t e was m a i n t a i n e d a t a b o u t 7 0 cm3s-' a t STP.
The s e r i e s was r e f e r r e d t o a s s i m u l a t e d a g i n g and was r u n c o n t i n o u s l y f o r 32
h o u r s . The l i q u i d p r o d u c t t h a t a c c u m u l a t e d d u r i n g e a c h hour o f o p e r a t i o n was
withdrawn f o r a n a l y s i s .

Series 4

A l i n k between s i m u l a t e d a g i n g and t r u e a g i n g w a s s o u g h t by a d d i t i o n a l t e s t s i n
t h e f o l l o w i n g manner. The s i m u l a t e d a g i n g c o n d i t i o n s were a p p l i e d f o r a p e r i o d
of t i m e a n d were t h e n changed t o m a t c h t h e t r u e a g i n g c o n d i t i o n s f o r a p p r o x i m a t e l y
two h o u r s d u r i n g which two l i q u i d s a m p l e s were o b t a i n e d . The r u n was t h e n
t e r m i n a t e d , thc r e a c t o r r c - l o ; i d c d w i t h a frcssli c a t a l y s t , and t h e t e s t was r e p -
eated for a d i f f e r e n t time p e r i o d under simulated a g i n g c o n d i t i o n s . Three
d i f f e r e n t time p e r i o d s - 2, 4 and 6 h o u r s , r e s p e c t i v e l y - u n d e r s i m u l a t e d a g i n g
c o n d i t i o n s were examined. N o i n s e r t was p l a c e d i n t h c r c a f t o r and t h e s i m u l a t e d
a g i p g t e s t w a s r u n a t 495OC w i t h t h e f e e d r a e of 760mL.h- , s p a c e v e l o c i t y of
5h , and t h e hydrogen f l o w r a t e a t 70 cm3s-' a t ST1'.

S e v e r a l p r o c e s s i n g c o n d i t i o n s were a p p l i e d d i f f e r e n t l y i n e a c h s e r i e s
of t e s t s . For i n s t a n c e , i n S e r i e s 2. t h e s p a c e v e l o c i t y was f i v e times g r e a t e r
t h a n i n S e r i e s 1, w h e r e a s t h e g a s f l o w r a t e was o n l y a b o u t t h r e e times g r e a t e r .
I n S e r i e s 1, t h e g a s f 1 o w : f e e d r a t i o w a s l o w e r t h a n i n S e r i e s 3 , b u t h i g h e r
than i n t h e simulated a g i n g i n S e r i e s 4 . I n a d d i t i o n , t h c 1ength:diameter r a t i o
was i n c r e a s e d i n S e r i e s 3 by p l a c i n g t h e i n s e r t i n t h e r e a c t o r , t h e r e b y i n c r e a s -
i n g t h e l i n e a r v e 1 o c i t y : s p a c e v e l o c i t y r a t i o t h r o u g h t h e c a t a l y s t b e d . The
u s e of t h e i n s e r t a n d v a r y i n g f l o w r e g i m e r e s u l t e d from e x p e r i e n c e w i t h t h e
e x p e r i m e n t a l s y s t e m and f a c i l i t a t e d smooth o p e r a t i o n . The c h a n g e s made were
n e c e s s a r y t o p r e v e n t t h e r e a c t o r p l u g g i n g and t o m a i n t a i n t e m p e r a t u r e p r o f i l e s
w i t h i n t h e c a t a l y s t bed.

Thc impact 01 i n c r c ; i s i n g t e m p e r a t u r e and s p a c e v c l o c i t y i s d i s c u s s e d

i n t h e next s e c t i o n of t h i s r e p o r t . V a r i a t i o n s i n hydrogen f l o w a r e n o t con-
s i d e r e d s i g n i f i c a n t f o r t h e purposc of t h i s i n v e s t i g a t i o n , because a n excess
of hydrogen was used i n a l l e x p o r i m e n t s and b e c a u s e hydrogen f l o w seemed t o
e x h i b i t o n l y a small e f f e c t o n p r o d u c t f o r m a t i o n ( 5 ) .

RESULTS AND DISCUSSION

T r u e Aging

The d e a c t i v a t i o n p a t t e r n is shown i n F i g . 1 i n terms of a n i n c r e a s e i n

t h e s p e c i f i c g r a v i t y of the l i q u i d p r o d u c t and a n i n c r e a s e i n i t s s u l p h u r
c o n t e n t . I t c a n b e p r e d i c t e d by e x t r a p o l a t i o n t h a t f u r t h e r d e a c t i v a t i o n would
148
be r e c o r d e d beyond 200 h o u r s of o p e r a t i o n . However, i t c a n b e s e e n t h a t d e -
a c t i v a t i o n i s more r a p i d i n t h e e a r l y s t a g e s of t h e t e s t t h a n i n t h e l a t e r
s t a g e s . S i n c e d e a c t i v a t i o n d e c e l e r a t e s w i t h t i m e . t h e c u r v e s i n F i g . 3 may
e v e n t u a l l y l e v e l o f f , i n d i c a t i n g a c o n s t a n t a c t i v i t y . The d e c e l e r a t i n g d e -
a c t i v a t i o n i s i n a g r e e m e n t w i t h r e s u l t s of a p r e v i o u s s t u d y which a l s o showed
t h a t t h i s l e v e l i n g - o f f is r e l a t i v e l y more pronounced and t a k e s p l a c e e a r l i e r
w i t h i n c r e a s i n g hydrogen p r e s s u r e ( 4 ) . Whether a s t a t e o f c o n s t a n t a c t i v i t y
i n f a c t e x i s t s is n o t known as t h e p a t t e r n s i n F i g . 1 c a n n o t b e e x t r a p o l a t e d
w i t h any p r e c i s i o n . Furthermore. t e s t s c a r r i e d o u t c o n t i n u o u s l y f o r l o n g e r
t h a n 200 h o u r s of o p e r a t i o n a r e n e c e s s a r y t o d e t e r m i n e d e a c t i v a t i o n p a t t e r n s
t h a t a r e u n a f f e c t e d by s t a r t - u p and shut-down p r o c e d u r e s . T h e s e l o n g - t e r m
t e s t s a r e t o be p e r f o r m e d on a s p e c i a l t e s t i n g s y s t e m p r e s e n t l y u n d e r con-
struction.

High S p a c e V e l o c i t y

The r e s u l t s of t h e h i g h s p a c e v e l o c i t y t e s t s i n c l u d e d a n a l y t i c a l
d a t a o n l i q u i d p r o d u c t s a m p l e s o b t a i n e d f o r b o t h h i g h and b a s e s p a c e v e l o c i t i e s
of t h i s s e r i e s . The r e s u l t s f o r t h e b a s e s p a c e v e l o c i t i e s s e r v e d a s a m e a s u r e
of d e a c t i v a t i o n a f t c r c o m p l e t i n g a p e r i o d w i t l i h i g h s p a c e v e l o c i t y . The de-
activation is indicated i n the left-hand s i d e of Fig.1,

A f i v e - f o l d i n c r e a s e i n f e e d r a t e had a n i n s i g n i f i c a n t e f f e c t o n t h e
r a t e of d e a c t i v a t i o n . One c o u l d r a t i o n a l i z e t h i s f i n d i n g by a s s u m i n g t h a t
lower c o n v e r s i o n s c a u s e d by r e d u c e d r e s i d e n c e t i m e would c o m p e n s a t e f o r t h e
g r e a t e r f e e d r a t e i n r e l a t i o n t o c o k e f o r m a t i o n . However. a more d e t a i l e d
a n a l y s i s would r e v e a l t h a t t h e r e l a t i o n s h i p between t h e s p a c e v e l o c i t y a n d t h e
r a t e o f d e a c t i v a t i o n may b e more complex, m a i n l y b e c a u s e o f t h e m u l t i c o m p o n e n t
s t r u c t u r e o f t h e r e a c t i o n s y s t e m . The c o n c e n t r a t i o n of r e a c t i o n c o n s t i t u e n t s
d e p e n d s o n t h e x a t e s o f t h e i r f o r m a t i o n and d e p l e t i o n . Thus t h e t o t a l y i e l d o f
a component may n o t h e a monotonic f u n c t i o n of t h e r e s i d e n c e t i m e . I f some
coke p r e c u r s o r s react f a s t e r t h a n o t h e r s , t h e n t h e i r p a r t i c i p a t i o n i n t o t a l cokc
f o r m a t i o n d e p e n d s o n t h e s p a c e v e l o c i t y , a c h a n g e i n which may c o n s e q u e n t l y be
r e f l e c t e d i n b o t h t h e q u a n t i t y a n d t h e q u a l i t y of t h e c o k e d e p o s i t s . In addition
t o c h e m i c a l phenomena, m e c h a n i c a l r e g e n e r a t i o n may t a k e p l a c e whereby p a r t i c l e s
of c o k e are d e t a c h e d from t h e s u r f a c e by a b r a s i o n or by d i s s o l u t i o n o f t h e b i n d -
ing carbonaceous m a t e r i a l . Should n s i m i l a r p r o c e s s t a k e p l a c e w h i l e b i t u m e n
is u s e d , i t would b e e n h a n c e d by i n c r e a s i n g t h e s p a c e v e l o c i t y .

The h i g h s p a c e v e l o c i t y s e r i e s i n d i c a t e d t h a t t h e d e s i r e d e f f e c t
c o u l d n o t b e e s t a b l i s h e d by c h a n g i n g t h e s p a c e v e l o c i t y a t b a s e t e m p e r a t u r e .
To a c c e l e r a t e a g i n g s u b s t a n t i a l l y , t h e c a t a l y s t f o u l i n g was s i m u l a t e d a t a
h i g h e r r e a c t i o n t e m p e r a t u r e . The term s i m u l a t e d a g i n g i s u s e d t o e m p h a s i z e
t h e s e v e r e consequences of t h e change i n t e m p e r a t u r e .

S i m u l a t e d Aging

The r e s u l t s o f t h e s i m u l a t e d a g i n g t e s t s a r e shown i n F i g . 2 . The

a c t i v i t y dropped r a p i d l y i n t h e f i r s t p e r i o d of t h e r u n , l e v e l e d o f f , and
remained a p p r o x i m a t e l y c o n s t a n t beyond 1 5 h o u r s o f o p e r a t i o n .

The p e r f o r m a n c e u n d e r s i m u l a t e d a g i n g r e f l e c t e d t h e e f f e c t of b o t h
h i g h t e m p e r a t u r e and h i g h space v c l o c i t y . The p e r f o r m a n c e seemed t o he more
s e n s i t i v e t o t e m p e r a t u r e , p a r t i c u l a r l y w i t l i r e s p e c t to’the p i t c h f r a c t i o n of
t h e bitumen. The i n i t i a l h i g h p i t c h c o n v e r s i o n o b s e r v e d c o u l d r e s u l t f r o m
m o l e c u l a r w e i g h t r e d u c t i o n o r g r o w t h . M o l e c u l a r g r o w t h would r e s u l t i n
p r e c i p i t a t i o n of c o k e , most o f which would be r e t a i n e d o n t h e c a t a l y s t s u r f a c e
and r e a c t o r w a l l s . The m o l e c u l o r w e i g h t r c d u c t i o n by c r a c k i n g would g e n e r a t e
compounds h a v i n g a lower b o i l i n g p o i n t t h a n t h o s e c o n t a i n e d i n t h e p i t c h . I t
149
is a p p a r e n t t h a t , w h e r e a s b o t h o f t h c l a t t e r p r o c e s s e s Iiavc t a k e n p l a c e s i m u l -
t a n e o u s l y , t h e g r o w t h r a t e was much s m a l l e r b e c a u s e t h e amount of c o k e formed
a c c o u n t s f o r o n l y a f r a c t i o n o f t h e p i t c h c o n v e r t e d . However, t h e h i g h temper-
a t u r e of s i m u l a t e d a g i n g compared w i t h t r u e a g i n g s h i f t e d t h e b a l a n c e t o w a r d s
coke formation a s r e f l e c t e d i n r a p i d c a t a l y s t d e a c t i v a t i o n .

L e s s e x t e n s i v e h y d r o g e n a t i o n under s i m u l a t e d a g i n g c o n d i t i o n s ,
i n d i c a t e d by a l o w H:C r a t i o , was presumably d u e t o a h i g h a r o m a t i c c a r b o n
c o n t e n t . An a n a l y s i s by F o u r i e r T r a n s f o r m C-13 N.M.R. indicated that the

1
u n s a t u r a t e d c a r b o n r e p r e s e n t e d a b o u t 30% of t h e t o t a l c a r b o n i n t h e i n i t i a l
p r o d u c t of s i m u l a t e d a g i n g com a r e d w i t h a b o u t 20% of t h a t o f t r u e a g i n g . The
f o l l o w i n g r e a s o n s may be c o n s ' c r c d to a c c o u n t f o r c h a n g e s i n t h e a r o m a t i c
c a r b o n c o n t e n t . More e x t e n s i v e s p l i t t i n g of s i d e c h a i n s from a r o m a t i c r l n g s
c a u s e d by t h e h i g h e r t e m p e r a t u r e c o u l d liave y i e l d e d more g a s i n t h e p r o d u c t .
A p a r t from h y d r o c r a c k i n g r e a c t i o n s , t h e h i g h e r t e m p e r a t u r e a l s o s h i f t s t h e
n a p h t h e n e s - a r o m a t i c s e q u i l i b r i a t o w a r d s f o r m a t i o n of a r o m a t i c s ( 6 ) . I n add-
i t i o n t o t h e t e m p e r a t u r e e f f e c t s , t h e h i g h s p a c e v e l o c i t y of s i m u l a t e d a g i n g
may h a v e h i n d e r e d t h e e x t e n t of h y d r o g c n a t i o n h c c a u s c of t h e s h o r t e r c o n t a c t
time .
L i n k between S i m u l a t e d and T r u e Aging

S i n c e t h e r a t e of d e a c t i v a t i o n u n d e r s i m u l a t e d a g i n g c o n d i t i o n s
could not e a s i l y be r e l a t e d t o t h e r a t e of d e a c t i v a t i o n under t r u e aging
c o n d i t i o n s , a s e r i e s o f e x p e r i m e n t s was p e r f o r m e d i n which a l i n k was s o u g h t
b e t w e e n s i m u l a t e d a n d t r u e a g i n g . The p u r p o s e of t h e s e e x p e r i m e n t s w a s t o
m e a s u r e t h e l e v e l of a c t i v i t y u n d e r t r u e a g i n g c o n d i t i o n s a f t e r t h e c a t a l y s t
had b e e n s u b j e c t e d t o s i m u l a t c d a g i n g c o n d i t i o n s f o r a c c r t a i n p e r i o d of
t i m e , and t h e n t o g r a p h i c a l l y e s t i m a t e t h e t i m e i n which t h e c a t a l y s t would
d e t e r i o r a t e enough t o r e a c h t h i s l e v e l of a c t i v i t y w h i l e b e i n g s u b j e c t e d t o
t r u e aging c o n d i t i o n s .

The a c t i v i t y l e v e l s d e t e r m i n e d f o r t h r e e d i f f e r e n t t i m e p e r i o d s u n d e r
s i m u l a t e d a g i n g a r e marked o n t h e r i g h t - h a n d s i d e of t h e c u r v e s i n F i g . 1 . By
a p p l y i n g t h e s e r e s u l t s i t was e s t i m a t e d t h a t 2 h o u r s o f o p e r a t i o n u n d e r s i m u l -
a t e d a g i n g c o n d i t i o n s would c o r r e s p o n d t o a b o u t 50-70 h o u r s u n d e r t r u e a g i n g .
and s i m i l a r l y , 4 h o u r s t o 100-150 h o u r s , and 6 h o u r s t o 150-200 h o u r s . Hence,
a s s u m i n g t h a t s i m u l a t e d a g i n g i s a p p r o x i m a t e l y 30 t i m e s f a s t e r t h a n t r u e a g i n g ,
o n e c o u l d e x t r a p o l a t e t h c p a t t c r n of t r u e a g i n g and s p c c u l a t e t h a t i t would
l e v e l o f f i n a b o u t 400 h o u r s of o p e r a t i o n .

E s t i m a t i n g t h e l i n k hetwecn t r u e and s i m u l a t e d a g i n g i n F i g . 1 i s a n
a p p r o x i m a t i o n o n l y . However, i t is a p p a r e n t t h a t by u s i n g s i m u l a t e d a g i n g
c o n d i t i o n s , t h e d e a c t i v a t i o n was a c c e l e r a t e d s u f f i c i e n t l y t o p r o c e e d s u b s t a n t -
i a l l y i n a very short t i m e . I t i s e x p e c t e d t h a t by a p p l y i n g t h i s method t o a
number of c a t a l y s t s , p r e l i m i n a r y i n f o r m a t i o n c a n be o b t a i n e d by comparing t h e i r
d e a c t i v a t i o n p a t t e r n s s u c h a s t h e one shown i n F i g . 2 . T h i s i n f o r m a t i o n would
t h e n be a v a i l a b l e e i t h e r i n a d d i t i o n t o t h e t r u e a g i n g d a t a , or f o r u s e w i t h
c a t a l y s t s on which t r u e a g i n g tests a r e n o t w a r r a n t e d .

ACKNOWLEDGEMENTS

The a u t h o r s w i c h t o e x p r e s s t h e i r s i n c e r e a p p r e c i a t i o n t o R.W. Taylor

f o r m o d i f y i n g t h e e x p e r i m e n t a l s y s t e m a n d t o L. G a l b r a i t h f o r t e c h n i c a l
assistance.
150
 REFERENCES

1. McColgan, E . C . and P a r s o n s , D . I . "The h y d r o c r a c k i n g of r e s i d u a l o i l s a n d

t a r s . P a r t 6: C a t a l y s t d e a c t i v a t i o n by c o k e a n d m e t a l s d e p o s i t i o n " ;
Department o f Energy, Mincs and R e s o u r c e s . Mines Branch ( s i n c e renamed
Canada C e n t r e f o r M i n e r a l and Energy Tcchnology (CANMET))Research R e p o r t
R273; 1974.

2. O'Grady, M.A. and P a r s o n s , B . I . "The h y d r o g e n a t i o n of A l b e r t a b i t u m e n

over c o b a l t molybdate c a t a l y s t " ; D e p a r t m e n t o f Energy, >!ines and R e s o u r c e s ,
Mines Branch, R e s e a r c h R e p o r t R194; 1967.

3. K r i z , J.F. and T e r n a n , M. "Development o f a s i m u l a t e d c a t a l y s t a g i n g

t e c h n i q u e " ; E n e r g y , Mines and R e s o u r c e s , Canada, CANMET R e p o r t 78-24; 1 9 7 8 .

4. Ranganathan, R . , L o g i e , R.B. and D e n i s , J.M. " C a t a l y t i c h y d r o c r a c k i n g of

A t h a b a s c a b i t u m e n i n a f l u i d i z e d bed r e a c t o r - e f f e c t o f p r e s s u r e o n c a t a -
l y s t decay"; Energy, Mines a n d R e s o u t c e s , Canada, CANMET R e p o r t 77-40;
1976.

5. M e r r i l l , W.H., L o g i c , R . H . and D c n i s , J . M . "The e f f e c t of h y d r o g e n r e c y c l e

r a t e on t h e n o n - c a t a l y t i c h y d r o c r a c k i n g o f G.C.O.S. s e p a r a t e d bitumen";
Department o f Energy, Mines a n d R e s o u r c e s , Mines Branch; D i v i s i o n a l R e p o r t
FRC 72/115-PPE; 1 9 7 2 .

6. G u l l y , A . J . and B a l l a r d , W.P. "Hydrogenation of c a t a l y t i c c r a c k i n g c h a r g e

stocks"; Adv P e t Chcm R c f i n (Ncw York, I n t e r s c i e n c e . P u b l i s h e r s ) 7:240-282;
1963.

