B u l l . SOC. Chim. Belg. vo1.

93/n0 8-9/1984
SB-D WOUSWP UKETINC Ow HYDWDTRUTINC CATALYSTS
Lowdn-lrUeuw, 29 -
30 Octobar, 1984

NiMo/Al2O3 CATALYSTS. Ni AND !40 CONCENTRATIONS EFFECT.

A COMPARATIVE STUDY OF PYRIDINE HDN AND THIOPHENE HDS REACTIONS
ON REDUCED AND SULFIDED CATALYSTS

M.J. Ledoux, G. A g o s t i n i , R. Benazouz and 0. Michaw

Laboratoire de C a t a l y s e e t de Chimie d e s S u r f a c e s , U n i v e r s i t b Lo u i s P a s t e u r ,
E.R.A. 385 au C.N.R.S., 4 , r u e B l a i s e P a s c a l 67000 STRASBOURG -
FRANCE

ABSTRACT
The N i and No c o n c e n t r a t i o n s e f f e c t on t h e p y r i d i n e HDN and thiophene HDS
undor normal H2 p r e s s u r e , on reduced o r s u l f i d e d classical N i M o / A 1 2 0 j has been
s t u d i e d by comparison of a c t i v i t i e s and by simultaneous a n a l y s i s of t h e selec-
t i v i t y i n d i f f e r e n t products. I f t h e expected promoting e f f e c t of N i f o r t h e
HDS reaction h a s been found, t h e b e s t c a t a l y s t f o r HDN was t h e pure Mo/Al2O3.
I t has 81.0 been found t h a t t h e s u l f i d e d MO c a t a l y s t is a b e t t e r hydrogenating
system t h a n t h e reduced o x i d i c form and t h e s u l f i d e d Ni promoted c a t a l y s t s . A n
a t t u a p t o e x p l a i n t h e promoting e f f e c t of N i on Mo based c a t a l y s t s is given.

INTRODUCTION
A l a r g e number of papers has been p u b l i s h e d on Co-promoted Mo/A1203 cata-
l y s t s d u r i n g t h e l a s t faw y e a r s (see (1) f o r most o f the r e f e r e n c e s ) . For t h e s e
c a t a l y s t s a s f o r unsupported ones, a s y n e r g i c interaction between Mo and t h e
promoter h a s been found f o r a n atomic r a t i o p = Co/Co + No o f about 0.30 ( 1 , 2 ) .
The o r i g i n of t h i s synergy is s t i l l a matter of c o n t r o v e r s y I i) p a r t i c u l e s of
nOS2 and Cogs8 o b t a i n e d from t h e b i l a y e r (3,4) are c l o s e l y a s s o c i a t e d , g i v i n g
rise t o t h e phenomenon of " c o n t a c t synergy" (2) where H 2 is d i s s o c i a t e d on Co
conters and s p i l l s over t h e MoS2 centers; ii) C o s t a b i l i z e s Mobs2 i n t h e form of
a monolayer ( 5 ) o r i n t h e form of c r y s ta l l i t e s ( 6 ) , w i t h consequences on t h e
number of edges which are considered a s a c t i v e s i t e a r e a s because a n i o n i c vacan-
cies a r o mainly l o c a t e d on t h e s e edges! iii) Co is i n t e r c a l a t e d i n nos2 ( o r wS2)
l a t t i c e ( 7 ) ; i v ) Co ir n o t i n t e r c a l a t e d b u t s u b s t i t u t e s Mo i n t h e nos2 l a t t i c e
i n t h e a c t i v e phase s o - c a l l e d "Co - Mo - S phase", Cogs8 being i n a c t i v e ( 8 ) .
D i f f e r e n t s t u d i e s ( 9 ) s t r o n g l y support t h i s l a s t p r o p o s a l , and a l i n e a r corre-
l a t i o n between t h e a c t i v i t y f o r HDS and t h e concentration of t h i s Co-no-S phase
determined by nijssbauer emission spectroscopy h a s even been found ( 1 0 ) . How-
ever, no a t t e m p t has boen made t o c o r r e l a t e t h e s t r u c t u r e of a s i t e i n t h e Co-
Mo-S pha8e and t h e mechanism o€ t h e r e a c t i o n . Following t h e d i s c u s s i o n of
V r i n a t e t a1 ( 1 1 , t h i s phase could be r e s p o n s i b l e f o r an e x t r a - s t a b i l i z a t i o n of
d i s o r d e r e d MoS2 w i t h a high p r o p o r t i o n of edges and i n consequence o f a c t i v e
HDS sites.
I n comparison, very few papers have been published on t h e N i M o couple and
no d i r e c t evidence f o r t h e presence of Ni-no-S phase h a s been given (11).
Thakur e t a l . (12) have shown e q u i v a l e n t behaviour between NiMo and CoMo bulk
c a t a l y s t s , f o r hydrogenation of cyclohexene and HDS o f thiophene, f o r t h r e e va-
lue. of p , 0, 0.01 and 0.25. However, t h e hydrogenation i s i n c r e a s e d s i x f o l d