151
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1IOUI~S

F i g . 1 S p e c i f i c g r a v i t y (15/lS°C) and s u l p h u r c o n t e n t (wt X)

i n t h e l i q u i d p r o d u c t v e r s u s t i m e on stream (h) d u r i n g
t r u e aging. 0 i n d i c a t e s high space v e l o c i t y experiments.
A c t i v i t y l e v e l s on right-hand s i d e r e l a t e t o d i f f e r e n t
t i m e p e r i o d s under s i m u l a t e d a g i n g .

-
........................
i
1 . . . . 10. . . . . . . . . . . . .
30
tIOUf(S 2o

Fig.2 S p e c i f i c g r a v i t y (15/lSoC) and s u l p h u r c o n t e n t ( u t I)

i n t h e l i q u i d p r o d u c t v e r s u s time on stream (h) d u r i n g
simulated aging.

152
 REMOVAL O F ORGANIC SULFUR FROM COAL: THE USE OF LIQUID SULFUR DIOXIDE
Duane F. Burow and Boris M. Glavincevski
Department of Chemistry, University of Toledo, Toledo, Ohio 43606

ABSTRACT
The u t i l i t y of liquid SO, f o r the removal of organic s u l f u r from
several Eastern bituminous coals has been explored. Reactions were carried
o u t in sealed f r i t t e d glass tubes a t elevated temperatures; a f t e r subse-
quent washing, the coal was analyzed for s u l f u r content. Approximately
40% of the organic s u l f u r could be removed in these simple exploratory
experiments. In addition, comminution of most of the coals occurred a n d a
portion of the coal was extracted. The extract from selected coals was
characterized by thin-layer chromatography, by nmr ('H and 1 3 C ) and infrared
spectroscopy, and by field-ionization mass spectrometry. For comparison,
extractions with phenol a n d p c r e s o l , under similar conditions, were also
examined. The results of these preliminary investigations warrant further
research to establish optimum conditions f o r the removal of s u l f u r compounds
from coal by treatment with liquid SO2 and t o f a c i l i t a t e removal of residual
SO2 from the coal.

I NTRO DUCT1ON
Sol vent extraction has been extensively used f o r compositional
characterization of coals. 1'2 Several existing coal refining p r o c e s s e ~ ~ - ~
use solvent treatment, along with pressurized hydrogen t o f a c i l i t a t e some
degree of desulfurization. Treatment w i t h 1 i q u i d SO, has been successfully
used t o remove organic s u l f u r compounds from petroleum on a commercial
scale.6 The a b i l i t y of liquid SO2 t o disintegrate various coals has been
exploited to produce low-sulfur coal powders via release of pyrite.7
Utilization of liquid SO2 treatment of coal f o r the removal of organic
s u l f u r , however, has not been investigated. In t h i s paper we report
t h e results of a s e t of preliminary experiments in which t h e effectiveness
of liquid SO2 f o r removal of organic sulfur from bituminous coals PSOC 194,
267, 270, and 319 was investigated.

EXPERIMENTAL
Procedures for the manipulation and preparation of the s u l f u r dioxide
(Matheson, anhydrous) have been described previously. Coal samples
were obtained from the Coal Research Section, Pennsylvania State University.
All other materials were of commercial origin a n d used as received.

153
 Reactions were c a r r i e d out i n b o r o s i l i c a t e glass tubes f i t t e d
w i t h a m d i u m - p o r o s i t y f r i t t e d glass f i l t e r t o p r o v i d e two chambers o f ca.
20 mL c a p a c i t y each. The chambers w e r e t e r m i n a t e d w i t h l a s s t u b i n g of-
d i f f e r e n t s i z e s : one end p e r m i t t e d i n t r o d u c t i o n o f lump f ~ .
and t h e o t h e r end f a c i l i t a t e d easy s e a l i n g under vacuum. For r e a c t i o n s
1 cm) coal

a t e l e v a t e d temperatures, these tubes were placed i n a P a r r model 4641

autoclave r e a c t o r .
I n a t y p i c a l experiment, t h e r e a c t i o n tube was charged w i t h a coal
sample (G. 5 g) sealed on one end, and thoroughly evacuated. A f t e r
d i s t i l l a t i o n o f s u l f u r dioxide (s. 8 mL) i n t o t h e tube a t -78"C, t h e
r e a c t i o n tube was cooled t o -196°C and sealed a t t h e o t h e r end. Upon
warming to room temperature, t h e tube, along w i t h o t h e r s , was p l a c e d i n
t h e autoclave and t h e autoclave was evacuated. The autoclave was then
charged w i t h g.100 mL o f l i q u i d SO, t o p r o v i d e backing pressure f o r t h e
r e a c t i o n tubes a t e l e v a t e d temperatures, closed, and heated a t z. 4"C/min
t o t h e r e a c t i o n temperature. A f t e r maintenance o f t h e r e a c t i o n temperature
f o r 60 min, t h e autoclave was cooled, depressurized, and opened. Each
r e a c t i o n tube was then i n v e r t e d i n a c o l d bath a t -78°C t o separate t h e
l i q u i d SO, from t h e coal by f i l t e r a t i o n v i a t h e i n t e r n a l frit. The r e d t o
orange c o l o r e d l i q u i d SO, s o l u t i o n was frozen, t h e tube was opened, t h e
coal was t r a n s f e r r e d t o another c o n t a i n e r , and a l l v o l a t i l e m a t e r i a l s were
a l l o w e d t o evaporate o v e r a two hour p e r i o d . The viscous, o i l y e x t r a c t
remaining a f t e r e v a p o r a t i o n o f the l i q u i d SO, was r e t a i n e d f o r subsequent
a n a l y s i s . The t r e a t e d coal was washed f o r a n a l y t i c a l purposes i n a
Buchner funnel w i t h s e q u e n t i a l a l i q u o t s o f d i s t i l l e d water, acetone, water,
3.8 M n i t r i c acid, water, and acetone u n t i l no y e l l o w c o l o r was observed i n
each wash l i q u i d . The coal was then d r i e d a t 110°C and analyzed f o r s u l f u r .
In separate washing experiments w i t h t h e raw coals, no y e l l o w c o l o r was
observed i n the wash l i q u i d s ; subsequent s u l f u r analyses o f t h e coal
i n d i c a t e d t h a t o n l y i n o r g a n i c s u l f u r was removed from t h e raw coal by t h i s
wash procedure.
F o r comparison o f t h e r e s u l t s o f these c o a l / l i q u i d SO2 experiments,
two o t h e r types o f experiments were a l s o run. A u t h e n t i c samples o f i r o n
p y r i t e were t r e a t e d w i t h l i q u i d SO2 and l i q u i d S0,/H20 m i x t u r e s a t 100°C
u s i n g procedures analogous t o those described above; no apparent r e a c t i o n
occurred. Samples (ca. 4 9) o f PSOC 267 were t r e a t e d w i t h 10 mL o f phenol
and p-cresol i n s e a l x tubes a t 181" and 2OOoC, r e s p e c t i v e l y . The coal was
subsequently washed i n a Buchner funnel w i t h d i s t i l l e d w a t e r and acetone,
d r i e d a t l l O ° C , and analyzed f o r s u l f u r .
A l l s u l f u r analyses, a t l e a s t i n t r i p l i c a t e , were accomplished w i t h a
, F i s h e r m d e l 470 s u l f u r analyser. F i e l d - i o n i z a t i o n mass spectra were obtained
on a Varian model MAT CH5 spectrometer w i t h sample temperatures from 120"-
280°C. The 'H and 1 3 C nmr spectra w e r e recorded on a JEOL FX9OQ F o u r i e r
t r a n s f o r m spectrometer f i t t e d w i t h a broadband probe and deuterium l o c k .
Samples were i n CDCl, s o l u t i o n w i t h i n t e r n a l TMS reference. I n f r a r e d spectra
of t h e e x t r a c t ( t h i n f i l m on NaCl p l a t e s ) were recorded on a Perkin E l m e r
model 621 spectrometer. T h i n - l a y e r chromatography o f t h e e x t r a c t was
c a r r i e d o u t w i t h t h e nmr sample s o l u t i o n s u s i n g s i l i c a gel ( S i - 3 0 ) p l a t e s .
E l u t i o n was accomplished w i t h 10% acetone/hexane, 30% acetone/hexane, and
absolute e t h a n o l ; e i t h e r I, vapor o r phosphomolybdic a c i d ( 5 % w/v i n ethanol)
was used t o develop t h e p l a t e s .

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RESULTS AND DISCUSSION

Precombustion d e s u l f u r i z a t i o n o f coal has been a t o p i c o f immense

i n t e r e s t and importancelO*ll since i t o f f e r s an a l t e r n a t i v e t o i n s t a l l a t i o n
and o p e r a t i o n o f expensive post-combustion scrubbers f o r conventional
combustion systems. Although a v a r i e t y o f processes are a v a i l a b l e f o r
precombustion removal o f i n o r g a n i c s u l f u r compounds, p r a c t i c a l procedures
f o r removal o f c o v a l e n t l y bound organic s u l f u r are r e l a t i v e l y uncommon.
Thus, a p p l i c a t i o n o f novel chemical approaches t o t h e problem would appear
t o be appropriate. E a r l y reports12 o f t h e a b i l i t y o f l i q u i d SO2 t o
d i s i n t e g r a t e a v a r i e t y o f coals and t o e x t r a c t a p o r t i o n o f t h e coal along
w i t h o u r previous experience w i t h t h i s s o l v e n t suggested i n v e s t i g a t i o n o f
t h e u t i l i t y o f l i q u i d SO2 as a means o f removing organic s u l f u r from coal.
Ifsuccessful, such a procedure would u t i l i z e a p o l l u t a n t t o remove t h e
source o f t h a t p o l l u t a n t .
L i q u i d s u l f u r d i o x i d e i s recognized as an e x c e l l e n t s o l v e n t f o r
aromatic, h e t e r o c y c l i c , and a l k y l s u l f i d e s 8 which can be d e r i v e d from
coa1.1,2y13 As a l i q u i d , SO2 i s n o t e a s i l y o x i d i z e d o r reduced and t h e
adducts responsible f o r i t s s o l v e n t p r o p e r t i e s are both t h e r m a l l y and
h y d r o l y t i c a l l y l a b i l e ; 8 thus any contamination o f t h e coal by r e s i d u a l
s u l f u r d i o x i d e should be r e a d i l y e l i m i n a t e d . Although o t h e r i n t e r a c t i o n s
and r e a c t i o n s w i l l be considered i n f u t u r e r e p o r t s , o n l y r e a c t i o n s based
on the m i l d Lewis a c i d c h a r a c t e r i s t i c s o f l i q u i d SO2 are o f importance
here. Thus, t h e r e a c t i o n o f s i g n i f i c a n c e i s summarized by Eq.1:
I I
-s:.. f so2 -+ -?:SO2 (1)
Products from t h i s r e a c t i o n are u s u a l l y h i g h l y c o l o r e d and h i g h l y s o l u b l e
i n l i q u i d SO,.8 Physical d i s i n t e g r a t i o n o f t h e coal by l i q u i d SO,, probably
v i a s i m i l a r donor-acceptor r e a c t i o n s w i t h aromatic, amine, and oxygen
c o n t a i n i n g f u n c t i o n a l groups, would serve t o promote t h e r e a c t i o n i n Eq.1.
I t should be emphasized t h a t f r e q u e n t l y , t h e chemical p r o p e r t i e s o f l i q u i d
SO2 can be s i g n i f i c a n t l y a l t e r e d by t h e presence o f cosolvents;8 o f t e n ,
undesirable side r e a c t i o n s occur i n such mixed media.
The c h a r a c t e r i s t i c s o f t h e bituminous c o a l s u t i l i z e d i n these
p r e l i m i n a r y i n v e s t i g a t i o n s are given i n Table I;o u r s u l f u r analyses are
given i n parentheses. PSOC 267 and 270 were chosen since t h e y c o n t a i n
s i g n i f i c a n t amounts o f o r g a n i c s u l f u r b u t l i t t l e p y r i t i c s u l f u r which
might confuse i n t e r p r e t a t i o n o f p r e l i m i n a r y r e s u l t s . Our analyses o f
PSOC 270 reveal t h a t , a l t h o u g h t h e lumps i n o u r sample had t h e composition
i n d i c a t e d i n Table I,t h e f i n e s i n o u r sample had a s u l f u r content o f
-
ca. 6% w i t h the a d d i t i o n a l s u l f u r being p y r i t i c . A l l r e s u l t s r e p o r t e d here
concern t h e lump coal o f PSOC 270. For comparison, PSOC 194 which c o n t a i n s
both p y r i t i c and o r g a n i c s u l f u r and PSOC 319 which contains o n l y p y r i t i c
s u l f u r were a l s o examined. Use o f t h e f r i t t e d glass r e a c t i o n tubes
f a c i l i t a t e d observation o f r e a c t i o n s , i s o l a t i o n o f t h e e x t r a c t e d m a t e r i a l ,
and r a p i d examination o f several coals and r e a c t i o n c o n d i t i o n s .
The r e s u l t s are summarized i n Table 11. A t room temperature,
l i q u i d SO2 r e a d i l y wets each o f t h e coals and begins t o develop a y e l l o w
c o l o r upon c o n t a c t . The y e l l o w c o l o r becomes more i n t e n s e upon s t a n d i n g
and changes t o intense orange o r red-orange a f t e r heating. The c o l o r
i n d i c a t e s t h e d i s s o l u t i o n o f donor-acceptor compounds formed between
t h e s o l v e n t and coal c o n s t i t u e n t s ; t h e i n c r e a s i n g i n t e n s i t y accompanies

155
an increasing concentration of these adducts. Disintegration of coal
lumps was observed f o r PSOC 267, 270, and 319; the extent of disinte-
gration increases progressively in the order l i s t e d . Although lumps of
PSOC 194 were not disintegrated, close examination revealed appreciable
swelling a n d expansion along fissures. I t should be realized t h a t t h e
only mechanical agitation used d u r i n g these experiments was a mild shaking
of the tubes t o i n i t i a l l y mix the materials. A t t h i s stage, there does n o t
appear t o be an obvious pattern which links maceral content t o degree of
disintegration .
Inspection of Table I1 reveals t h a t significant amounts of SO, are
retained on the coal (Exp. 1 ) . Effective removal of t h i s residual SO2 i s
essential. Mild heating (110°C) and washing with water or aqueous detergent
solutions were l e s s e f f e c t i v e t h a n the wash solution used in Exp. 2 . When
used alone, organic solvents are more e f f e c t i v e than mineral acid o r base
(compare Exp. 2 and 3 with Exp. 4 , 5, and 6 ) . The u t i l i t y of washing with
the organic liquids f o r removal of the yellow SO2 adducts increases in the
order: hexane, benzenesCClpethano1, and acetone. A sequence of washes
u s i n g acetone, water, and HN03 (Exp. 7) effectively removes the residual
SO, in most cases. Since the wash sequence was carried out during a
f i l t e r a t i o n operation contact time with the HNO, was insufficient t o
appreciably modify the coal material i t s e l f ; separate wash experiments
using the acetone, water, HN03 sequence with the raw coal (PSOC 267 a n d 270)
i t s e l f indicated t h a t no appreciable mass change occurred and t h a t no
yellow materials were obtained under these wash conditions. Where pyrite
i s n o t present, t h e s u l f u r content of the coal a f t e r t h i s wash sequence
represents the organic s u l f u r remaining in the coal a f t e r t h e liquid SO2
treatment. For PSOC 267 and 270, G. 37%and 25%, respectively, of the
organic sulfur can be removed by simple treatment of t h e lump coal with
liquid Sop. Grinding the lump coal PSOC 270 (-60 mesh) improves the
percentage organic s u l f u r removal t o g.48%. Present results with coals
containing pyrite are l e s s e a s i l y interpreted since the wash sequence
probably does n o t completely remove the pyrite. Furthermore, in separate
experiments with authentic pyrite samples, i t was demonstrated t h a t neither
liquid SO2 nor l i q u i d S02/H,0 mixtures react with pyrite. For PSOC 319,
where virtually a l l t h e s u l f u r i s p y r i t i c , the measured value of 1.6%
s u l f u r a f t e r SO, treatment probably represents pyrite which i s not removed
in the wash sequence. For PSOC 194, the measured value of 2.1% s u l f u r a f t e r
liquid SO2 treatment more t h a n likely represents both unreacted organic
and p y r i t i c s u l f u r . With PSOC 194, the f a i l u r e of liquid SO, to disintegrate
the coal probably limited extraction o f the organic s u l f u r by the SO,.
Extraction o f powdered PSOC 267 with phenol and p-cresol resulted
in 52% and 66%, respectively, remval of organic s u l f u r compared to 37%
by liquid SO,. The r e s u l t s of the extractions with phenol and p c r e s o l
are similar to those reported elsewhere for other coals.
Although these r e s u l t s with liquid SO, a r e n o t a s impressive
as those with phenol and e-cresol, i t has been demonstrated t h a t organic
Sulfur can be removed by extraction with l i q u i d SO,. I t i s also important
to note that optimum conditions f o r liquid SO2 extraction and f o r residual
So2 removal have as y e t t o be established. Furthermore, these preliminary
results when compared with other worker's r e s u l t s l 0 f o r a variety of organic
sol vents, are s u f f i c i e n t l y encouraging t o indicate t h a t treatment with
liquid So2 should be investigated further. Experiments t o define conditions

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more c a r e f u l l y and t o i n v e s t i g a t e t h e use o f a p p r o p r i a t e reagents t h a t
w i l l enhance t h e removal o f s u l f u r compounds f r o m coal by l i q u i d SO2
are underway.
The m a t e r i a l o b t a i n e d by evaporation o f t h e SO2 e x t r a c t i o n l i q u i d
comprises 5-10% o f the o r i g i n a l coal. F b s t o f t h i s o i l y e x t r a c t d i s s o l v e s
i n chloroform, acetone, and concentrated HC1 ; t h i s m a t e r i a l i s o n l y p a r t i a l l y
s o l u b l e i n benzene and i s i n s o l u b l e i n hexane. Very f i n e l y d i v i d e d
p a r t i c u l a t e matter, observed t o be i n suspension i n t h e c h l o r o f o r m and
acetone s o l u t i o n s appears t o resemble h i g h m l e c u l a r weight m a t e r i a l
o b t a i n e d by Larsen and Choudhury13 d u r i n g t h e i r i n v e s t i g a t i o n o f t h e
effectiveness o f coal depolymerization r e a c t i o n s . Although i t i s l i k e l y
t h a t l i q u i d SOn under these c o n d i t i o n s merely e x t r a c t s lower m o l e c u l a r
w e i g h t m a t e r i a l a1 ready i n t h e coal, some small degree o f depolymerization
c o u l d a1 so be o c c u r r i n g .
T h i n - l a y e r chromatography o f t h e l i q u i d SOn e x t r a c t from PSOC 267
was c a r r i e d o u t u s i n g a c h l o r o f o r m s o l u t i o n f o r d e p o s i t i o n and e l u t e d w i t h
P r o g r e s s i v e l y more p o l a r solvents; long-wavelength UV i l l u m i n a t i o n was used
t o observe fluorescence i n t h e samples. Although no d i s t i n c t bands were
developed upon e l u t i o n , three d e f i n i t e f r a c t i o n s t h a t d i f f e r by p o l a r i t y
o f c o n s t i t u e n t s were apparent on t h e p l a t e s . Several conclusions can be
drawn from these TLC experiments. The complete sample contains e a s i l y
o x i d i z a b l e f u n c t i o n s . A l l a l k y l f u n c t i o n s are attached t o aromatic
residues. The l e s s conjugated ( b l u e f l u o r e s c e n t ) f r a c t i o n i s l e s s p o l a r
than the more conjugated (orange f l u o r e s c e n t ) f r a c t i o n . A very p o l a r
f r a c t i o n , n o t t r a n s p o r t e d by any e l u e n t used, i s even m r e h i g h l y conjugated
(red fluorescent). These observations are c o n s i s t e n t w i t h t h e types o f
s t r u c t u r e s 1 4 known t o e x i s t i n c o a l s as w e l l as w i t h t h e spectroscopic
measurements t o be described n e x t .
The f i e l d i o n i z a t i o n mass spectrum o f t h e l i q u i d SOn e x t r a c t from
PSOC 267 i s i l l u s t r a t e d i n Fig. 1; t h e corresponding spectrum o f t h e e x t r a c t
f r o m PSOC 270 i s s i m i l a r i n several f e a t u r e s . The molecular weight
d i s t r i b u t i o n i n these spectra are n o t as broad n o r i s t h e average m o l e c u l a r
weight as h i g h as might have been expected.14 The presence o f very f i n e l y
d i v i d e d p a r t i c u l a t e m a t t e r , which presumably has h i g h e r molecular weight
components t h a t are n o t v o l a t i l i z e d under t h e measurement conditions, c o u l d
be responsible f o r such observations. The s p e c t r a c o n t a i n s t r i k i n g p a t t e r n s
i n which the mass d i f f e r e n c e among major components i s 14 amu. These
p a t t e r n s suggest t h e presence o f a v a r i e t y o f CH2 c o n t a i n i n g s t r u c t u r e s .
I t i s tempting t o assign another p a t t e r n near m/e = 184 t o dibenzothiophene
s i n c e i t s t r o n g l y resembles t h a t o b t a i n e d w i t h an a u t h e n t i c dibenzothiophene
sample. The l a c k o f h i g h r e s o l u t i o n mass s p e c t r a l data, however, makes such
an assignment pure s p e c u l a t i o n a t t h i s stage.
The i n f r a r e d spectrum o f t h e l i q u i d SO2 e x t r a c t o f PSOC 267 ( n e a t ,
t h i n f i l m ) i s shown i n Fig. 2. I t i s apparent t h a t t h e e x t r a c t c o n t a i n s
0-H, N-H, aromatic and a l i p h a t i c C-H groups, a v a r i e t y o f s u b s t i t u t e d aromatic
s t r u c t u r e s , and probably ethers. There i s no evidence o f e i t h e r r e s i d u a l
so2 o r o f o r g a n i c s t r u c t u r e s c o n t a i n i n g SO2 s u b s t i t u t i o n ; no procedures o t h e r
than evaporation o f the l i q u i d SOn under ambient c o n d i t i o n s were used t o
process t h i s e x t r a c t .

157
 Proton and l 3 C ( p r o t o n n o i s e decoupled) nmr spectra o f t h e l i q u i d
SO2 e x t r a c t of PSOC 267 are shown i n Fig. 3. Q u a l i t a t i v e l y , t h e p r o t o n
spectrum resembles t h a t o f CS2 e x t r a c t s o f o t h e r bituminous coals as
r e p o r t e d by Retcofsky and F r i e d e l ;15 o u r assignments f o l l o w those o f
these workers. The s i g n a l s w i t h 6 ~ 1 . 8are assignable t o a l k y l t y p e protons,
those with 2.0 <6<3.5 are assignable t o b e n z y l i c t y p e protons and those
w i t h 6.9 < 6 < 8.8 are assignable t o aromatic type protons; t h e s i g n a l
a t 6 G.4.8 i s a t t r i b u t e d t o p h e n o l i c and a l c o h o l i c t y p e protons.
I n t e g r a t e d i n t e n s i t i e s p r o v i d e t h e f o l l o w i n g d i s t r i b u t i o n o f protons:
20.9% aromatic, 1.9% -OH, 32.1% b e n z y l i c , and 45.1% o t h e r a l k y l types.
I t would appear t h a t t h e alkyl-H/aromatic-H r a t i o i s h i g h e r f o r t h i s e x t r a c t
than f o r CS2 e x t r a c t s o f bituminous coals w i t h s i m i l a r carbon c o n t e n t
(84.6% C i n PSOC 267).
The 1 3 C nmr spectrum r e v e a l s f u r t h e r d e t a i l concerning t h e types o f
s t r u c t u r e s found i n t h e l i q u i d SO2 e x t r a c t o f PSOC 267 s i n c e assignments are
r e a d i l y made by r e f e r e n c e t o the work o f F i s c h e r e t a1.16 Features i n
common w i t h b o t h SRC e x t r a c t s and methylnaphthalene e x t r a c t s o f bituminous
coal a r e found i n t h e l i q u i d SO2 e x t r a c t . The sharp s i g n a l a t 14.1 ppm
i s assigned t o t e r m i n a l methyl groups on a l i p h a t i c s i d e chains, t h a t a t
19.8 ppm t o unhindered a r y l i c methyl groups, and those a t 22.7 and 31.9 ppm
t o a and 6 methylene carbons, r e s p e c t i v e l y , on t e t r a l i n t y p e s t r u c t u r e s .
The sharp, dominant resonance a t 29.7 ppm i s r e a d i l y assigned t o methylene
carbons i n Ar-CH2-CH2-Ar' groups whereas t h e weaker s i g n a l s a t 32.6, 37.4,
and 39.2 ppm are c h a r a c t e r i s t i c o f s i n g l e methylene carbons b r i d g i n g aromatic
s t r u c t u r e s . The broad, low f i e l d band w i t h a h i g h e r f i e l d asymmetry i s
t y p i c a l o f a composite o f aromatic type carbons. I n d i v i d u a l sharp s i g n a l s
w i t h i n t h i s band correspond t o a1 t e r n a t e p o l y n u c l e a r aromatics t h a t are
p a r t i a l l y s u b s t i t u t e d . 1 6 The apparent absence o f s i g n a l s a t even l o w e r
f i e l d s from carbon atoms w i t h o u t p r o t o n s u b s t i t u e n t s i s a t t r i b u t e d t o l a c k
o f NOE enhancement f o r these n u c l e i .
Thus t h e l i q u i d SO2 e x t r a c t o f PSOC 267 has been shown t o c o n t a i n
coal c o n s t i t u e n t s s i m i l a r t o those o b t a i n e d by e x t r a c t i o n w i t h common organic
solvents. Although an abundance o f a l k y l groups (methyl and e s p e c i a l l y
methylene) i s found i n t h e carbon s t r u c t u r e s as i l l u s t r a t e d by t h e i n f r a r e d ,
1 3 C nmr, and mass spectra, i t i s n o t c l e a r whether t h i s i s r e p r e s e n t a t i v e
of PSOC 267 composition o r i s a consequence o f t h e p r o p e r t i e s o f l i q u i d SO2.
Less i s known about t h e composition o f heteroatom compounds i n t h e e x t r a c t :
OH, NH and probably e t h e r groups are apparent b u t a v a i l a b l e s p e c t r a l data
do n o t r e v e a l o t h e r groups such as might be found i n organic s u l f u r
compounds. U n f o r t u n a t e l y , t h e spectra o b t a i n e d a r e n o t s e n s i t i v e t o d i v a l e n t
s u l f u r c o n t a i n i n g o r g a n i c s t r u c t u r e s and r e 1 i a b l e elemental analyses were
precluded by 1 ack o f s u f f i c i e n t m a t e r i a l . Since b e t t e r c h a r a c t e r i z a t i o n
of t h i s e x t r a c t may e v e n t u a l l y provide clues concerning the a b i l i t y o f
l i q u i d SO2 t o remove o r g a n i c s u l f u r compounds, such e f f o r t s a r e t o be
ma de.
I n summary, p r e l i m i n a r y experiments have demonstrated t h a t l i q u i d SO2
can be used t o remove o r g a n i c t y p e s u l f u r compounds from bituminous coals
and t h a t t h e l i q u i d SO2 e x t r a c t contains c o a l components s i m i l a r t o those
found by e x t r a c t i o n w i t h o r g a n i c solvents. The a b i l i t y o f l i q u i d SO2 t o
d i s i n t e g r a t e some c o a l s and t o f r a c t u r e o t h e r s has been confirmed. Conditions
t o optimize t h e removal o f s u l f u r compounds from coal and t o f a c i l i t a t e
removal o f r e s i d u a l SO2 from t h e coal a r e under i n v e s t i g a t i o n .

158
 ACKNOWLEDGEMENTS

The support o f t h i s research by t h e Department o f Energy, under

Contract No. ET-78-G-01-3316, i s g r a t e f u l l y acknowledged.

REFERENCES

1. D.W. van Krevelen, "Coal: Typology, Chemistry, Physics, and C o n s t i t u t i o n " ,

E l s e v i e r , Amsterdam, 1961.

2. H.H. Lowry, "chemistry o f Coal U t i l i z a t i o n " , Wiley, New York, 1945, Vol. 1,
Chapter 19.

3. R.M. Baldwin, J.O. Golden, J.H. Gary, R.L. Bain, and R.J. Long, i n "Coal
Processing Technology", American I n s t i t u t e o f Chemical Engineers, New York,
Vol. 2, p. 128 (1975).

4. R.P. Anderson, x.,

p. 130.

5. S. Morooka and C.E. Hamrin, Jr., Chem. Eng. Science, 8,521 (1979).

6. L. F. Audrieth and J. Kleinberg, "Non-Aqueous Solvents", Wiley, New York,

1953, Chapter 11.

7. W.K.T. Gleim, U.S. Patent 4, 120, 664, 1978.

8. D.F. Burow, " S u l f u r Dioxide" i n The Chemistry o f Non-Aqueous Solvent

Systems, J.J. Lagowski, Ed., Vol. 3, 1970, p. 138.

9. D.F. Burow, Inorg. Chem., 2,573 (1972).

10. R.A. k y e r s , "Coal D e s u l f u r i z a t i o n " , Marcel Dekker, New York, 1977.

11. "Coal D e s u l f u r i z a t i o n " , T.D. Wheelock, Ed., ACS Symposium S e r i e s No. 64,
ACS, Washington, D.C., 1977.

12. F. Fischer and W . Gluud, Chem. Ber., g , 147 (1916).

13. J.W. Larsen and P. Choudhury, J. Org. Chem., ~, 2856 (1979).

14. "Organic Chemistry o f Coal", J.W. Larsen, Ed., ACS Symposium S e r i e s

No. 71, ACS, Washington, D.C., 1978.

15. H.L. Retcofsky and R.A. F r i e d e l i n "Spectrometry o f Fuels", Plenum,

New York, 1970, Chapter 6.

16. P. Fischer, J.W. Stadelhofer, and M. Zander, 3 , 345

H, (1978).

159
TABLE 1 . C h a r a c t e r i s t i c s of Bituminous Coals Treated w i t h L i q u i d SO2

COAL (PSOC NO.)

194 26 7 2 70 31 9

Type HVB H VA H VA LV

Origin OH VA AL PA

Macerals ( % / v )
Vitrinite 73.3 60.9 68.1 85.5
P. V i t r i n i t e 12.6 5.3 3.2 4.2
Micrini te 3.3 15.6 9.1 1 .o
Fusi n i t e 2.2 8.7 8.6 4.3
S. F u s i n i t e 2.3 3.4 4.6 4.0
Res in it e 3.6 1.5 0.8 0.0
SDorini t e 1.8 3.2 5.0 0.5

Elemental Analysis (DAF)

%C 78.23 84.63 83.34 86.49
%H 5.56 5.58 5.55 4.57
%N 1.72 2.53 1.74 1.61
%0(d i f f ) 10.97 5.18 6.59 0.16
%S( t o t a l ) 3.51 2.08 2.77 7.17
(1 .967)a (2.682)a

organic 1.26 2.01 2.70 0.10

pyri t i c 2.19 0.02 0.02 7.00
s u l f a ti c 0.07 0.05 0.05 0.07

aAnalyses done i n t h i s work.

160
TABLE 2. Experimental Results
Sample Exp. React ion Organic
Wash %S Sulfur
(PSOC No.) No.
Temp.( "C) Removed

2 70
1 ump 150 5.756
1ump 150 1.5M NaOH,H20 3.802
1 ump 150 3M HC1 ,H20 3.522
1ump 150 H20 .C6H6 2.682
1ump 100 CC14 2.602
1 ump 100 acetone 2.316
1 ump b 2.005
150 mu1t i p l e 25%
1ump 100 3.089
b
1 ump 100 mu1t i p l e 1.992 25%
d b
powder 75 mu1t ip l e 1.397 4 8%

26 7
b
1 ump 75 mu1t i p l e 1.241 3 7%
d
powder 180 H20 ,acetone 0.9394 52%
d
powder 200 H20 ,acetone 0.6580 66%

194
b
1ump 100 mu1 t i p l e 2.134

31 4
b
1 ump 100 mu1t i p l e 1.584

a. F o r l i q u i d SO2 r e a c t i o n s , 60 min r e a c t i o n time was used and f o r o r g a n i c

s o l v e n t r e a c t i o n s , 5 h r was used.
b. The m u l t i p l e wash c o n s i s t e d o f t h e use o f s e q u e n t i a l a l i q u o t s o f acetone,
H20, 3.8 M HN03, H20, acetone (see t e x t ) .
c. The S02/benzene s o l u t i o n was s. 1:l ( v o l ) .
d. Lump coal was crushed and ground t o -60 mesh.

161
 h
W
N
V
0
LL
v,

c
m
0
U

4-
0
u
u
m
L
u
x
W
N
0
v,
-0
.r
3
0-
.r
c

W
u
.c
4-
0

162
163
B ..

. . . . . .

..
6 9 PPm

FIGURE 3. Nuclear magnetic resonance spectra o f the liquid SO2 extract o f

coal PSOC 267 ( C D C 1 , ,solution, 5 mm tube). A . l 3 C nmr spectrum,
proton noise decoupled, 2000 pulses 8. 'H nmr spectrum, 10 pulses.

164
 E v a l u a t i o n o f O x y d e s u l f u r i z a t i o n Processes f o r Coal
I. The E f f e c t o f t h e Ames Process on Model O r g a n o s u l f u r Compounds

L. W. Chang, W. F. Goure, T. G . S q u i r e s , and T . J. B a r t o n

Ames L a b o r a t o r y , US DOE and Department o f Chemistry

Iowa S t a t e U n i v e r s i t y
Ames, Iowa 50011

INTRODUCT I ON

One o f t h e main o b s t a c l e s t o t h e use of c o a l as an a l t e r n a t e energy source i s

t h a t i t c o n t a i n s s u l f u r w h i c h c o n t r i b u t e s t o a i r p o l l u t i o n when t h e c o a l i s burned.
I t i s e s t i m a t e d t h a t o n l y few p e r c e n t of c o a l s i n t h e U n i t e d S t a t e s w i l l be a b l e t o
meet EPA SO emission s t a n d a r d s ( I ) . A l t i o u g h some chemical procedures have been
2
r e p o r t e d t o be e f f e c t i v e f o r d e s u l f u r i z a t i o n o f c o a l s , most, i f n o t a l l , o f t h e s u l -
f u r t h a t i s removed i s i n o r g a n i c . There i s l i t t l e i n f o r m a t i o n about what a c t u a l l y
happens t o t h e o r g a n i c s u l f u r when c o a l s a r e s u b j e c t e d t o these process c o n d i t i o n s .
A major reason f o r t h i s ignorance i s t h e l a c k o f i n f o r m a t i o n about t h e n a t u r e and
d i s t r i b u t i o n o f t h e o r g a n o s u l f u r f u n c t i o n a l groups i n t h e c o a l .
R e c e n t l y , s e v e r a l workers have r e p o r t e d t h a t o r g a n i c s u l f u r as w e l l a s i n o r g a n i c
s u l f u r can be removed by o x i d a t i v e processes ( 2 - 6 ) . Wheelock, e t . a l . ( 2 ) r e p o r t e d
t h a t under t h e f o l l o w i n g c o n d i t i o n s : 150OC, 200 p s i g 0 0 . 2 M aq. NaZC03, 1 hour;
up t o 40% o f t h e o r g a n i c s u l f u r can be removed f r o m c o a j ’ w i t h o u t significantly r e -
ducing the recovery o f combustible organic matter.
I n t h i s paper we w i s h t o r e p o r t o u r e v a l u a t i o n o f t h e e f f e c t i v e n e s s of t h i s Ames
process i n t h e d e s u l f u r i z a t i o n o f c o a l . I n s t e a d o f u s i n g c o a l , model o r g a n o s u l f u r
compounds were s u b j e c t e d t o Ames process c o n d i t i o n s . Our approach i s based on t h e
assumption t h a t a d e f i n i t i v e knowledge o f t h e o r g a n o s u l f u r f u n c t i o n a l groups and
t h e i r d i s t r i b u t i o n i n coal i s not a p r e r e q u i s i t e f o r i n v e s t i g a t i n g the v i a b i l i t y o f
d e s u l f u r i z a t i o n processes. Thus, i t i s s u f f i c i e n t t o measure t h e p r o p e n s i t y o f a
r e p r e s e n t a t i v e spectrum o f o r g a n o s u l f u r model m a t e r i a l s toward d e s u l f u r i z a t i o n under
process c o n d i t i o n s .
I n o u r study, t h e f o l l o w i n g o r g a n o s u l f u r compounds have been s u b j e c t e d t o Ames
process c o n d i t i o n s e i t h e r by themselves o r i n t h e presence o f c o a l . For comparison,
some model s u l f u r compounds were also r u n under t h e same c o n d i t i o n s except t h a t n i -
trogen was used i n p l a c e o f oxygen. The r e s u l t s o f o u r s t u d y a r e summarized i n
Tables I and 1 1 .

m
 E X P E R I MENTAL

Reactions i n t h e Absence o f Coal

The r e a c t i o n s were run e i t h e r i n an 1 l i t e r o r a 300 m l a u t o c l a v e . In a t y p i c a l

r u n , a p p r o x i m a t e l y 5 g ( f o r t h e I l i t e r a u t o c l a v e ) o r 1 gram ( f o r t h e 300 m l a u t o -
c l a v e ) of o r g a n i c s u l f i d e was p l a c e d i n a g l a s s l i n e r o f an a u t o c l a v e . A f t e r adding
300 m l ( I 1 a u t o c l a v e ) or 50 m l (300 m l a u t o c l a v e ) o f 0 . 2 M aqueous sodium c a r b o n a t e
s o l u t i o n , t h e r e a c t o r was s e a l e d , f l u s h e d w i t h N2, and heated as r a p i d l y as p o s s i b l e
t o 150OC. A f t e r t h e r e a c t o r had e q u i l i b r a t e d a t 15OoC (10-15 m i n u t e s ) , t h e system
was p r e s s u r i z e d t o 200 p s i g w i t h oxygen and t h e r e a c t o r was f l u s h e d w i t h a slow
stream o f oxygen f o r 3 m i n u t e s . A c o l d t r a p was connected t o t h e v e n t tube o f t h e
a u t o c l a v e t o c o l l e c t t h e s t a r t i n g s u l f i d e ( u s u a l l y a s m a l l amount) w h i c h escaped
from t h e r e a c t o r d u r i n g t h e f l u s h i n g process ( t h e c o l l e c t e d s u l f i d e was combined
w i t h t h e r e a c t i o n m i x t u r e i n t h e a u t o c l a v e a f t e r t h e r e a c t i o n ) . The r e a c t o r was
t h e n sealed, and t e m p e r a t u r e (I5O0C), s t i r r i n g (1500 rpm) and p r e s s u r e (200 p s i g )
were m a i n t a i n e d f o r one hour. D u r i n g t h e i n i t i a l p r e s s u r i z a t i o n and t h e f i r s t 20-
30 minutes o f t h e r e a c t i o n , c o o l i n g o f t h e r e a c t o r w i t h water was sometimes r e q u i r e d .
A f t e r one h o u r , t h e h e a t e r was t u r n e d o f f ; t h e r e a c t o r was c o o l e d t o room tem-
p e r a t u r e and t h e c o n t e n t s w e r e p o u r e d i n t o a beaker. The r e a c t o r and t h e g l a s s l i n e r
were washed w i t h benzene and w i t h w a t e r . The r e a c t i o n m i x t u r e and t h e s e washings
were combined and e x t r a c t e d w i t h benzene, and t h e benzene e x t r a c t was d r i e d (Na SO4)
and f i l t e r e d . To t h e r e a c t i o n s r u n i n t h e 300 m l a u t o c l a v e an i n t e r n a l s t a n d a r 8 was
added d i r e c t l y t o t h e d r i e d benzene e x t r a c t and t h e s o l u t i o n was a n a l y z e d by gas
chromatography ( G C ) t o d e t e r m i n e t h e q u a n t i t y o f s t a r t i n g s u l f i d e l e f t and v o l a t i l e
compounds formed i n t h e r e a c t i o n . GC response f a c t o r s f o r t h e s u l f i d e s , p r o d u c t s
and t h e standards were g e n e r a t e d i n t h e form o f c a l i b r a t i o n t a b l e u s i n g s t a n d a r d so-
l u t i o n s c o n t a i n i n g t h e s u l f i d e , p r o d u c t s and t h e s t a n d a r d . For t h e r e a c t i o n s r u n i n
t h e 1 l i t e r a u t o c l a v e , t h e volume o f d r i e d and f i l t e r e d benzene e x t r a c t was a d j u s t e d
t o 500 rnl, and a 50 m l of a l i q u o t o f t h e benzene s o l u t i o n was w i t h d r a w n . An i n t e r -
n a l standard was added t o t h e 50 m l s o l u t i o n ; t h e s o l u t i o n was a n a l y z e d w i t h GC.
The e x t r a c t e d aqueous l a y e r of t h e benzyl phenyl s u l f i d e o r t h e b e n z y l methyl
s u l f i d e r e a c t i o n m i x t u r e was a c i d i f i e d w i t h c o n c e n t r a t e d h y d r o c h l o r i c a c i d , and wash-
ed w i t h benzene. The benzene washings were d r i e d (Na SO4) and f l a s h evaporated t o
a f f o r d a r e s i d u e w h i c h N M R and I R a n a l y s i s showed t o 6 e b e n z o i c a c i d . The r e m a i n i n g
aqueous l a y e r was e v a p o r a t e d t o d r y n e s s , and t h e r e s i d u e was a n a l y z e d b y NMR, IR,
and UV spectroscopy.