- 635 -
and t h o HDS twofold on N U 4 0 c a t a l y r t r . The " c o n t a c t rynargy" i r propored am an
axplanation o f the synargic i n t e r a c t i o n .
Studying d i f f e r e n t couples on a c i d i c s u p p o r t s and u r i n g d i f f a r e n t t e a t
r e a c t i o n r , Franck and La Paga (13) have shown t h a t N i W , N i M o , COHO and Cow cou-
p l a r p r e s e n t a s y n e r g i c e f f e c t f o r v a l u e r of p of . b o u t 0.25. For hydrogenation
of t o l u e n a , HDS o r HDN (whatever t h e f e e d , modal molecular o r i n d u s t r i a l f a a d r )
the r e l a t i v e a c t i v i t i e r o f t h a d i f f a r e n t coupler can be C h r a i f i e d , whatevar
the rupport as N i W > NiMo > CoMo > COW w i t h an a x c e p t i o n f o r HDS a t l o w hydro-
gen p a r t i a l p r e s s u r e whara CoMo a x h i b i t r t h e b e a t performancar. For y-alumina
rupported N i M o and CoMo CAtalyStr prepared i n t h o I.ID. condition. b u t s u l f i d e d
by d i f f e r e n t ways, U r z t e l a n a t a1 ( 1 4 ) found A r l i g h t l y b e t t e r i n t r i n s i c acti-
v i t y i n t h e t o l u e n e and cyclohexana hydrogenation f o r Nino than f o r CoMo.
Working on bulk N i M o c a t a l y r t r , P r a t t e t a1 (15) have found the maximum
s y n e r g i c e f f e c t f o r HDS a t a valua of p of about 0 . 5 5 which i r a r a t h e r high
value compared t o t h e u r u a l 0.25 - 0.35 range. I n a l a t e r r t u d y ( 1 6 ) , they
have c l e a r l y shown by u s i n g high r a r o l u t i o n e l a c t r o n microrcopy t h a t t h e r o l e
of n i c k e l i n t h e 0.55 c a t a l y r t ( i n t h e i r p r e p a r a t i v e condition.) i r t o increasa
d r a m a t i c a l l y t h e d i s p e r s i o n of nos2 w i t h A high p r o p o r t i o n of adgem. T h i r n i c -
k e l i r n o t i n t e r c a l a t e d i n t h e nos2 l a t t i c e . Tha e f f e c t of Co on t h e nos2 dim-
pornion has also been obrerved, b u t a t a lower r e s o l u t i o n , by rcanning e l e c t r o n
microscopy ( 1 ) . These o b r a r v a t i o n r arm n o t i n c o n t r a d i c t i o n w i t h the e x i s t e n c e
of a rmall amount of N i - - no 8 phare ( n o t d e t e c t a b l e by microscopy) similar
t o tho Co - -
Mo S r e p o r t e d by Toprde a t a l . ( 1 0 ) .