R e a c t i o n i n t h e Presence o f Coal Under Oxygen o r Under N i t r o g e n Atmosphere

The coal used was Iowa c o a l ( L o v i l i a , 200 mesh) and was d r i e d a t llO°C o v e r n i g h t .
The r e a c t i o n s i n t h e p r e s e n c e o f c o a l were r u n i n a 300 m l a u t o c l a v e . The r e a c t i o n
procedures were t h e same as t h o s e mentioned above e x c e p t t h a t E 4.0 g o f c o a l was
added t o t h e r e a c t i o n m i x t u r e f o r each r u n . A f t e r t h e r e a c t i o n , t h e r e a c t i o n m i x t u r e
and washings were combined and f i l t e r e d , and t h e f i l t r a t e was e x t r a c t e d w i t h benzene.
The c o a l c o l l e c t e d w i t h f i l t r a t i o n was washed w i t h acetone, t h e n benzene s e v e r a l
times. The benzene and t h e acetone-benzene e x t r a c t s were combined, d r i e d (Na2S04)
and analyzed w i t h GC u s i n g i n t e r n a l s t a n d a r d s .

RESULTS AND DISCUSSION

Tables I and I I d e m o n s t r a t e t h a t among t h e model compounds t h a t we s t u d i e d , o n l y

t h i o p h e n o l and compounds c o n t a i n i n g a b e n z y l i c s u l f i d e l i n k a g e were o x i d i z e d t o an
a p p r e c i a b l e e x t e n t . T h i o p h e n o l was c o n v e r t e d t o phenyl d i s u l f i d e which was r e s i s t a n t
t o further oxidation. Benzyl phenyl s u l f i d e was o x i d i z e d and c l e a v e d t o g i v e benzlde-
hyde, benzoic a c i d and b e n z e n e s u l f o n i c a c i d ; b e n z y l m e t h y l s u l f i d e gave s i m i l a r r e -
sults. The o t h e r model compounds were u n r e a c t i v e under t h e Ames proces's c o n d i t i o n s
e i t h e r b y themselves or i n t h e presence of c o a l . Even i n t h e presence o f c o a l , more
t h a n 70% of t h e s t a r t i n g s u l f i d e was recovered. The reduced r e c o v e r i e s o f s t a r t i n g

166
 Table I . R e a c t i o n R e s u l t s o f Compounds Run Under t h e Ames Process C o n d i t i o n s
i n t h e Absence o f Coala

Recovered Y i e l d (%)
Compound o f Starting Sulfide Product

Benzothiophene 87 -- - - -- -
Dibenzothiophene 96 - --- - - -
Th iphenol 0 Phenyl D i s u l f i d e

Phenyl s u l f i d e 98 -- - -- --

Phenyl m e t h y l s u l f i d e 89 -- - - - - -

Benzyl m e t h y l s u l f i d e 36 Benzoic a c i d
Benzaldehyde
Methanesulfonic a c i d

Benzyl phenyl s u l f i d e 29 Benzoic a c i d

Ben za 1 de hyd e
Benzenesulfonic a c i d

N-Octyl s u l f i d e 90 ----- --

a Ames p r o c e s s c o n d i t i o n s : 150°C, 200 p s i g 02, 0.2M aqueous Na C O 1 hour.

2 3’

Table I I . R e a c t i o n R e s u l t s o f Compounds Run Under t h e Ames Processa

b
C o n d i t i o n i n t h e Presence o f Coal

Recovered Y i e l d ( % )
Compound o f Starting Sulfide

NC
, 021!
- -
Dibenzothiophene 83 76
Phenyl s u l f i d e 76 74
Benzyl methyl s u l f i d e 75 13
N-octyl s u l f i d e -_ a2

a Ames process c o n d i t i o n s : 15OoC, 200 p s i g 02, 0.2M aqueous Na2C0 , 1

hour. blows L o v i l i a Coal. C R e a c t i o n r u n under n i t r o g e n atmosJhere.
R e a c t i o n r u n under oxygen atmosphere.

167
m a t e r i a l s i n t h e presence o f c o a l ( s e e T a b l e I I ) can be a t t r i b u t e d t o a b s o r p t i o n o f
t h e o r g a n o s u l f u r compound by t h e microporous s t r u c t u r e o f c o a l and t h e mechanical
loss a s s o c i a t e d w i t h w o r k i n g up t h e r e a c t i o n m i x t u r e . T h i s h y p o t h e s i s was confirmed
by t h e c o r r e s p o n d i n g l y low r e c o v e r i e s o f s t a r t i n g s u l f i d e s from r e a c t i o n s r u n i n
t h e presence o f c o a l under n i t r o g e n atmosphere--an i n e r t atmosphere. Furthermore,
no o x i d a t i o n p r o d u c t s were d e t e c t e d i n t h e r e a c t i o n m i x t u r e s . C l e a r l y , o f t h e com-
pounds i n v e s t i g a t e d t h u s f a r , o n l y benzyl s u l f i d e s and t h i o p h e n o l underwent any
chemical r e a c t i o n , and ( t h e benzyl s u l f i d e s were t h e o n l y compounds i n which carbon
s u l f u r bond c l e a v a g e o c c u r r e d .
The b a s e - c a t a l y z e d r e a c t i o n of compounds c o n t a i n i n g a b e n z y l i c s u l f i d e l i n k a g e
w i t h m o l e c u l a r oxygen has been s t u d i e d under a v a r i e t y o f c o n d i t i o n s . Wallace et.
-
a l . (7) r e p o r t e d t h a t benzyl phenyl s u l f i d e can be o x i d i z e d w i t h m o l e c u l a r oxygen i n
2M potassium t-butoxide-HMPA a t 80°C t o y i e l d b e n z o i c a c i d . The a u t h o r s proposed
t h a t t h e r e a c t i o n proceeded via t h e f o r m a t i o n o f an a - c a r b a n i o n f o l l o w e d by r e a c t i o n
between t h e i o n and oxygen.

@-CH
2
-S-@ base > 0-?H-S-@

0
@-EH-s-Q 2
> @-c-s-g
I
o-o-

The r e s u l t i n g a - p e r o x i d e a n i o n can then decompose i n e i t h e r a s t e p w i s e o r concerted

manner t o form benzaldehyde and b e n z e n e s u l f e n a t e which a r e o x i d i z e d t o t h e c o r r e s -
ponding c a r b o x y l i c and s u l f o n i c a c i d s . I n t h e f i r s t s t e p of t h i s mechanism, t h e
a - c a r b a n i o n i s s t a b i l i z e d by t h e d - o r b i t a l o f t h e a d j a c e n t d i v a l e n t s u l f u r atom.

0-

168
We b e l i e v e t h a t a s i m i l a r mechanism i s i n v o l v e d i n t h e o x i d a t i o n o f b e n z y l p h e n y l
s u l f i d e under Ames process c o n d i t i o n s .
O x y d e s u l f u r i z a t i o n o f t h e o r g a n i c s u l f i d e s i n c o a l has been f o r m u l a t e d as a
t w o - s t e p process (8): I . S e l e c t i v e o x i d a t i o n o f t h e s u l f u r t o s u l f o x i d e s and S U I -
fones w i t h t h e l a t t e r as t h e f a v o r a b l e p r o d u c t ; and 2 . Thermal d e c o m p o s i t i o n o f

- -
t h e o x i d a t i o n p r o d u c t s , u s u a l l y under b a s i c c o n d i t i o n s .

Step 1 .

R R 0
R\ '&
R"'s R'/s=o R,/ \o

Step 2 .

or .A >
Hydrocarbons + SOx

In t h i s f o r m u l a t i o n , t h e r e a c t i o n i s i n i t i a t e d by o x i d a t i o n o f t h e s u l f u r and, i n
f a c t , i s made p o s s i b l e by t h i s o x i d a t i o n w h i c h r e s u l t s i n p o l a r i z a t i o n and weakening
o f t h e carbon t o s u l f u r bonds ( 8 ) .
We f i n d no e v i d e n c e t o s u p p o r t t h i s h y p o t h e s i s ; o x i d a t i o n o f t h e s u l f u r was de-
t e c t e d o n l y in t h i o p h e n o l and i n t h e b e n z y l s u l f i d e s . I n t h e f i r s t case, o x i d a t i o n
o f mercaptans t o d i s u l f i d e s i s a f a c i l e r e a c t i o n known t o o c c u r under c o n d i t i o n s
such as t h e Ames p r o c e s s . No f u r t h e r o x i d a t i o n o f t h e d i s u l f i d e was d e t e c t e d . In
t h e l a t t e r case, we submit t h a t c a r b o n - s u l f u r bond c l e a v a g e i s i n i t i a t e d by o x i d a -
t i v e a t t a c k a t t h e b e n z y l p o s i t i o n i n s t e a d o f a t s u l f u r . T h i s p o s t u l a t e i s supported
by o u r r e c e n t d i s c o v e r y t h a t , under Ames p r o c e s s c o n d i t i o n s , f l u o r e n e was o x i d i z e d
r a p i d l y and q u a n t i t a t i v e l y t o f l u o r e n o n e w h i l e d i b e n z o t h i o p h e n e was removed unchanged
f r o m t h e same r e a c t i o n m i x t u r e .
O x i d a t i o n o f b e n z y l i c carbon hydrogen bonds i n p r e f e r e n c e t o s u l f u r would have
a s u b s t a n t i a l impact on t h e development o f processes for t h e o x y d e s u l f u r z a t i o n o f
c o a l . We i n t e n d t o i n v e s t i g a t e t h i s phenomenon and e x p l o r e methods f o r e d u c i n g or
r e v e r s i n g the r a t i o o f b e n z l i c t o s u l f u r o x i d a t i o n .

ACKNOWLEDGEMENTS

T h i s work was s u p p o r t e d by t h e U . S. Department o f Energy, c o n t r a c t No.

W-7405-Eng-82, D i v i s i o n o f F o s s i l Energy, budget code AA-10-03-03.

169
 REFERENCES

1. J. A. C a v a l l a r o , M. T. Johnston, and A. W. Deurbrouck, " S u l f u r Reduction Po-

t e n t i a l o f t h e Coals o f t h e U n i t e d S t a t e s ; A R e v i s i o n o f Report of I n v e s t i g a -
-
t i o n s 7633," R I 8118, U. S . Bureau o f Mines, 1976.

2. T . D . Wheelock, R . T . Greer, R . Markuszewski, and R. W. F i s h e r , "Advanced

Development o f F i n e Coal D e s u l f u r i z a t i o n and Recovery Technology," Annual
T e c h n i c a l P r o g r e s s Report, Oct. 1977 -
Sept. 1978. IS-4688 p r e p a r e d f o r
DOE-Fossil Energy, b y Ames L a b o r a t o r y , Iowa S t a t e U n i v e r s i t y , Arnes, Iowa.
A p r i l , 1979.

3. R. A. Meyers, "Coal Desulfurization," Mercel Dekker, I n c . , New York (1977).

4. P. S . G a n g u l i , G. C. Hus, G. R. Gavalas, and 5. H. K a l f a y a n , Am. Chem. SOC.,

D i v . Fuel Chem., P r e p r i n t , 3, 118 (1976).

5. S . S . Sareen, R. A. G i b e r t i , P. F. I r m i n g e r , and L . J . P e t r o v i c , AICHE Symp.

-
Ser., 2, 183 (1977).
6. S . Friedman and R . P . W a r z i n s k i , J. Eng. f o r Power, 2,361 (1977).
7. T. J. Wallace, H . P o b i n e r , F. A. Baron, and A. S c h r i e s h e i m , J. Org. Chem., 0,
3147 (1965).
8. A. A t t a r and W. H. Corcoran, Ind. Eng. Chem., Prod. Res. Dev., 1,
ID2 (1978).

170
 HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY SEPARATION
OF OLEFIN, SATURATE, AND AROMATIC HYDROCARBONS I N HIGH-BOILING
DISTILLATES AND RESIDUES OF SHALE O I L

John F . ElcKay and D . R . Latham

Laramie Energy Technology C e n t e r , DOE, P . 0 . Box 3395, L a r a m i e , Wyo. 8 2 0 7 1

ABSTFXT

A h i g h - p e r f o r m a n c e l i q u i d chromatography (HPLC) method h a s been d e v e l o p e d f o r t h e

s e p a r a t i o n of o l e f i n , s a t u r a t e , and a r o m a t i c h y d r o c a r b o n s found i n h i g h - b o i l i n g d i s -
t i l l a t e s and r e s i d u e s of s h a l e o i l and i n whole s h a l e o i l s . The dual-column c h r o -
m a t o g r a p h i c system u s e s s i l i c a g e l i n o n e column and s i l i c a g e l c o a t e d w i t h s i l v e r
n i t r a t e i n a second column. S e p a r a t e d f r a c t i o n s a r e a n a l y z e d by i n f r a r e d and
carbon-13 n u c l e a r m a g n e t i c r e s o n a n c e s p e c t r o m e t r y t o d e m o n s t r a t e t h e v a l i d i t y o f t h e
s e p a r a t i o n . The t i m e r e q u i r e d f o r a s e p a r a t i o n i s a b o u t two h o u r s . The s e p a r a t i o n s
a r e r e p r o d u c i b l e , and r e c o v e r y o f m a t e r i a l a f t e r s e p a r a t i o n i s g e n e r a l l y b e t t e r t h a n
90 p e r c e n t . The o l e f i n , s a t u r a t e , and a r o m a t i c f r a c t i o n s o b t a i n e d from a s e p a r a t i o n
are suitable for further analysis.

INTRODUCTION

A s i n c r e a s e d amounts o f s h a l e o i l a r e p r o c e s s e d t o g e t h e r w i t h p e t r o l e u m , i t becomes
i n c r e a s i n g l y i m p o r t a n t t o have methods a v a i l a b l e f o r t h e a n a l y s e s o f s h a l e o i l . A
f u n d a m e n t a l d i f f e r e n c e i n t h e c o m p o s i t i o n o f s h a l e o i l and p e t r o l e u m i s t h a t s h a l e o i l
c o n t a i n s t h r e e m a j o r h y d r o c a r b o n compound t y p e s - - o l e f i n s , s a t u r a t e s , and a r o m a t i c s - -
w h i l e p e t r o l e u m c o n t a i n s o n l y s a t u r a t e s and a r o m a t i c s . O l e f i n s , because they a r e
hydrogen d e f i c i e n t and u n s t a b l e , c a u s e problems i n t h e p r o c e s s i n g o f s h a l e o i l t h a t
a r e n o t e n c o u n t e r e d i n t h e p r o c e s s i n g o f p e t r o l e u m . They a r e a l s o of s p e c i a l i n t e r e s t
b e c a u s e t h e amounts, and p e r h a p s k i n d s , o f o l e f i n s i n s h a l e o i l a r e r e l a t e d t o t h e
r e t o r t i n g conditions t h a t produce t h e s h a l e o i l . Techniques f o r t h e a n a l y s i s of
s a t u r a t e s and a r o m a t i c s i n p e t r o l e u m a r e w e l l known; however, methods f o r d e t e r m i n i n g
o l e f i n , s a t u r a t e , and a r o m a t i c h y d r o c a r b o n s i n t h e heavy d i s t i l l a t e and r e s i d u e p o r -
t i o n s of s h a l e o i l a r e needed.

Many t e c h n i q u e s f o r t h e d e t e r m i n a t i o n o f o l e f i n s , s a t u r a t e s , and a r o m a t i c s have been

reported i n the l i t e r a t u r e (1-11). The methods u s u a l l y i n v o l v e l i q u i d chromatography
w i t h s i l i c a g e l ( 3 , 4 , 10) o r l i q u i d chromatography combined w i t h c h e m i c a l r e a c t i o n s
( 1 , 11, 1 2 ) . The methods work w e l l i n t h e a n a l y t i c a l a p p l i c a t i o n s f o r w h i c h t h e y were
designed--primarily t h e determination of hydrocarbon types i n l i g h t d i s t i l l a t e s .
D i f f i c u l t i e s , such a s incompleLe s e p a r a t i o n o f compound t y p e s , o f t e n a r i s e when t h e
methods a r e a p p l i e d t o t h e a n a l y s e s o f h e a v i e r h y d r o c a r b o n f r a c t i o n s . The p u r p o s e of
t h e work d i s c u s s e d i n t h i s p a p e r i s t o e x t e n d t h e a n a l y s i s o f o l e f i n , s a t u r a t e , and
a r o m a t i c hydrocarbons t o t h e h i g h - b o i l i n g d i s t i l l a t e and r e s i d u e f r a c t i o n s o f s h a l e
oil. S e v e r a l r e q u i r e m e n t s were e s t a b l i s h e d f o r a s a t i s f a c t o r y a n a l y t i c a l method: 1 )
t h e d e t e r m i n a t i o n s h o u l d be f a s t ; 2 ) t h e r e s u l t s s h o u l d be r e p r o d u c i b l e ; 3 ) t h e sam-
p l e s s h o u l d have minimum e x p o s u r e t o a i r , l i g h t , and h e a t ; and 4 ) t h e s e p a r a t e d hydro-
c a r b o n Lypes s h o u l d be c h e m i c a l l y u n a l t e r e d and t h e r e E o r e s u i t a b l e f o r f u r t h e r a n n l y -
ses.

T h i s p a p e r d e s c r i h e s a dun 1-column h i g h - p e r f o r m a n c e l i q u i d chromatogcaphy (tipLC)

method f o r t h e s e p a r a t i o n and d e t e r m i n a t i o n o f o l e f i n , s a t u r a t e , and a r o m a t i c hydro-
c a r b o n s i n h i g h - b o i l i n g d i s t i l l a t e and r e s i d u e f r a c t i o n s o f sli:ile o i l . The method can
a l s o he u s e d t o s e p a r a L e hydrocnrbon t y p e s i n whole s h a l e o i l s . The dual-column
t e c h n i q u e uses s i l i c a g e l t o s e p a r a t e a r o m a t i c h y d r o c a r b o n s from o l e f i n and s a t u r a t e
h y d r o c a r b o n s and s i l i c a g e t c o a t e d w i t h s i l v e r n i t r a t e t o s e p a r a t e o l e f i n from s a t u -
171
r a t e hydrocarbons. Cyclohexane i s used a s s o l v e n t f o r t h e h y d r o c a r b o n s a m p l e s . The
t i m e r e q u i r e d f o r a s e p a r a t i o n i s a b o u t two h o u r s .

EXPERIMENTAL

Apparatus

S h a l e o i l d i s t i l l a t e s and r e s i d u e s were o b t a i n e d u s i n g a n ASCO ( A r t h u r F. Smith C o . )

2 - i n . Rota-Film ( w i p e d - w a l l ) s t i l l . A c i d s , b a s e s , and n e u t r a l n i t r o g e n compounds were
removed from t h e s a m p l e s u s i n g a g r a v i t y - f l o w g l a s s column ( 2 . 5 cm x 90 cm) packed i n
t h r e e s e c t i o n s w i t h anion r e s i n , c a t i o n r e s i n , and f e r r i c chloride/Attapulgus c l a y .
The column was wet-packed u s i n g c y c l o h e x a n e .

Hydrocarbon s e p a r a t i o n s were made u s i n g a dual-column s y s t e m i n a Waters A s s o c i a t e s

AGC/CPC-202 l i q u i d c h r o m a t o g r a p h e q u i p p e d w i t h r e f r a c t i v e i n d e x a n d u l t r a v i o l e t de-
t e c t i o n u n i t s . The f i r s t column c o n t a i n e d s i l i c a g e l , and t h e s e c o n d column c o n t a i n e d
s i l i c a gel coated w i t h s i l v e r n i t r a t e . Both columns were s t a i n l e s s s t e e l ( 7 . 8 mm i . d .
x 6 1 cm) a n d were s u p p l i e d w i t h 5-micron f r i t t e d e n d f i t t i n g s . I n f r a r e d s p e c t r a were
r e c o r d e d o n a P e r k i n - E l m e r model 621 s p e c t r o p h o t o m e t e r , and c a r b o n - 1 3 NMR s p e c t r a were
o b t a i n e d u s i n g a V a r i a n CFT-20 s p e c t r o m e t e r .

Materials

Arnberlyst IRA-904 a n i o n - e x c h a n g e r e s i n (Rohm and Haas) was used f o r removal o f a c i d s ,

and Amberlyst A-15 c a t i o n - e x c h a n g e r e s i n (Rohm and Haas) was u s e d f o r removal o f
bases. A t t a p u l g u s c l a y , 5 0 / 8 0 mesh ( E n g e l h a r d M i n e r a l s and Chemical C o r p . ) c o a t e d
w i t h f e r r i c c h l o r i d e (Baker and Adamson) removed n e u t r a l n i t r o g e n compounds from t h e
samples. The p r e p a r a t i o n o f r e s i n s and f e r r i c c h l o r i d e / A t t a p u l g u s c l a y has b e e n
described (13).

S i l i c a g e l 60G (E. Merck) f o r t h i n - l a y e r c h r o m a t o g r a p h y was used a s r e c e i v e d t o s e p a -

r a t e a r o m a t i c s from s a t u r a t e s and o l e f i n s . The same s i l i c a g e l c o a t e d w i t h 20 p e r c e n t
s i l v e r n i t r a t e (Baker and Adamson) s e p a r a t e d s a t u r a t e s from o l e f i n s . The s i l v e r
n i t r a t e - c o a t e d g e l was p r e p a r e d by d i s s o l v i n g t h e s i l v e r n i t r a t e i n w a t e r , mixing t h e
s o l u t i o n w i t h s i l i c a g e l , and removing t h e w a t e r on a r o t a r y e v a p o r a t o r . The g e l was
activated a t 1 l O O C f o r 12 hours. Cyclohexane, b e n z e n e , and m e t h a n o l were commercial
HPLC-grade s o l v e n t s f r o m v a r i o u s s u p p l i e r s and were u s e d a s r e c e i v e d .

S h a l e O i l Samples

The s h a l e o i l s used i n t h i s s t u d y were produced by i n s i t u and aboveground r e t o r t i n g

processes (14). The S i t e 9 o i l was o b t a i n e d from t h e Laramie Energy Technology C e n t e r
(LETC) i n s i t u e x p e r i m e n t n e a r Rock S p r i n g s , Wyo. The 1 5 0 - t o n r e t o r t o i l i s from t h e
LETC s i m u l a t e d i n s i t u 1 5 0 - t o n r e t o r t n e a r L a r a m i e , Wyo. P a r a h o and S u p e r i o r o i l s a r e
from aboveground r e t o r t s l o c a t e d a t A n v i l P o i n t s , C o l o . , C l e v e l a n d , O h i o , r e s p e c -
tively.

D i s t i l l a t i o n of Shale O i l s

Crude s h a l e o i l s t h a t had b e e n c e n t r i f u g e d t o remove p a r t i c u l a t e m a t t e r and w a t e r were

d i s t i l l e d u s i n g a w i p e d - w a l l s t i l l . The s t i l l was o p e r a t e d a t 20 t o r r t o remove o i l
b o i l i n g below 210'C ( c o r r e c t e d t o a t m o s p h e r i c p r e s s u r e ) . D i s t i l l a t e f r a c t i o n s b o i l i n g
from c o r r e c t e d t e m p e r a t u r e s of 210 t o 370°C and 370 t o 535'C were o b t a i n e d a t l o w e r
p r e s s u r e s and i n c r e a s e d t e m p e r a t u r e s . The r e s i d u e was r e c o v e r e d m a t e r i a l t h a t d i d n o t
d i s t i l l aL 25OOC ( c o r r e c t e d ) and 0 . 2 t o r r . The r e s i d u e was a c t u a l l y exposed t o a
t e m p e r a t u r e o f 250'C f o r o n l y a tew s e c o n d s s o t h a t t h e r m a l d e g r a d a t i o n was minimal.

172
P r e p a r a t i o n o f Hydrocarbon Samples

A sample ( 1 g ) o f d i s t i l l a t e , r e s i d u e , o r whole s h a l e o i l was d i s s o l v e d i n c y c l o h e x a n e

(100 ml) and p a s s e d t h r o u g h a g r a v i t y - f l o w g l a s s column c o n t a i n i n g s u c c e s s i v e b e d s o f
a n i o n ( 8 0 g ) and c a t i o n ( 8 0 g ) r e s i n s and f e r r i c c h l o r i d e / A t t a p u l g u s c l a y (100 9).
The column was washed w i t h c y c l o h e x a n e (500 ml) t o r e c o v e r t h e h y d r o c a r b o n s . The
c y c l o h e x a n e was removed from t h e h y d r o c a r b o n s u s i n g a r o t a r y e v a p o r a t o r .

P r e p a r a t i o n and Assembly o f HPLC Columns

A r e s e r v o i r column was a t t a c h e d t o a n empty HPLC column, and b o t h columns were f i l l e d

w i t h d r y s i l i c a g e l o r s i l v e r n i t r a t e / s i l i c a g e l ( a b o u t 20 9 ) . Cyclohexane was t h e n
pumped t h r o u g h t h e s y s t e m t o w e t and compress t h e p a c k i n g m a t e r i a l i n t o t h e HPLC
column. The r e s e r v o i r column was t h e n d e t a c h e d . Columns packed u s i n g t h i s t e c h n i q u e
c o n t a i n e d 15 g o f g e l w e t t e d w i t h C y c l o h e x a n e , and t h e g e l was u n i f o r m l y d i s t r i b u t e d
i n t h e column. A f t e r a s e p a r a t i o n , t h e s i l v e r n i t r a t e l s i l i c a g e l column c o u l d be
r e a c t i v a t e d by washing w i t h c y c l o h e x a n e (100 m l ) . The s i l i c a g e l column was n o t
reusable. F i g u r e 1 shows t h e dual-column a s s e m b l y , c h r o m a t o g r a p h , and d e t e c t o r s .

Column C a l i b r a t i o n

D u r i n g r o u t i n e a n a l y s e s , t h e c u t p o i n t f o r 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 o l e f i n s
from a r o m a t i c s o n t h e s i l i c a column was made a c c o r d i n g t o e l u t i o n volume. The p r o p e r
e l u t i o n volume was e s t a b l i s h e d p r i o r t o t h e s e p a r a t i o n s by p a s s i n g s a m p l e s t h r o u g h t h e
s i l i c a g e l column and m o n i t o r i n g t h e s e p a r a t i o n w i t h u l t r a v i o l e t and r e f r a c t i v e i n d e x
d e t e c t o r s . Once t h e p r o p e r e l u t i o n volume had b e e n e s t a b l i s h e d , t h e d e t e c t o r s were
removed from t h e c h r o m a t o g r a p h i c s y s t e m .

Separation Procedure

A r o u t i n e s e p a r a t i o n was made i n t h e f o l l o w i n g manner. A s h a l e o i l h y d r o c a r b o n sample

(200 mg), d i s s o l v e d i n c y c l o h e x a n e (1 ml), was p l a c e d on t h e s i l i c a g e l column, and
c y c l o h e x a n e was pumped t h r o u g h t h e two columns f o r 40 m i n u t e s a t a r a t e o f 1 mlfmin
and a p r e s s u r e o f a b o u t 350 p s i g . Under t h e s e e l u t i o n c o n d i t i o n s a r o m a t i c s a r e re-
t a i n e d on column 1, w h i l e s a t u r a t e s a n d o l e f i n s p a s s t h r o u g h t o column 2 . V a l v e s
between t h e columns a n d a s e c o n d s o l v e n t r e s e r v o i r a l l o w e d c o n t i n u e d pumping c y c l o -
hexane t h r o u g h t h e second column where o l e f i n s and s a t u r a t e s were s e p a r a t e d . Satu-
r a t e s were e l u t e d w i t h c y c l o h e x a n e from t h e s i l v e r n i t r a t e column w i t h c o n t i n u e d
pumping f o r 30 m i n u t e s a t 1 m l l m i n . O l e f i n s were t h e n e l u t e d from t h e s i l v e r n i t r a t e
column by pumping b e n z e n e l c y c l o h e x a n e , 2 0 / 8 0 p e r c e n t , t h r o u g h t h e column f o r 30 min-
u t e s a t 1 mllmin. S i m u l t a n e o u s l y , b e n z e n e / m e t h a n o l , 4 0 / 6 0 p e r c e n t , was pumped t h r o u g h
t h e f i r s t column f o r 60 m i n u t e s t o e l u t e a r o m a t i c s . The t o t a l s e p a r a t i o n t i m e was
about 2 hours.

DISCUSSION

I d e n t i f i c a t i o n o f Hydrocarbon Types

I n f r a r e d and carbon-13 NEIR s p e c t r o m e t r y were u s e d t o a n a l y z e t h e h y d r o c a r b o n f r a c t i o n s

p r e p a r e d by t h e dual-column c h r o m a t o g r a p h i c s y s t e m . The a n a l y s e s d e m o n s t r a t e t h e
v a l i d i t y of t h e s e p a r a t i o n s . Both s p e c t r o m e t r i c t e c h n i q u e s h a v e s p e c i a l a n a l y t i c a l
a d v a n t a g e s and l i m i t a t i o i l s ; when used t o g e t h e r t h e y p e r m i t a s a t i s f a c t o r y a n a l y s i s of
t h e hydrocarbon f r a c t i o n s .

The f r a c t i o n s o f s a t u r a t e s , o l e f i n s , and a r o m a t i c s were f i r s t examined u s i n g i n f r a r e d

s p e c t r o m e t r y . Two a b s o r p t i o n b a n d s - r e r e u s e d t o a n a l y z e t h e f r a c t i o n s : 1) t h e mono-
o l e f i n s t r e t c h i n g band a t 1630 cm t o - i d e n t i f y o l e f i n s and 2 ) t h e a r o m a t i c r i n g
c a r b o n - c a r b o n s t r e t c h i n g band a t 1600 cm t o i d e n t i f y aromatics. S a t u r a t e s h a v e no
a b s o r p t i o n bands i n t h e i n f r a r e d t h a t d i s t i n g u i s h t h e m from o t h e r h y d r o c a r b o n t y p e s .
An example o f t h e u s e of i n f r a r e d s p e c t r o m e t r y i n a n a l y z i n g h y d r o c a r b o n f r a c t i o n s
p r e s e n t e d i n F i g u r e 2 , which shows t h e p a r t i a l i n f r a r e d s p e c t r u m o f t h e t o t a l hydro-
c a r b o n s from a 21O-37O0C d i s t i l l a t e t o g e t h e r w i t h t h e p a r t i a l i n f r a r e d s p e c t r a o f
separated fractions. I n F i g u r e Za, b o t h m o n o - o l e f i n and a r o m a t i c a b s o r p t i o n may be
seen i n t h e spectrum of the t o t a l hydrocarbons. F i g u r e s 2 b , Z C , and 2d show t h a t a
s e p a r a t i o n of a r o m a t i c s , o l e f i n s , _a d s a t u r a t e s has been a c h i e v e d . Only t r a c e amounts
o f a r o m a t i c s a b s o r b i n g a t 1600 cm c a n be o b s e r v e d i n t h e s p e c t r u m o f t h e s a t u r a t e s
( F i g . 2d) and o l e f i n s ( F i g . 2 c ) . O l e f i n s a r e observed i n only t h e o l e f i n f r a c t i o n
(Fig. 2 c ) .

I n g e n e r a l , i n f r a r e d s p e c t r o m e t r y i s a v e r y u s e f u l method f o r a n a l y z i n g t h e h y d r o c a r -
bon f r a c t i o n s b e c a u s e i t i s f a s t and s e n s i t i v e . I t d o e s , however, h a v e l i m i t a t i o n s .
F i r s t , i n a m i x t u r e o f h y d r o c a r b o n t y p e s , satu! t e s c a n n o t h e d i s t i n g u i s h e d from
o l e f i n s or aromatics, S e c o n d , u s e of t h e 1630 cm band d o e s n o t a l l o w t h e d e t e c t i o n
o f c o n j u g a t e d d i - and t r i - o l e f i n s . T h i r d , i n f r a r e d a n a l y s e s o f complex m i x t u r e s o f
o l e f i n s c a n n o t be q u a n t i t a t i v e b e c a u s e t h e m o l a r a b s o r p t i v i t i e s o f i n d i v i d u a l o l e f i n i c
compounds a r e q u i t e v a r i a b l e . The c o r r e c t v a l u e of m o l a r a b s o r p t i v i t y t o u s e i n a n
i n f r a r e d c a l c u l a t i o n i n v o l v i n g B e e r ' s l a w i s n o t known.

Carbon-13 NNR s p e c t r o m e t r y was u s e d t o complement i n f r a r e d s p e c t r o m e t r y i n t h e a n a l y -

ses of separated f r a c t i o n s . T h e s e d a t a c o n f i r m e d i n f r a r e d d a t a and p r o v i d e d a d d i -
t i o n a l information about the hydrocarbon t y p e s , e s p e c i a l l y t h e o l e f i n s .

F i g u r e 3 shows c a r b o n - 1 3 NMR s p e c t r a o f s a t u r a t e s ( F i g . 3 a ) , o l e f i n s ( F i g . 3 b ) , and

a r o m a t i c s ( F i g . 3 c ) from a 370-535OC h y d r o c a r b o n c o n c e n t r a t e . For q u a n t i t a t i v e d e t e r -
m i n a t i o n o f o l e f i n s , t h e s p e c t r a l r e g i o n o f i n t e r e s t i s between 1 1 0 a n d 1 4 0 ppm r e l a -
t i v e t o t e t r a m e t h y l s i l a n e (TMS). S a t u r a t e s show no carbon-13 a b s o r p t i o n i n t h i s
r e g i o n . O l e f i n s show a b s o r p t i o n bands between 114 and 138 ppm ( 1 5 , 1 6 ) ; t h e p o s i t i o n
o f a b s o r p t i o n i s d e p e n d e n t upon t h e t y p e o f o l e f i n . Alpha o l e f i n h a n d s a r e o b s e r v e d
a t 11'. and 138 ppm, w h i l e i n t e r n a l o l e f i n s h a v e a b s o r p t i o n bands between 114 and 138
ppm. Aromatic c a r b o n s a r e s e e n a s a b r o a d , s y m m e t r i c a l a b s o r p t i o n e n v e l o p e c e n t e r e d
a t a b o u t 128 ppm. F i g u r e 3 a shows t h a t , i n t h i s p a r t i c u l a r s e p a r a t i o n r u n , t h e s a t u -
r a t e s contain 1 o r 2 p e r c e n t of another hydrocarbon type, probably aromatics. Olefins
a r e observed only i n t h e o l e f i n f r a c t i o n , n o t i n t h e s a t u r a t e o r aromatic f r a c t i o n s .
T r a c e amounts o f a r o m a t i c s a p p e a r t o b e i n t h e o l e f i n f r a c t i o n , c o n f i r m i n g t h e i n f r a -
red d a t a .

Carbon-13 NHR is u s e f u l n o t o n l y b e c a u s e i t a i d s i n j u d g i n g t h e q u a l i t y o f s e p a r a t i o n
t h a t h a s been a c h i e v e d b u t a l s o b e c a u s e it p r o v i d e s d e t a i l e d i n f o r m a t i o n a b o u t molecu-
l a r structure. F o r e x a m p l e , i n a n o l e f i n m i x t u r e , t h e number o f d o u b l e bonds of a n
a v e r a g e o l e f i n m o l e c u l e c a n b e c a l c u l a t e d i f t h e a v e r a g e m o l e c u l a r w e i g h t of t h e
o l e f i n m i x t u r e i s known a n d i f t h e r a t i o o f a l i p h a t i c / o l e f i n i c c a r b o n s c a n be measured
b y c a r b o n - 1 3 NNR. However, c a r b o n - 1 3 NMR a l s o h a s l i m i t a t i o n s . F i r s t , i n a mixture
o f h y d r o c a r b o n s , s a t u r a t e s c a n n o t be d i s L i n g u i s h e d from o l e f i n s a n d a r o m a t i c s . Sec-
o n d , o l e f i n s may n o t be o b s e r v a b l e i n a c o n c e n t r a t e o f s a t u r a t e s o r a r o m a t i c s i f t h e
amount of o l e f i n s i s l o w e r t h a n a b o u t 3 o r 4 p e r c e n t . T h i r d , w i t h carbon-13 s p e c t r o -
m e t r y a l o n e , i t may b e d i f f i c u l t t o d i s t i n g u i s h between i n t e r n a l o l e f i n s and aroina-
t i c s ; i n such a case u l t r a v i o l e t analyses a r e u s e f u l .