EXPERINENTAL PROCEDURE
c a t a l y r t preparation -
oxidic precursor
The oxide p r e c u r r o r war prepared by a two a t o p impregnation p r o c e r s u r i n g
i n both s t e p s the pore f i l l i n g method. y-alumina powder of high pu i t y (Ketjan
CK 300, 217 m2/g a f t e r a c t i v a t i o n f o r 2 h i n a i r a t 6OO0C, 0.62g/cm , 0.2-0.5 5
mm, a n a l y s i s of impurity i n ( 1 7 ) , w a s f i r s t l y impregnated w i t h a water r o l u t i o n
of ammonium heptamolybdate (Merck) a t a pH between 5 and 7 dapending on tha Mo
c o n c e n t r a t i o n . They wore than l a f t 1 2 h i n a i r a t room temperatura, d r i e d 2 1
h i n a i r a t 12OoC, and c a l c i n e d 2 h i n a i r a t 500'C. Nickel n i t r a t e (Merck)
water r o l u t i o n a t n e u t r a l pH war then added a t room temperature and t h e same
d r y i n g and c a l c i n i n g procedure war used. The Mo/Al2O3 c a t a l y r t h.8 been im-
pregnated a t pH 11. 100 mg of each c a t a l y s t wefa ground i n t o f i n e powder and
Analy8ed by atomic a d s o r p t i o n a f t a r m i n e r a l i z a t i o n . The r u r f a c a composition
8hoUld n o t be very d i f f a r e n t t o the bulk AnAlyrir according to t h a XPS mamure-
mentr p u b l i r h e d by Karztalan e t (11. (14). Some BET r p e c i f i c arear w e e d e t e r -
mined on Mo/Al2O3 and two NiMo/Al203 and ware a l l found a t 180 f 10 m 5/g.
An i n d u s t r i a l c a t a l y r t , Nino PROCATALYSE no HR 346 har bean t e n t e d i n the
same c o n d i t i o n s . Before use, the e x t r u d a t e s were broken and r i f t a d i n 0.2-0.5
mm p a r t i c u l e s .

Apparatus
Information about t h e a p p a r a t u r (flow system on fixed-bed reactor) urad
f o r t h a non-rulfided c a t a l y r t r has baan given alrawhare (17, 1 8 ) . A s i m i l a r
a p p a r a t u r war used f o r t h e s u l f i d a d c a t a l y r t r b u t w i t h a t r i p l a g a r i n l e t rys-
tern ( p u r i f i e d H 2 , N 2 o r high grade p u r i t y H2S/H2 28 vol. L ' A i r Liquide) and A
KOH t r a p t o d e s t r o y the e x c e r r of H2S a f t a r tha pumping ryrtem.

A c t i v a t i o n procedure and c o n d i t i o n of r e a c t i o n
A l l t h e r e c o n d i t i o n s arm r a p o r t e d i n Table 1 t o g e t h e r w i t h the a n a l y t i c a l
procadura.
On non-rulfidad catalyst., r a a c t i o n product. warm analyrad only a f t e r t h e f l o -
wing of 20 u 1 of p y r i d i n a i n the working c o n d i t i o n r . Thir q u a n t i t y ha. been

- 636 -
 Phara Reduced o x i d e Sulf ided

Pretre. tment H2 1 atm, flow 7Oml/min 390°C, H ~ S / H 1~ atm, 70 ml/min, room

16 h. temperature 8 To 450°C i n 30
nm 8 4 5 O D C ~ 4 O O 0 C 5, min 8
pure H 2 , 400DC, 1 6 h 8 H2S/H2
4 0 O 0 A 4 5 O 0 , 5 min 8 450°, 55
min 8 pure H 2 , 2 h.

Reaction P y r i d i n e HDN - 275'C P y r i d i n e HDN - 450°C

4 torrs pyr 4 t o r r s pyr
1 atm H2 1 atm H2
1.5 t o 4 rl/min pyr 0 . 5 ul/min pyr
50 to 500 ml/min H2 30 ml/min H2
20 t o 50 mg c a t a l y s t 0.3 g
(150 mg f o r E(o/Al2O3)
+ 100 mg of pure Si02 f luks)
0.2 - 0.5 mm
2h, pure H 2 , 27SoC, 150 m l /
min
Thiophene HDS 275'C -
6 torrs thiophene
1 atm H2
= 3 u l / m i n thiophene
2 5 0 m l / m i n H2

Sampling A f t e r 20 u 1 o f p y r i d i n e have HDN. After 5 u 1 of pyridine

(See t e x t been pasoed over t h e c a t a l y s t (% 1 0 min)
f o r steady ( T i m depending upon the flow HDS. After 15 ul of t h i o -
state) rate) phene ( s 5 min)