I n f r a r e d and NHR a n a l y s e s e s t a b l i s h e d t h a t s a t u r a t e , o l e f i n , and a r o m a t i c compound

c l a s s e s were s e p a r a t e d i n t o t h r e e d i s c r e t e f r a c t i o n s by t h e d u a l - c o l u m n s y s t e m . T h i s
a l l o w e d t h e q u a n t i t a t i v e d e t e r m i n a t i o n o f e a c h c l a s s t o h ) c iiiilcle g r a v i m e t r i c a l l y .

Separation Results

a. Hydrocarbons i n H i g h - R o i l i n g D i s t i l l a t e s and R e s i d u e s . -
The dual-column method
was u s e d t o s e p a r a t e h y d r o c a r b o n s from t h r e e d i f f e r e n t b o i l i n g r a n g e s of f o u r s h a l e
oils. The r e s u l t s o f t h e s e p a r a t i o n s a r e shown i n T a b l e 1. A l l d a t a were o b t a i n e d
g r a v i m e t r i c a l l y . D u p l i c a t e d e t e r m i n a t i o n s were made t o show t h e r e p r o d u c i b i l i t y t h a t
174
can b e e x p e c t e d w i t h t h e s e p a r a t i o n t e c h n i q u e . I n most c a s e s t h e r e p r o d u c i b i l i t y i s
s i m i l a r t o t h a t experienced i n t h e s i l i c a g e l s e p a r a t i o n o f s a t u r a t e and aromatic
hydrocarbons i n petroleum. The c a u s e o f t h e poor r e p r o d u c i b i l i t y e x p e r i e n c e d i n some
r u n s i s n o t known. The r e c o v e r y o f s e p a r a t e d hydrocar,bon types was g e n e r a l l y b e t t e r
t h a n 90 p e r c e n t .

From a c h a r a c t e r i z a t i o n p o i n t o f v i e w , t h e d a t a i n T a b l e 1 show some i n t e r e s t i n g

t r e n d s . F i r s t , d i s t i - l l a t e s a n d r e s i d u e s from t h e S i t e 9 i n s i t u o i l and t h e 1 5 0 - t o n
r e t o r t o i l c o n t a i n s m a l l e r amounts o f o l e f i n s and l a r g e r amounts o f s a t u r a t e s t h a n t h e
other oils. T h u s , it. a p p e a r s ' t h a t t h e S i t e 9 and 1 5 0 - t o n r e t o r t o i l s were p r o d u c e d
u n d e r m i l d e r r e t o r t i n g c o n d i t i o n s t h a n t h e Paraho and S u p e r i o r o i l s . Second, t h e
d i s t r i b u t i o n s o f h y d r o c a r b o n compound t y p e s a s r e l a t e d t o d i s t i l l a t i o n t e m p e r a t u r e c a n
be s e e n . For example, i n t h e S i t e 9 o i l , t h e a r o m a t i c s i n c r e a s e a s t h e d i s t i l l a t i o n
temperature i n c r e a s e s . The o l e f i n s a r e c o n s t a n t i n t h e d i s t i l l a t e s a n d i n c r e a s e i n
the residue. These changes a r e a t t h e e x p e n s e of s a t u r a t e s w h i c h d e c r e a s e a s t h e
d i s t i l l a t i o n temperature i n c r e a s e s .

b. Hydrocarbons from Whole S h a l e O i l s . - The dual-column method p e r m i t t e d t h e f a s t

d e t e r m i n a t i o n o f s a t u r a t e s , o l e f i n s , and a r o m a t i c s i n whole s h a l e o i l s . The r e s u l t s
o f t h e s e p a r a t i o n s a r e shown i n T a b l e 2 . B o t h r e p r o d u c i b i l i t y and r e c o v e r y v a l u e s a r e
s i m i l a r t o t h o s e s e e n i n t h e s e p a r a t i o n of d i s t i l l a t e s and r e s i d u e s . Unknown amounts
of l i g h t h y d r o c a r b o n s from t h e whole s h a l e o i l s were l o s t d u r i n g t h e s o l v e n t - r e m o v a l
procedure.

SUMMARY AND CONCLUSIONS

An HPLC method has b e e n d e v e l o p e d f o r t h e s e p a r a t i o n o f s a t u r a t e s , o l e f i n s , and a r o -

m a t i c s i n h i g h - b o i l i n g d i s t i l l a t e s a n d r e s i d u e s o f s h a l e o i l and i n whole s h a l e o i l s .
The dual-column c h r o m a t o g r a p h i c s y s t e m uses s i l i c a g e l i n o n e column and s i l i c a g e l
c o a t e d w i t h 20 p e r c e n t s i l v e r n i t r a t e i n a s e c o n d column. The t i m e r e q u i r e d f o r a
s e p a r a t i o n is a b o u t two h o u r s . The s e p a r a t i o n s a r e r e p r o d u c i b l e ; r e c o v e r y o f i i i a t e r i a l
a f t e r s e p a r a t i o n i s g e n e r a l l y b e t t e r t h a n 90 p e r c e n t . The s a t u r a t e , o l e f i n , a n d
a r o m a t i c f r a c t i o n s o b t a i n e d from a s e p a r a t i o n a r e s u i t a b l e f o r f u r t h e r a n a l y s e s .

ACKNOWLEDGMENTS

The a u t h o r s t h a n k Mr. Shawn C . T a p l e y f o r t h e c h r o m a t o g r a p h y work, D r . D a n i e l A .

N e t z e l f o r t h e carbon-13 NMR a n a l y s e s , a n d Dr. Shuang-Ling Chong f o r h e l p f u l d i s c u s -
sions.

DISCLAIMER

Mention of s p e c i f i c models o r b r a n d names o f equipment i s made f o r i n f o r m a t i o n only

and does n o t imply endorsement by t h e Department o f E n e r g y .

LITERATURE CITED

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3. G . U. Dinneen, J. R . S m i t h , R . A . Van M e t e r , C . S. A l l b r i g h t , and W. R . Anthoney,

Anal. Chem., 7,
185 ( 1 9 5 5 ) .

4. E. L. Saier, A. P o z e f s k y , and N . D . C o g g e s h a l l , Anal. Chem., 26, 1258 (L'354).

5. tl. 6 . J e n s e n , J. R . H o r a n d i , and G . L . Cook, P r e p r i n t s , ACS Div. P e t r o l . Chem.,

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13 ( 2 1 , 698 ( 1 9 6 8 ) .

175
 6. J . R . Elorandi a n d H . B. J e n s e n , J . Org. Chem., 34, 1889 ( 1 9 6 9 ) .

7. H. B. J e n s e n , R . E . Poulson, and G . L . Cook, P r e p r i n t s , ACS Div. F u e l Chem., -

15
(11, 113 ( 1 9 7 1 ) .
8. R . E . P o u l s o n , H . B . J e n s e n , J . J . D u v a l l , F. L. H a r r i s , and J . R . Morandi, P r o c .
1 8 t h Annual TSA A n a l y s i s I n s t r u m e n t a t i o n Symposium, San F r a n c i s c o , C a l i f . , May
1972, p . 193.

9. J . R . M o r a n d i , D . G . E a r n s h a w , and H . B . J e n s e n , A b s t r a c t s , P i t t s b u r g h C o n f e r e n c e
on A n a l y t i c a l C h e m i s t r y and A p p l i e d S p e c t r o s c o p y , C l e v e l a n d , O h i o , March 1972, p .
170.

10. ASTM Book o f S t a n d a r d s , 1 9 7 5 , P a r t 2 4 , Method D 2003-64, p . 1 4 4 .

11. L . P. J a c k s o n , C . S . A l l b r i g h t , and R . E . P o u l s o n , A n a l . Chem., 5 , 604 (1974).

12. L. P . J a c k s o n , C . S. A l l b r i g h t , and R . E . Poulson, " A n a l y t i c a l C h e m i s t r y o f

Liquid Fuel Sources: T a r S a n d s , O i l S h a l e , C o a l , and P e t r o l e u m , " P e t e r C . Uden,
Sidney S i g g i a , a n d Howard B . J e n s e n , E d . , Advances i n C h e m i s t r y S e r i e s 1 7 0 ,
American C h e m i c a l S o c i e t y , Wash., D . C . 1 9 7 8 , p. 232.

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Chem., +, 1 3 9 1 (1972).

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1978, D e n v e r , C o l o . , 80210.

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V a r i e , P r o c . EPA O i l S h a l e Symposium: S a m p l i n g , A n a l y s i s , a n d Q u a l i t y A s s u r a n c e ,
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176
 TABLE 1. - Hydrocarbon s e p a r a t i o n r e s u l t s of d i s t i l l a t e s and r e s i d u e s

W t . D e r c e n t of
t o t a l hydrocarbon f r a c t i o n Percent
Sample Saturate Olefin Aromatic r e c o v e r y
1 5 0 - t o n , 210-370°C dist. 64 5 19 88
11
63 7 20 90

370-535OC d i s t . 61 6 29 96
It
59 7 34 100

>535OC r e s i d u e 45 11 43 99
11
45 11 38 94

Site 9, 210-370°C dist. 70 5 17 92

It
72 6 23 101

370-535OC d i s t . 64 6 24 94
11
59 5 29 93

>535OC r e s i d u e 48 8 40 96
11
40 10- 47 97

Paraho, 210-370°C dist. 25 27 30 82

It
36 23 26 85

370-535OC d i s t . 38 24 34 96
II
31 23 35 89

>535OC r e s i d u e 19 10 48 77
It
23 13 44 80

S u p e r i o r , 210-370°C dist. 25 29 30 84
It
27 36 28 91

370-535OC d i s t . 32 21 42 95
It
32 22 42 96

>535OC r e s i d u e 27 22 47 96
I,
31 19 48 98

177
 TABLE 2 . - Hydrocarbon s e p a r a t i o n r e s u l t s o f whole s h a l e o i l s

W t . p e r c e n t of hydrocarbons
from t o t a l o i l Percent
S h a l e o i l sample Saturate Olefin Aromatic recovery
150-ton r e t o r t 53 17 22 92
II 40 21 22 83

Site 9 retort 46 18 18 82
It
55 15 20 90

Paraho r e t o r t 41 27 24 92

Superior r e t o r t 41 26 32 99
11
36 31 28 95

178
, , ’3’
i!
(Y

‘1- >
4
U
v)
3
*
 b) AROMATICS

c) OLEFINS

d) SATURATES

1800 1600
WAVELENGTH, cm-’

FIGURE 2. P a r t i a l infrared spectra o f shale oil 210-370°C

distillate total hydrocarbon a n d fractions

180
 a) SATURATES

JL
l
b) OLEFINS

I i I 1
150 50 0
loo PPM

FIGURE 3. Carbon-13 NMR spectra o f hydrocarbon fractions

from Paraho 370-535OC distillate
181
 LOW TEMPERATURE CLEAVAGE REACTIONS OF ILLINOIS NO. 6 COAL

F r a n k R . Mayo, David H. Buchanan,l and Lee A . P a v e l k a

S R I I n t e r n a t i o n a l , Menlo P a r k , C a l i f o r n i a 94025

T h i s paper p r e s e n t s a p r o g r e s s r e p o r t on our e f f o r t s t o d e t e r m i n e t h e k i n d s and

p r o p o r t i o n s o f s i n g l e bond i n I l l i n o i s No. 6 c o a l t h a t c a n b e broken below 100°C. The
p r i n c i p a l o b s t a c l e t o t h e u s e of p r e s e n t l i q u e f a c t i o n p r o c e s s e s i s t h e h i g h c o s t of
p l a n t s t h a t would employ t h e r e q u i r e d h i g h t e m p e r a t u r e s and p r e s s u r e s . Our work d e a l s
o n l y w i t h low-temperature p r o c e s s e s near a t m o s p h e r i c p r e s s u r e . I t h a s focused o n ( 1 )
t h e a s p h a l t o l f r a c t i o n of I l l i n o i s No. 6 c o a l , which i s t h e p y r i d i n e - s o l u b l e , toluene-
i n s o l u b l e f r a c t i o n t h a t comprises about t w o - t h i r d s of t h e 15% of c o a l t h a t can be ex-
t r a c t e d by p y r i d i n e , and ( 2 ) t h e p y r i d i n e - e x t r a c t e d c o a l , which i s about 85% of t h e
i n i t i a l d r y c o a l , and which r e p r e s e n t s t h e e s s e n c e of t h e l i q u e f a c t i o n problem.

Oxidations

P r e v i o u s work by Huntington e t a12 d e s c r i b e d t h e e f f e c t s on t h e same two sub-

s t r a t e s of (1) A I B N - i n i t i a t e d o x i d a t i o n s i n p y r i d i n e s o l u t i o n a t 50°C, and ( 2 ) r e f l u x -
i n g w i t h a l c o h o l i c KOH (781) w i t h o u t oxygen. E i t h e r r e a g e n t would r e d u c e t h e number-
a v e r a g e molecular weight (Mn, by vapor-phase osmometry) of t h e a s p h a l t o l by n e a r l y 50%
b u t s e q u e n t i a l t r e a t m e n t w i t h b o t h r e a g e n t s produced l i t t l e a d d i t i o n a l e f f e c t , a s i f
t h e two r e a g e n t s were a f f e c t i n g s i m i l a r bonds. Only about 10% of t h e e x t r a c t e d c o a l
w a s made s o l u b l e i n p y r i d i n e , b u t some s u b s t r a t e became s o l u b l e i n a l c o h o l i c KOH.

N a O C l o x i d a t i o n of v e r y f i n e l y d i v i d e d e x t r a c t e d c o a l i n w a t e r s u s p e n s i o n a t 30"
and pH 1 3 h a s been much more e f f e c t i v e i n d i s s o l v i n g t h i s m a t e r i a l . 3 76% of t h e
c a r b o n i n t h e e x t r a c t e d c o a l h a s been converted t o b l a c k a c i d s (M, about 1000) s o l u b l e
i n aqueous b a s e , and 7% t o w a t e r - s o l u b l e acids; 4 % of t h e i n i t i a l carbon w a s undis-
s o l v e d ; t h e remaining 12% i s presumably i n c a r b o n o x i d e s . Oxygen o x i d a t i o n of ex-
t r a c t e d c o a l i n w a t e r s u s p e n s i o n a t pH 13 and 50" is much s l o w e r b u t h a s l e d t o 85%
d i s s o l u t i o n of t h e c o a l and r e c o v e r y of 66% of t h e o r i g i n a l c o a l i n b l a c k a c i d s . Oxi-
d a t i o n s of a s p h a l t o l , w e l l d i s p e r s e d i n water a t pH 1 3 , gave b e t t e r r e s u l t s : w i t h
N a O C l a t 3 0 ° , 99% d i s s o l u t i o n and 93% of t h e carbon i n b l a c k a c i d s ; w i t h oxygen a t 5 0 ° ,
98% d i s s o l u t i o n and 80% o f t h e c a r b o n i n b l a c k a c i d s .

These o x i d a t i o n s i n w a t e r s u s p e n s i o n a t pH 1 3 and o x i d a t i o n s w i t h A I B N and oxygen

i n p y r i d i n e s o l u t i o n 2 a t 50°C a p p e a r t o proceed by d i f f e r e n t mechanisms. I n r a d i c a l -
i n i t i a t e d o x i d a t i o n s of e x t r a c t e d c o a l , t h e H/C r a t i o d e c r e a s e s from . 7 3 t o .69, a s
i f b e n z y l i c hydrogen were b e i n g removed p r e f e r e n t i a l l y . However, i n b o t h N a O C l and
oxygen o x i d a t i o n s of b o t h a s p h a l t o l and e x t r a c t e d c o a l i n w a t e r , H / C i n c r e a s e s some-
what, n o t w i t h s t a n d i n g r e p l a c e m e n t of some H by 0 , s u g g e s t i n g p r e f e r e n t i a l removal of
a r o m a t i c groups. P o s s i b l y some h y d r o x y l a t e d a r o m a t i c r i n g s a r e s i t e s o f a t t a c k . The
p r i n c i p a l p r o d u c t s , b l a c k a c i d s , from oxygen and NaOCl o x i d a t i o n s i n w a t e r a t pH 1 3
have similar c o m p o s i t i o n s .

Cleavages of A s p h a l t o l s

R e s u l t s of c l e a v a g e s of a s p h a l t o l s , p r o b a b l y a t e t h e r l i n k s , a r e summarized i n
F i g u r e s 1 and 2 . E_ach h a l f of e a c h t a b l e s t a r t s from t h e c e n t e r w i t h a s p h a l t o l w i t h
s l i g h t l y d i f f e r e n t Mn. I n g e n e r a l , r e a c t i o n s were r u n u n d e r n i t r o g e n , and a t room
t e m p e r a t u r e e x c e p t a s n o t e d . P r o d u c t s were sometimes s e p a r a t e d by s o l u b i l i t y b u t
always washed f r e e o f r e a g e n t s and s o l v e n t s and d r i e d i n a n Abderhalden d r i e r a t
<0.001 t o r r , u s u a l l y a t 14OoC i n F i g u r e 1, u s u a l l y a t 76OC i n F i g u r e 2. (The o n l y
need f o r 140' d r y i n g seems to-be w i t h samples t h a t c o n t a i n p y r i d i n e o r amines and
have n o t been acid-washed.) M n s were determined by VPO in p y r i d i n e , i n which a l l pro-
d u c t s were s o l u b l e , a t c o n c e n t r a t i o n s of 0 . 5 t o 3g/L. Keys t o a b b r e v i a t i o n s and
182
arrangement of d a t a a r e g i v e n i n F i g u r e 2 . Thus, m o l e c u l a r w e i g h t s of p r o d u c t s a r e i n
t h e middle of each second l i n e of each b l o c k of d a t a .

Experiments i n t h e upper l e f t q u a r t e r of F i g u r e 1 show t h a t e i g h t e x t r a c t i o n s of

a s p h a l t o l with 5% KOH a t room t e m p e r a t u r e r e s u l t e d i n s o l u t i o n and r e c o v e r y of 9% of
s o l u b l e carbon. 23% o f t h e o r i g i n a l C was l o s t , a t l e a s t p a r t l y a s w a t e r - s o l u b l e
a n d / o r v o l a t i l e p r o d u c t s . Molecular w e i g h t r e d u c t i o n s w i t h o u t h e a t i n g p a r a l l e l t h o s e
a t 78O.2

R e a c t i o n s of a s p h a l t o l w i t h benzylamine ( l o w e r l e f t q u a r t e r i n F i g u r e l ) , and
t h e n drowning t h e r e a c t i o n i n e t h e r or methanol, r e s u l t e d i n p a r t of t h e a s p h a l t o l
becoming s o l u b l e i n t h e s e s o l v e n t s and a d e c r e a s e i n fin of a b o u t o n e - h a l f . Treatment
of the e t h e r - i n s o l u b l e p r o d u c t w i t h a l c o h o l i c KOH r e s u l t e d i n f r a c t i o n a t i o n of t h e
p r o d u c t b u t n o t f u r t h e r d e g r a d a t i o n . The butylamine-methanol c o m b i n a t i o n a p p e a r s t o
behave s i m i l a r l y .

P y r i d i n e h y d r o i o d i d e i n p y r i d i n e a t room t e m p e r a t u r e d e c r e a s e s t h e En of a s p h a l t o l
t o one-half t o o n e - t h i r d of t h e o r i g i n a l (upper r i g h t i n F i g u r e 1 ) . T h i s e x p e r i m e n t
w a s r u n on t h e p r e m i s e t h a t p y r i d i n e h y d r o i o d i d e would be an a c i d i n p y r i d i n e , which
i s an e x c e l l e n t s o l v e n t f o r a s p h a l t o l . However, methyl i o d i d e w a s n e a r l y as e f f e c t i v e
a s H I . A s p h a l t 0 1 was t r e a t e d w i t h methyl i o d i d e a t room t e m p e r a t u r e i n t h e hope of
making sulfonium as w e l l as p y r i d i n i u m s a l t s . The p r o d u c t was t h e n h e a t e d t o 140' a t
reduced p r e s s u r e i n t h e e x p e c t a t i o n of s p l i t t i n g o u t methyl i o d i d e from p y r i d i n i u m
s a l t s ( w i t h o u t n e t c o a l bond c l e a v a g e ) and c o n v e r s i o n of t h e o r i g i n a l s u l f i d e s t o
methyl s u l f i d e s and c o a l a l k y l i o d i d e s , w i t h n e t c l e a v a g e of s u l f i d e bonds. However,
t h e r e d u c t i o n i n En from 1250 t o 660 i s s u r p r i s i n g l y h i g h , s i n c e t h e 1 . 7 % S c o n t e n t
c o r r e s p o n d s t o o n l y 0.66 S / a s p h a l t o l m o l e c u l e , of which most is e x p e c t e d t o be i n
h e t e r o c y c l i c a r o m a t i c r i n g s . A somewhat g r e a t e r r e d u c t i o n i n Mn is reported for a
d u p l i c a t e experiment i n F i g u r e 2 . I t i s t h e r e f o r e p o s s i b l e t h a t I a l o n e may be a b l e
t o c l e a v e e t h e r l i n k s , a c o n c l u s i o n t o be s u p p o r t e d i n d i s c u s s i o n of F i g u r e 2. Thus,
a b i l i t i e s of Me.Si14 and of h e x a m e t h y l d i s i l a z a n e p l u s MEsSiCl ( t h e l a t t e r i n t e n d e d f o r
t r i m e t h y l s i l y l a t i o n ? t o c l e a v e a s p h a l t o l s may be due a s much or more t o h a l i d e i o n s
generated a s to t h e o r i g i n a l reagent.

We t r i e d sodium i n l i q u i d ammonia as an e t h e r - c l e a v i n g r e a g e n t , b u t found t h a t

a d d i t i o n of sodium i n l i q u i d ammonia t o a c o l d s o l u t i o n of a s p h a l t o l i n b u t y l a m i n e
gave b e t t e r c o n t r o l , less r e d u c t i o n of t h e a s p h a l t o l , and a d e c r e a s e i n Mn by n e a r l y
50%. Treatment of t h i s p r o d u c t w i t h p y r i d i n e h y d r o i o d i d e ( r i g h t c e n t e r of F i g u r e 1)
t h e n gave f u r t h e r r e d u c t i o n i n m o l e c u l a r w e i g h t . However, our d a t a s u g g e s t t h a t com-
b i n a t i o n of t h e sodium and H I r e a c t i o n s gave no more c l e a v a g e t h a n H I a l o n e .

F i g u r e 2 summarizes c l e a v a g e r e a c t i o n s of two o t h e r a s p h a l t o l s w i t h H I ( c h e c k of
F i g u r e 1 e x p e r i m e n t ) , H B r , t o l u e n e s u l f o n i c a c i d , and some m e t a l s a l t s , (except
t h e Me1 e x p e r i m e n t ) i n p y r i d i n e s o l u t i o n . The o t h e r a c i d s , even a t 5 0 ° , are n o t a s
e f f e c t i v e a s H I a t room t e m p e r a t u r e , b u t z i n c bromide, and e s p e c i a l l y z i n c c h l o r i d e
and L i I * H z 0 , 6 have g i v e n more m o l e c u l a r w e i g h t r e d u c t i o n t h a n any of t h e a c i d s . How-
e v e r , a l l of t h e s e r e a c t i o n s have a p p a r e n t l y r e s u l t e d i n i n c o r p o r a t i o n of p y r i d i n e i n
t h e p r o d u c t s , a s shown by t h e h i g h r e c o v e r i e s and h i g h n i t r o g e n c o n t e n t s . Some p r o -
d u c t s a l s o l o s e w e i g h t s l o w l y and p e r s i s t e n t l y on h e a t i n g a t 140" i n v a c u o . A p o s s i b l e
e x p l a n a t i o n i s t h a t c l e a v a g e of an a r y l a l k y l e t h e r by m e t a l h a l i d e g i v e s m e t a l pheno-
l a t e and a l k y l h a l i d e ; some of t h e l a t t e r t h e n r e a c t s w i t h p y r i d i n e s o l v e n t t o g i v e
u n s t a b l e q u a t e r n a r y p y r i d i n i u m s a l t s . However, t h e r e m a r k a b l e r e a c t i v i t y of t h e s e r e -
a g e n t s a t low t e m p e r a t u r e s may be a s s o c i a t e d w i t h t h e use of p y r i d i n e as s o l v e n t .

Conclusions

T h i s p r o g r e s s r e p o r t shows t h a t a s p h a l t o l from I l l i n o i s No. 6 c o a l c a n be e x t e n -

s i v e l y degraded a t or n e a r room t e m p e r a t u r e by s e v e r a l a c i d i c and b a s i c r e a g e n t s and
by some o x i d i z i n g and r e d u c i n g a g e n t s , w i t h good t o e x c e l l e n t r e c o v e r y of o r i g i n a l
183
carbon. These a g e n t s a p p e a r t o a t t a c k e t h e r l i n k s , o r maybe a r o m a t i c r i n g s i n oxida-
t i o n s a t pH 1 3 , b u t a s y e t we know of no p r e c e d e n t f o r r e a c t i o n s of a l i p h a t i c amines
o r a l c o h o l i c KOH w i t h e t h e r s a t t h e s e t e m p e r a t u r e s . To d e t e r m i n e t h e p r o p o r t i o n s of
v a r i o u s kinds o f b r e a k a b l e s i n g l e bonds i n I l l i n o i s No. 6 c o a l , we p l a n t o c a r r y o u t
f u r t h e r d e g r a d a t i o n s on a s p h a l t 0 1 by combinations of r e a g e n t s , and t h e n e x t e n d t h e
most promising of t h e s e r e a c t i o n s t o e x t r a c t e d c o a l . We e x p e c t t h a t t h i s k i n d of
i n f o r m a t i o n w i l l p r o v i d e t h e b a s i s f o r new and economical approaches t o c o a l l i q u e f a c -
t i o n , which w i l l employ much m i l d e r c o n d i t i o n s and much less e x p e n s i v e p r o c e s s e s and
plants.

Acknowledgement

Most o f t h e r e s e a r c h d e s c r i b e d h e r e was s u p p o r t e d by t h e U.S. Department of Energy

under C o n t r a c t No. ET-78-C-01-3293.

References

(1) P r e s e n t a d d r e s s , Department of Chemistry, E a s t e r n I l l i n o i s U n i v e r s i t y ,

C h a r l e s t o n , I L , 61920.

(2) J. G. H u n t i n g t o n , F. R . Mayo, and N. A . K i r s h e n , F u e l , 58, 24 (1979).

(3) F. R. Mayo and N. A . Kirshen, F u e l , i n p r e s s .

( 4 ) M. E. Jung and M. A . L y s t e r , J . Org. Chem., 42, 3761 (1977).

(5) S . Friedman, M. L. Kaufman, W. A. S t e i n e r , and I . Wender, F u e l , 40, 33 (1961).

(6) I . T. H a r r i s o n , Chem. Communications, 1969, 616.

184
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cn
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3-?

185
 23-A 82/.7T/.lY 244 81/.790/.133
03.6/ 524/ - 03.4/ 616/ -

11-A 104/.784/ -
Asph 100/.787/.125 104/ 555/ -
174 100/ 980/ -

9-A 99/.769/
102/ 363/
-
-
LiI'H$ As@
28-A
1Qd.782f.140
lOp/lW/ -
HI .
6-8 84/.787/
89/ 430/
-
-

@-A 95/.804/ - I-A i o s / . n s / - 42-A 96/.810/ -

108/ 379/ - r19/ 4281 - 102/ 392/ -
Key t o a-gement of data: Abbreviations :

Sanple Atom $ C/ H/C /.O/C

+
Yield
A s = asphalt01
Bn = benzyl Py = pyridine
Bu, Et, Me = n-butyl, ethyl, methyl
4 HbDS = hemethyldisilazme
No. Vt. $ /-weq.OH/rnole d, h, rn = days, hours, minutes

Figure 2. Cleavages of asphaltole in pyridine eolution (except with HeI)

and at room temperature (except a8 noted o t h e n i s e ) .

186
 OXYDESULFURIZATION OF COAL TREATED WITH METHYL IODIDE --
IMPLICATIONS FOR REMOVAL OF ORGANIC SULFUR

R. Warkuszewski, C.-K. Weia, and T. D . Wheelock

A m e s L a b o r a t o r y , USDOE, and
Department o f Chemical E n g i n e e r i n g
Iowa S t a t e U n i v e r s i t y ,
A m e s , Iowa 50011

Introduction

Zn t h e c h e m i c a l d e s u l f u r i z a t i o n p r o c e s s b e i n g d e v e l o p e d a t t h e
Ames L a b o r a t o r y , c o a l i s l e a c h e d w i t h a d i l u t e s o l u t i o n of sodium
c a r b o n a t e c o n t a i n i n g d i s s o l v e d oxygen u n d e r p r e s s u r e and a t e l e v a t e d
temperature. F o r many c o a l s , most o f t h e i n o r g a n i c ' s u l f u r c a n b e
removed, and t h e o r g a n i c s u l f u r c o n t e n t c a n b e r e d u c e d by 25-40%
(1,Z). I n some i n s t a n c e s , as much as 70% of t h e o r g a n i c s u l f u r h a s
been removed. An e s s e n t i a l p i e c e o f i n f o r m a t i o n i n e v a l u a t i n g t h e
e f f e c t i v e n e s s of a p r o c e s s f o r t h e removal of o r g a n i c s u l f u r i s t h e
i d e n t i . t y and r e a c t i v i t y of t h e v a r i o u s s u l f u r f u n c t i o n s grouped u n d e r
t h e term " o r g a n i c s u l f u r . "

Although much d a t a i s a v a i l a b l e on t h e c o n t e n t and d i s t r i b u t i o n of

the s o - c a l l e d p y r i t i c , s u l f a t i c , a n d o r g a n i c s u l f u r i n v a r i o u s c o a l s ,
rei-atively l i t t l e h a s b e e n p u b l i s h e d on t h e n a t u r e and a b u n d a n c e of
t h e o r g a n i c s u l f u r g r o u p s i n c o a l . E s s e n t i a l l y no d a t a a r e a v a i l a b l e
on t h e r e a c t i v i t y of such f u n c t i o n a l groups under o x i d i z i n g c o n d i t i o n s ,
such a s t h o s e found d u r i n g o x y d e s u l f u r i z a t i o n . I n f a c t , no c o m p l e t e l y
s a t i s f a c t o r y method e x i s t s as y e t f o r t h e d i r e c t d e t e r m i n a t i o n o f o r -
g a n i c s u l f u r i n c o a l , a l t h o u g h a few methods a r e b e i n g d e v e l o p e d .
These methods are b a s e d e i t h e r on m i c r o p r o b e a n a l y s i s ( 3 , 4 ) , o r o n low-
k m p e r a t u r e a s h i n g o f t h e o r g a n i c components of c o a l ( 5 ) , o r on t h e i r
t h e r m o k i n e t i c r e d u c t i o n t o hydrogen s u l f i d e ( 6 ) . A s a r o u t i n e , however,
o r g a n i c s u l f u r i s s t i l l b e i n g d e t e r m i n e d as t h e d i f f e r e n c e b e t w e e n t h e
t o t a l s u l f u r and t h e amount o f t h e i n o r g a n i c ( i . e . , p y r i t i c p l u s s u l -
f a t i c ) s u l f u r , a c c o r d i n g t o ASTM p r o c e d u r e s .

A t t e m p t s t o i d e n t i f y and q u a n t i t a t i v e l y d e t e r m i n e o r g a n i c s u l f u r
f u n c t i o n s i n c o a l h a v e b e e n few. On t h e b a s i s o f v e r y s p a r s e d a t a , i t
i s g e n e r a l l y assumed t h a t t h e o r g a n i c s u l f u r i n c o a l c a n b e d e s c r i b e d
a l m o s t c o m p l e t e l y by t h e f o l l o w i n g c l a s s e s :

a P r e s e n t a d d r e s s : D e p t . of C h e m i c a l E n g i n e e r i n g , U n i v e r s i t y o f M i n n e s o t a ,
M i n n e a p o l i s , MN 5 5 4 5 5

187
 Class 1. A l i p h a t i c o r aromatic t h i o l s (mercaptans,
t h i o p h e n o l s ) : R-SH, Ar-SH

Class 2. A l i p h a t i c , a r o m a t i c , o r mixed s u l f i d e s
( t h i o e t h e r s ) : R-S-R, Ar-S-Ar, R-S-Ar

Class 3. A l i p h a t i c , a r o m a t i c , or mixed d i s u l f i d e s
(bisthioethers): R-SS-R, Ar-SS-Ar, R-SS-Ax

Class 4 . H e t e r o c y c l i c compounds o f t h e t h i o p h e n e t y p e :
e .g., d i b e n z o t h i o p h e n e

I t i s g e n e r a l l y assumed t h a t any c h e m i c a l d e s u l f u r i z a t i o n p r o c e s s
that c a n remove o r g a n i c s u l f u r w i l l do s o b e c a u s e of t h e r e a c t i v i t y o f
compounds i n C l a s s 1, 2 , a n d 3. H e t e r o c y c l i c compounds i n Class 4 are
e x t r e m e l y s t a b l e t o c h e m i c a l a t t a c k and h i g h t e m p e r a t u r e .

The f u n d a m e n t a l a p p r o a c h i n t h i s s t u d y i s b a s e d on t h e d i f f e r e n t
r e a c t i v i t y of methyl i o d i d e toward d i f f e r e n t o r g a n o s u l f u r f u n c t i o n s t o
p r o d u c e s u l f o n i u m compounds. The g e n e r a l scheme o f r e a c t i o n s f o r t h e
v a r i o u s c l a s s e s o f s u l f u r g r o u p s c a n b e summarized a s f o l l o w s ( 7 ) :

1. Hercaptans:

R-SH + CH I
3
---t R-S-CH
3
+ HI
+-(CH -
R-S-CH3 + CH I *R-S
3
)
3 2 I

-
2. Sulfides:

R-S-R + CH I
+
R2S -CH I-
3 3 3)

3. Disulf i d y :

R-SS-R + 4 CH 1 - 2 R-S
+ (CH3)2 I- + I2 4)
3
4. H e t e r o c y c l i c compounds:

Dibenzothiophene + CH I + n o
3
reaction

The r e a c t i o n of c o a l w i t h m e t h y l i o d i d e w a s u s e d p r e v i o u s l y ( 8 )
t o d e t e r m i n e t h e t h i o e t h e r c o n t e n t of c o a l by m e a s u r i n g t h e u p t a k e o f
i o d i n e , p r e s u m a b l y a s s o c i a t e d as i o d i d e w i t h t h e s u l f o n i u m compounds.
But t h e i o d i n e u p t a k e i s n o t a t r u e m e a s u r e of t h e t h i o e t h e r c o n t e n t
b e c a u s e o t h e r compounds, n o t a b l y h e t e r o c y c l i c n i t r o g e n compounds, c a n
al.so r e a c t r e s u l t i n g i n u p t a k e o f i o d i n e . To overcome t h i s d i f f i c u l t y ,
t h e s u l f o n i u m compounds w e r e washed o u t w i t h a s o l v e n t l i k e a c e t o n e ,
and t h e d e c r e a s e i n t h e s u l f u r c o n t e n t was t h e n t a k e n as t h e i n d i c a t o r
of t h e t h i o e t h e r c o n t e n t ( 7 ) . A s i m i l a r p r o c e d u r e w a s a d o p t e d i n t h i s
work.
 Experimental

Ma t er i a l s

The c o a l used i n t h i s s t u d y was a h i g h - v o l a t i l e b i t u m i n o u s c o a l

from t h e S t a r mine i n Mahaska County, Iowa. The c o a l w a s p u l v e r i z e d ,
s c r e e n e d u s i n g U.S. S t a n d a r d sieves, d r i e d , a n d a n a l y z e d f o r a s h , h e a t -
i n g v a l u e , and s u l f u r d i s t r i b u t i o n b y ASTM p r o c e d u r e s .

F r e s h m e t h y l i o d i d e was used d i r e c t l y from t h e r e a g e n t b o t t l e . In

some e x p e r i m e n t s , t h e r e a g e n t was c l e a n e d by s h a k i n g w i t h m e r c u r y , b u t
no s i g n i f i c a n t d i f f e r e n c e was n o t i c e d i n t h e r e s u l t s .

Methyl I o d i d e R e a c t i o n

A s l u r r y o f 2 0 g c o a l and 30 m l m e t h y l i o d i d e was p l a c e d i n a l a r g e
t e s t t u b e , c o v e r e d w i t h f o i l , and a l l o w e d t o s t a n d f o r 3 d a y s a t room
t e m p e r a t u r e . The s l u r r y was t h e n f i l t e r e d a n d washed w i t h a b o u t 2 1.
a c e t o n e t o remove r e a c t i o n p r o d u c t s and u n r e a c t e d m e t h y l i o d i d e , u n t i l
t h e t e s t f o r i o d i d e ( s i l v e r n i t r a t e ) was n e g a t i v e . The t r e a t e d c o a l
was d r i e d and a n a l y z e d a g a i n . Q u a l i t a t i v e tests f o r r e s i d u a l i o d i d e
i n t h e t r e a t e d c o a l ( h y d r o g e n p e r o x i d e t r e a t m e n t f o l l o w e d by e x t r a c t i o n
o f i o d i n e i n t o a b e n z e n e l a y e r ) showed o n l y t r a c e s o f i o d i d e . The
m e t h y l i o d i d e t r e a t m e n t s w e r e r e p e a t e d on enough c o a l s a m p l e s t o p r o v i d e
a s t o c k of t r e a t e d c o a l t o b e used f o r t h e o x y d e s u l f u r i z a t i o n e x p e r i m e n t s .

O x y d e s u l f u r i z a t i o n of C o a l i n A u t o c l a v e

The c o a l ( 4 0 g ) was l e a c h e d f o r 1 h r w i t h 400 m l s o l u t i o n i n a

I - l i t e r a u t o c l a v e d e s c r i b e d p r e v i o u s l y (1). The l e a c h i n g w a s d o n e a t
1 5 O o C u n d e r 50 o r 200 p s i a oxygen p a r t i a l p r e s s u r e . For non-oxidizing
c o n d i t i o n s , a p a r t i a l p r e s s u r e of 5 0 p s i a n i t r o g e n was u s e d . Water o r
0 . 2 E sodium c a r b o n a t e was used as t h e l e a c h i n g s o l u t i o n . The r e s i d u e s
from t h e a 1 k a l i ; e l e a c h i n g s t e p w e r e l e a c h e d f o r a s e c o n d t i m e , a l s o
f o r 1 h r a t 150 C , u s i n g w a t e r , 0 . 1 E s u l f u r i c a c i d , 0 . l M p h o s p h o r i c
a c i d , o r 0 . 2 M sodium c a r b o n a t e i n a n i t r o g e n a t m o s p h e r e .

Calculations

In o r d e r t o account f o r t h e d i f f e r e n t l e v e l s of ash i n t h e v a r i o u s c o a l
r e s i d u e s , t h e s u l f u r c o n t e n t was c o n v e r t e d from w e i g h t p e r c e n t t o pounds
o f s u l f u r p e r m i l l i o n Btu. T h i s c o n v e r s i o n , i n e f f e c t , a l l o w e d t h e com-
p a r i s o n of t h e o r g a n i c s u l f u r c o n t e n t i n t h e o r g a n i c ( i . e . , c o m b u s t i b l e )
p o r t i o n of t h e c o a l .