VPC 1 colum O V l O l u l t r a c a p i l l a r y Si02, 50m : C3 t o Cl0 hydro-

carbons
analysis - 15'C t o SO°C +r amines excepted pipe-
ridine
- f o r HDN 1 a l u m SE30, 1 / 8 ' , 5 m, + 60.C : C1 t o C7 hydrocarbons
1 colum Carbowax 20 m/KOH 59, 1 / 8 ' , 5 m + 22OoC : pyr. + pip.
- f o r HDS 1 colum O V l O l
1 colum SE30 - high r e s o l u t i o n C 4 t o C8 hydrocarbons
C, t o C 4 + thiophene
+ thio-
phene

found l a r g e enough t o e s t a b l i r h a pseudo s t e a d y state. The f i r s t poisoning was

very r a p i d a t atmospheric p r e s r u r e o f H 2 and t h e s t e a d y state was reached i n a
fow minutes ( 3 t o 10 min. i n our wotking c o n d i t i o n s ) . The second poisoning de-
ponded o n l y upon t h e amount o f feed passed over t h e c a t a l y s t ( d e a c t i v a t i o n < 5%
i n one hour i n o u r working c o n d i t i o n s ) and l e d t o complete d e a c t i v a t i o n a f t e r
several days. On s u l f i d e d c a t a l y s t s , t h e s t e a d y s t a t e was reached a f t e r 5 min.
f o r HDN and 1 min f o r H D S . The amount of c a t a l y s t and t h e c o n d i t i o n s o f flow
have been chosen t o keep the conversion a lower t h a n 109 (30% f o r c e r t a i n HDS
reaction on very a c t i v a c a t a l y r t r ) i n o r d e r t o work i n the c o n d i t i o n of d i f f e -
r e n t i a l fixed-bed reactor.

- 637 -
ExpreSSiOn of activities
The specific activity r in mole/r.g (cata) ha8 been calculated from equa-
tion

p being the flow of reactant (pyr or thio) in ul/min, p it@ w l u m i c mass, M it8
molecular weight and w the catalymt ma~s.
For a more accurate compariion, tho activity reported on the difforent figure
is R in mole per second per gram of active phase ( 9 MOO3 + 9 NiO).

RESULTS AND DISCUSSION

FIG. 1-a shows a clear promoting effect on the HDS of thiophene due to the
incorporation of Ni to Mo sulfide. The maximum promotion appear8 for p 0.35.
In FIG. 1-b, S measurem directly the value of the promotion when r for pure
-
F 0
0

8
HDS R.lO”

l-7-J s .to-’

FIG. 1. The full sylnbol refer to our preparation, th. open symbols to HiMD PrOCa-
talyse. a) thiophene HDS - 275OC - b) 1. eynergy S A % of butane in C,,
fraction. c) % of butane in Cq fraction versus contnrsion.

Mo/A1203 and pure Ni/A1203 have been 8ubtraCt.d (25). Only the value for p
0.864 is negative and corre8pondr to an antipromotion (or poironing) effect of
-
small m o u n t of Mo in N i (catalyrt composition : Ni 5.329 Mo 1.369).
There i8 no correlation between the amount of butane formed and the promo-
ting effect. A detailed study of the comporition (19) of tho hydrocarbon pro-
ducts obtained from thiophene show8 that, in the conditions of reaction, the
three n-butenem in thermodynamic equilibrium concentration are the only product8
at initial conversion. No butadiener, neither C, nor butane (FIG. lc) are found
at zero conversion. The but-1-ene is preferentially hydrogenated in butane by
ruccessive reaction or readsorption while the concentrations remains at thermo-
dynamic equilibrium level for but-2-enes cis and trans. The easier hydrogena-

- 638 -
t i o n of a - o l e f i n s coapared t o t h e i r corresponding i n t e r n a l o l e f i n s is a common
o b s e r v a t i o n on metallic c a t a l y s t and is u s u a l l y e x p l a i n e d through a classical
Horiuti-Polanyi mechanism ( 2 0 ) .
I n FIG. 2 , t h e HDN of p y r i d i n e on t h e same p r e s u l f i -
ded e a t a l y o t does n o t show such a promoting e f f e c t due t o
nickel. I n f a c t , t h e b e s t c a t a l y s t is pure No s u l f i d e /
Al2O3. In addition, a l l t h e o t h e r p values give a c t i v i t y

two maxima, one around p -

v a l u e s l y i n g between 1 and 2.10-' mole/s.g (act. @ ) w i t h
0.25 and a second f o r p - 0.75.
These r e s u l t s , a t l e a s t a t normal p r e s s u r e , are d i f f e r e n t
from the o b s e r v a t i o n s r e p o r t e d by Franck and Le Page ( 1 3 ) .
However a s i m i l a r v a r i a t i o n h a s been found by V r i n a t a t
a l . (1) a t d i f f e r e n t p r e s s u r e f o r the s e l e c t i v i t y o f hy-
drogenation of dibenzothiophene over CoWo bulk c a t a l y s t s .
I n a d d i t i o n , f i g u r e l c s u g g e s t s t h a t the promoting e f f e c t
on HDS h a s probably no connection w i t h t h e hydrogenation
c a p a c i t y of t h e c a t a l y s t .