I n a few cases, t h e h e a t i n g v a l u e was n o t a c t u a l l y d e t e r m i n e d b u t

was c a l c u l a t e d u s i n g a f o r m u l a (l), b a s e d on t h e a s s u m p t i o n t h a t t h e
a s h - f r e e h e a t i n g v a l u e is r e l a t i v e l y c o n s t a n t f o r t h e same c o a l , r e g a r d -
l e s s of t h e t r e a t m e n t c o n d i t i o n s .

189
 R e s u l t s and D i s c u s s i o n

Removal of S u l f u r b y t h e Methyl I o d i d e T r e a t m e n t

The r e s u l t s of t r e a t i n g c o a l w i t h m e t h y l i o d i d e are p r e s e n t e d i n
T a b l e 1. Based on t h e pounds o f s u l f u r p e r m i l l i o n B t u , t h e m e t h y l
i o d i d e t r e a t m e n t removed, on t h e a v e r a g e , 4 8 . 3 % of t h e o r g a n i c s u l f u r .
T h i s seems t o i n d i c a t e t h a t a t l e a s t o n e - h a l f of t h e o r g a n i c s u l f u r
i s i n t h e c l a s s t h a t i s reactive toward m e t h y l i o d i d e . Since thiophenic
compounds a r e u n r e a c t i v e and d i s u l f i d e g r o u p s r e a c t t o o s l o w l y a t room
t e m p e r a t u r e , t h e r e a c t i v e p o r t i o n of t h e o r g a n i c s u l f u r i s p r o b a b l y of
t h e s u l f i d e and m e r c a p t a n c l a s s e s .

F u r t h e r t e s t s were r u n by t r e a t i n g m i n e r a l p y r i t e w i t h m e t h y l
i o d i d e under s i m i l a r c o n d i t i o n s and t h e n w a s h i n g w i t h a c e t o n e . No
r e a c t i o n was o b s e r v e d ; t h e s u l f u r c o n t e n t w a s u n a f f e c t e d . A l s o ,
s i m p l e washing o f c o a l w i t h 2 1. of a c e t o n e ( w i t h o u t p r i o r m e t h y l i o d i d e
treatment) did not alter s i g n i f i c a n t l y the ash content, heating value,
and s u l f u r d i s t r i b u t i o n of t h e c o a l .

Another p o s s i b l e e x p l a n a t i o n f o r t h e r e d u c t i o n of t h e o r g a n i c
s u l f u r may b e o f f e r e d i f m e t h y l i o d i d e s i m p l y m e t h y l a t e s t h e c o a l ,
t h u s i n c r e a s i n g i t s o r g a n i c c o n t e n t and d e c r e a s i n g t h e s u l f u r c o n t e n t
by " d i l u t i o n . " I f t h i s o b s e r v a t i o n w e r e a r e f l e c t i o n of a m e t h y l a t i n g
e f f e c t , t h e n t h e h e a t i n g v a l u e s h o u l d have i n c r e a s e d , t h e a s h c o n t e n t s h o u l d
h a v e d e c r e a s e d , and t h e " d i l u t i o n " s h o u l d a p p l y t o a l l t y p e s of s u l f u r
i n c o a l . Yet t h e c h a n g e s i n a s h c o n t e n t , h e a t i n g v a l u e , and w e i g h t
r e c o v e r y were i n s i g n i f i c a n t ; and t h e p y r i t i c a n d s u l f a t i c s u l f u r v a l u e s
w e r e f a i r l y constant. It seems, t h e r e f o r e , t h a t o r g a n i c s u l f u r was
r e a l l y removed by t h i s p r o c e d u r e . I t i s n o t known, however, by what
mechanism t h e s u l f o n i u m s a l t s are washed away.

Removal of S u l f u r by O x i d a t i v e L e a c h i n g

The r e s u l t s o f l e a c h i n g t h e m e t h y l i o d i d e - t r e a t e d c o a l are pre-

s e n t e d i n T a b l e 2 . The s u l f u r c o n t e n t s h o u l d b e compared n o t o n l y
t o t h a t of t h e i n i t i a l c o a l b u t a l s o t o t h a t o f t h e m e t h y l i o d i d e -
t r e a t e d c o a l ir! T a b l e 2 . I t c a n b e s e e n t h a t l e a c h i n g w i t h a l k a l i o n l y ,
(sample'No. 016D), i n t h e a b s e n c e of oxygen, d i d n o t h a v e any e f f e c t
on t h e s u l f u r c o n t e n t . When l e a c h i n g i n t h e p r e s e n c e of oxygen, t h e
t o t a l s u l f u r c o n t e n t d e c r e a s e d , l a r g e l y b e c a u s e of a d e c r e a s e i n t h e
i n o r g a n i c s u l f u r c o n t e n t . The t o t a l s u l f u r c o n t e n t w a s l o w e r when
h i g h e r oxygen p a r t i a l p r e s s u r e s were used o r when t h e l e a c h i n g s o l u t i o n s
were a l k a l i n e . The o r g a n i c s u l f u r c o n t e n t was r e l a t i v e l y c o n s t a n t , a l -
though i t a p p e a r e d s l i g h t l y h i g h e r u n d e r n o n - a l k a l i n e c o n d i t i o n s when
water o n l y w a s u s e d as t h e l e a c h a n t .

190
 I n T a b l e 3 r e s u l t s are p r e s e n t e d f o r d e s u l f u r i z a r i o n e x p e r i m e n t s
i n which a s e c o n d l e a c h i n g s t e p was added a f t e r t h e f i r s t l e a c h i n g
s t e p with an a l k a l i n e solution. The a d d i t i o n a l l e a c h i n g was d o n e i n
a n o n - o x i d i z i n g n i t r o g e n a t m o s p h e r e , u s i n g water, s u l f u r i c a c i d ,
p h o s p h o r i c a c i d , o r sodium c a r b o n a t e s o l u t i o n s . A s i d e from o n e r u n
which a p p e a r s t o b e a n o m a l o u s , t h e t o t a l s u l f u r c o n t e n t d i d n o t seem
t o be r e d u c e d by t h e s e c o n d l e a c h i n g s t e p .

The o r g a n i c s u l f u r c o n t e n t , h o w e v e r , a p p e a r s t o b e s l i g h t l y h i g h e r
than that obtained a f t e r one l e a c h i n g s t e p , under a l k a l i n e c o n d i t i o n s
and i n t h e p r e s e n c e o f oxygen. I t may b e p o s s i b l e t h a t u n d e r t h e n i t -
r o g e n a t m o s p h e r e o f t h e s e c o n d s t e p , some o f t h e p y r i t e may b e c o n v e r t e d
t o elemental s u l f u r . Such a c o n v e r s i o n would be c h a r a c t e r i z e d by a de-
c r e a s e i n t h e p y r i t i c s u l f u r , an i n c r e a s e i n t h e o r g a n i c s u l f u r , b u t no
c h a n g e i n t h e t o t a l s u l f u r . Such a c o n v e r s i o n would a l s o b e f a v o r e d
by a c i d i c c o n d i t i o n s .

M e t b l I o d i d e Treatment of Oxydesulfurized Coal

I

The r e s u l t s i n T a b l e 4 show t h e e f f e c t of m e t h y l i o d i d e t r e a t m e n t
on S t a r c o a l t h a t h a d b e e n p r e c l e a n e d b y a f l o a t - s i n k t e c h n i q u e and
s u b s e q u e n t l y l e a c h e d f o r 1 h r w i t h 0.2 fl sodium c a r b o n a t e a t 15OoC
u n d e r 50 o r 200 p s i a p a r t i a l p r e s s u r e of oxygen. By c o m p a r i s o n w i t h t h e
s u l f u r v a l u e s i n T a b l e 1, t h e c l e a n i n g a n d l e a c h i n g a p p a r e n t l y removed
only the inorganic sulfur, leaving the organic s u l f u r content largely
unaffected. L e a c h i n g a t h i g h e r oxygen p a r t i a l p r e s s u r e seemed t o remove
more t o t a l s u l f u r .

C u r i o u s l y , s u b s e q u e n t t r e a t m e n t of t h e l e a c h e d c o a l w i t h m e t h y l
i o d i d e d i d n o t seem t o remove any o r g a n i c s u l f u r a s i t d i d when
a p p l i e d t o t h e r a w , u n l e a c h e d c o a l ( s e e Tab1.e 1). T h i s l a c k o f
r e a c t i v i t y may b e d u e o t o p h y s i c a l c h a n g e s i n t h e c o a l c a u s e d by t h e
h i g h t e m p e r a t u r e (150 C) o f t h e l e a c h i n g . A l t e r n a t i v e l y , t h e c h e m i c a l
l e a c h i n g may have c a u s e d a c o n v e r s i o n o f r e a c t i v e o r g a n o s u l f u r g r o u p s
i n t o u n r e a c t i v e groups. Perhaps a l s o t h e d i f f e r e n c e i n t h e p a r t i c l e
s i z e (-200 mesh i n t h i s s e t of e x p e r i m e n t s compared t o -150/+200 mesh
i n previous experiments) can be a c o n t r i b u t i n g f a c t o r .

Conclusions

T r e a t m e n t o f c o a l w i t h m e t h y l i o d i d e f o l l o w e d by e x t e n s i v e
washing w i t h a s o l v e n t t o remove t h e r e a c t i o n p r o d u c t s h a s b e e n u s e d
t o remove a p p r o x i m a t e l y o n e - h a l f o f t h e o r g a n i c s u l f u r c o n t e n t i n a n
Iowa h i g h v o l a t i l e b i t u m i n o u s c o a l . The p y r i t i c and s u l f a t i c s u l f u r
c o n t e n t was n o t a f f e c t e d by t h e m e t h y l i o d i d e t r e a t m e n t . Washing t h e
c o a l w i t h s o l v e n t o n l y d i d n o t p r o d u c e any e f f e c t e i t h e r . On t h e b a s i s
of c h e m i c a l r e a c t i o n s r e p o r t e d i n t h e l i t e r a t u r e , i t i s assumed t h a t
t h e r e a c t i v e s u l f u r g r o u p s t h a t were removed by t h i s t r e a t m e n t may
be o r g a n i c s u l f i d e s or m e r c a p t a n s .

191
 Subsequent l e a c h i n g s of t h e methyl i o d i d e - t r e a t e d c o a l under v a r i o u s
conditions of oxydesulfurization did not reduce f u r t h e r t h e organic
s u l f u r c o n t e n t . The i n o r g a n i c s u l f u r c o n t e n t , however, was r e d u c e d
by t h e o x y d e s u l f u r i z a t i o n s t e p s . I t c a n b e assumed t h a t a l l t h e
r e a c t i v e and a c c e s s i b l e o r g a n i c s u l f u r was removed b y t h e methyl
i o d i d e t r e a t m e n t , and f u r t h e r chemical d e s u l f u r i z a t i o n w a s d i r e c t e d
only against the inorganic sulfur.

When t h e c o a l was f i r s t p r e c l e a n e d by a f l o a t - s i n k t e c h n i q u e and

t h e n l e a c h e d by t h e o x y d e s u l f u r i z a t i o n p r o c e d u r e , t h e o r g a n i c s u l f u r
c o n t e n t was n o t a f f e c t e d by s u b s e q u e n t t r e a t m e n t w i t h m e t h y l i o d i d e .
T h i s l a c k o f r e a c t i v i t y o f t h e o r g a n i c s u l f u r t o w a r d m e t h y l i o d i d e may
be c a u s e d by p h y s i c a l o r c h e m i c a l c h a n g e s i n t h e c o a l b r o u g h t a b o u t
by the h i g h t e m p e r a t u r e o r c h e m i c a l n a t u r e of t h e o x y d e s u l f u r i z a t i o n
process.

Acknowledgment

T h i s work was p e r f o r m e d u n d e r C o n t r a c t No. W-7405-eng-82 with

the U.S. Department o f Energy, D i v i s i o n o f F o s s i l Energy.

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Methods, T. D. Wheelock ( e d . ) , ACS Symposium S e r i e s 64, Am. Chem.
SOC., Washington, D.C., 1977.

6. Attar, A . a n d D u p u i s , F . , Am. Chem. SOC. Div. of F u e l Chem. P r e -

p r i n t s z ( 2 ) , 44 ( 1 9 7 8 ) .

7. Angelova, G . K. a n d S y s k o v , K. I . , I z v . Akad. Nauk SSSR, M e t . T o p l . ,

No. 5, 1 5 3 ( 1 9 5 9 ) .

8. Postowsky, J . J . and H a r l a m p o v i c h , A. B., F u e l 1 5 ( 8 ) , 229 ( 1 9 3 6 ) .

192
T a b l e 1. E f f e c t of m e t h y l i o d i d e (MeI) t r e a t m e n t and a c e t o n e (Me2CO)
washing on s u l f u r c o n t e n t of c o a l . a
6
Treat- H.V., Ash, S C o n t e n t , l b . / 1 0 Btu. S Redn., %
No. ment Btu./lb. % Tot. Pyr. S u l f . Org. Org. T o t .

OOlD None 12579 8.34 2.02 0.98 0.15 0.89 -- --

029D Me2C0 12495 8.95 2.06 1.08 0.20 0.78 -- --
003 Me1 + Me2C0 12552 8.29 1.68 1.08 0.17 0.43 50.6 16.8
004 Me1 + Me2C0 12490 8.46 1.62 1.18 0.14 0.30 66.3 19.8
005 Me1
2
+
Me CO 12506 8.57 1.78 -1.04 0.10 0.64 28.1 11.9
Ave (of 0 0 3 , 0 0 4 , 005) 12516 8.44 1.70 1.10 0.14 0.46 48.3 15.8

a s t a r c o a l (-150/+200 mesh).

b'lD" denotes average of d u p l i c a t e a n a l y s i s .

T a b l e 2. One-step o x y d e s u l f u r i z a t i o n o f Me1 - t r e a t e d c o a l . a

6
SampAe Leach 0 Press., H.V., Ash, S C o n t e n t , l b . / 1 0 Btu.
No. soln. psia Btu./lb. % T o t . Pyr. S u l f . Org.

OOlD -- None -- 12579 8.34 2.02 0.98 0.15 0.89

Ave. of 003, __ Me1 -- 12516 8.44 1.70 1.10 0.14 0.46
0 0 4 , 005
50 12046 6.75 1.28 0.44 0.17 0.67
013 H2°
006 Na2C03 50 10220 12.90 1.21 0.52 0.16 0.53
200 11818 6.68 1.06 0.20 0.12 0.75
014D H2°
012 Na2C03 200 11787 13.02 0.91 0.39 0.08 0.44
016D Na2C03 OC 12245 7.41 1.63 0.95 0.11 0.57

astar c o a l (-150/+200 m e s h ) , t r e a t e d w i t h Me1 and t h e n l e a c h e d 1 h r a t

150°C w i t h H20 o r 0 . 2 Na2C03 u n d e r 5 0 o r 200 p s i a 02.

b''D" d e n o t e s a v e r a g e of d u p l i c a t e a n a l y s i s .

%on-oxidizing atmosphere of 50 p s i a N p a r t i a l pressure.

2

193
T a b l e 3. Two-step d e s u l f u r i z a t i o n of Me1 - t r e a t e d c o a l . a
-
6
Sarnphe 2nd s t e p H.V., Ash, S C o n t e n t , l b . / 1 0 Btu.
No. Leach B t u . /lb. % Tot. Pyr. S u l f . Org.

1st Leach S t e p w i t h 0 . 2 Na2C03 u n d e r 5 0 p s i a O2

018D 11119 14.28 1.30 0.67 0.03 0.60

HZO
020D 0.1 H2S04 11529 6.72 1.24 0.46 0.05 0.73
023 0.1 H3P04 11479 12.26 1.31 0.53 0.03 0.63
024D 0.2 5 Na2C03 9042 13.33 1.20 0.52 0.07 0.61

1 s t Leach S t e p w i t h 0 . 2 E Na2C03 u n d e r 200 p s i a 0

2
02 7D 11763' 9.32 0.86 0.21 0.05 0.60
H2°
035D 0 . 1 E H2S@4 11614' 6.03 1.03 0.30 0.08 0.65
03in 0.1 fi H3P04 11478' 12.27 1.16 0.52 0.05 0.59
033D 0 . 2 _M Na CO 9831 19.65 1.20 0.65 0.08 0.47
2 3
__ -
a S t a & coal (-150/+200 m e s h ) , t r e a t e d w i t h Me1 a n d t h e n l e a c h e d 1 h r a t
150 C w i t h 0 . 2 Na CO3 u n d e r 50 o r 200 p s i a @?. For 2nd s t e p , l e a c h e d
1 a d d i t i o n a l h r a t f 5 0 W under 50 p s i a N2 w i t h i n d i c a t e d l e a c h s o l u t i o n .

b''D" denotes average o f d u p l i c a t e a n a l y s i s

"H.V. calculated.

T a b l e 4. M e t h y l i o d i d e (MeI) t r e a t m e n t of l e a c h e d c o a l . a
~~ ~~ ~~ ~ ~ ~~

6
SampAe H.V., Ash, S C o n t e n t , lb./10 B t u .
No. Treatment Btu./lb. % T o t . P y r . S u l f . Org.

06OD Leached u n d e r
50 p s i a O2 9162 9.53 1.29 0.24 0.05 1.00
062D Me1 t r e a t m e n t of
Sample 060D 11370 10.63 1.26 0.24 0.01 1.01
@64 Leached u n d e r 200
psia 0 10810 11.71 1.04 0.11 0.02 0.91
065D Me1 t r e a t m e n t o f
Sample 064 11534 10.56 0.96 0.10 0.01 0.85

a s t a r c o a l (-200 mesh) p r e c l e a n e d and l e a c h e d 1 h r a t 15OoC w i t h 0 . 2 E Na2C03

u n d e r 50 o r 200 p s i a 0
2'
b*fD" d e n o t e s a v e r a g e o f d u p l i c a t e a n a l y s i s .
194
 MOLECULAR COMPONENTS OF C U L AND COAL STXUCTUFG D. Bodzek and
A. hlarzec. Departmect o f petroleum and Coal Chemistry. P o l i s h
Academy o f Sciences. 44-100 Gliwice, 1 Naja 6 2 St. Poland.
High v o l a t i l e bituminous coal was e x t r a c t e d a t room temperature by
means o f 18 s o l v e n t s having t L e i r electron-donor /DH/ end -acceptor /AN/
p r o p e r t i e s q u a n t i t a t i v e l y determined. E x t r a c t s were analysed by f i e l d
i o n i z a t i o n and h i g h r e s o l u t i o n mass spectrometry. E x t r a c t a b l e compounds
havicg molecular masses i n 200-600 8.xn.u. range c o n s t i t u t e 30% wi;. o f
c o a l organic material. Hydrocarbons /CnH2n,6 up t o C,U2n-34/, nitrogen
comgounds /CHIT, CHN2, CH.N3/, oxxygen compounds /CHO, CH02/ and nitrogen-
oxygen compounds /CEJO, C€!N20, CHN02, CIIIi202, CID130/ were i d e n t i f i e d i n
t h e e x t r a c t s . On t h e b a s i s of e x t r a c t i o n d a t a / e x t r a c t y i e l & * solvent
DN acd AB numbers/ end LS a n a l y s i s t h e conclusion has been drawn t h a t
e x t r a c t a b l e compounds a r e bonded to c o a l macromolecular network by
electron-donor-acceptor bonds. These bonds a r e destroyed during extrac-
t i o n by s u b s t i t u t i o n a c t i v i t y o f solveots. Solvent s u b s t i t u t i o n capabi-
l i t i e s depend on t h e i r donor and acceptor ~ w b e r 3 .

135