Ll
p I F I G . 2. Wridinc HDN-450°C. (0 : NiMn PROCATALYSE)

The r e a c t i o n o f p y r i d i n e HDN h a s been used t o test the m o d i f i c a t i o n o f t h e

c a t a l y s t due t o s u l f i d a t i o n and v a r i a t i o n o f metal c o n c e n t r a t i o n s because, con-
t r a r y t o t h e thiophene €IDS r e a c t i o n , t h e d i s t r i b u t i o n o f p r o d u c t s (hydrocarbons
s e l e c t i v i t y ) is profoundly changed by t h e s e m o d i f i c a t i o n s . The s t u d y o f t h i s
s e l e c t i v i t y can g i v e information concerning t h e n a t u r e and t h e p r o p e r t i e s o f
t h e c a t a l y s t s u r f a c e working c o n d i t i o n s .

1 i 4 1 tb hy'*.

Rb
Y

Jo

PIC. 3.. Fyridine MIB on reduced oxi- FTC. 3. F'yridine MIH on rulfidcd
- n5oc
dic c a t s l y r t oatdyit - 4 W C
A5.0861i45.57 - 0 6 . 7 4 ~ 0 4 8 . 2- ONiMO PROCATUYSE

- 639 -
 On reduced o x i d i c c a t a l y s t s ( F I G. 3.) one observes a very f a s t i n c r e a s e o f
a c t i v i t y , w i t h i n c r e a s i n g N i c o n c e n t r a t i o n a t c o n s t a n t 8 Mo (19). The a c t i v i -
t y is almost independent o f t h e Mo c o n c e n t r a t i o n . On pure N i / A 1 2 0 3 t h e aelec-
t i v i t y of t h e products (mainly 389 5 C1, 279 C 4 + C1 ( 8 5 8 of b u t a n e ) , 179 C3 +
2C1) has a t y p i c a l metallic c h a r a c t e r w i t h i n i t i a l cracking on ensembles o f low
coordinated atoms a b l e t o form rnultibondinq with t h e d i f f e r e n t fragments ( 1 9 ) .
This mechanism is not t h e Hofmann e l i m i n a t i o n . 129 C3 + C 2 and 68 C5 (909 of
s a t u r a t e d producta) are obtainod by t h e Hofmann e l i m i n a t i o n ( 2 1 ) . When Mo con-
c e n t r a t i o n i n c r e a a a s , t h e a c t i v i t y slowly d e c r o a r e s and t h e metallic c h a r a c t e r
of t h e d i s t r i b u t i o n d i s a p p e a r s i n favor of t h e Hofmann r e a c t i o n c h a r a c t e r i z e d
by C 5 molecules. On pure Mo/A1203 t h e d i s t r i b u t i o n becomes C5 = 709, C3 + C 2 =
109 and C 4 + C1 = 209.
On s u l f i d e d c a t a l y s t s , FIG. 3b, t h e a c t i v i t y is s t i l l dependent upon t h e
amount of N i and roughly independent of t h e No c o n c e n t r a t i o n with, however, a
r e v e r s e e f f e c t of N i I i n t r o d u c t i o n of t h i s metal h a s now a s t r o n g poisoning
e f f e c t on t h e r e a c t i o n a t c o n s t a n t Mo. I n a d d i t i o n , one can observe, f o r a g i -
-
ven N i l 4 0 c a t a l y s t ( f o r i n s t a n c e Ni 2.20% Mo 7 . 4 4 % ) , a s t r o n g d e a c t i v a t i o n ori-
g i n a t e d by t h e s u l f u r treatmont (646.10-8 a t 275OC on t h e o x i d i c form and
16.10-lo on t h e s u l f i d e d form). I n o r d e r t o understand t h i s double poisoning
( i . e . s u l f u r and n i c k e l ) , t h e HDN of p y r i d i n e ham been s t u d i e d on pure Mo/A1203
i n i t s p a r t i a l l y reduced o x i d i c form, and on i t r p r o g r e s s i v e l y p r o s u l f i d e d form.
In FIG. 4a ( l e f t p a r t ) , one can see t h a t t h e c a t a l y s t a l r e a d y reaches a f t e r
only 3 minutes of s u l f u r a t i o n the a c t i v i t y found f o r 2h30 of p r e s u l f u r a t i o n .
This a c t i v i t y is one o r d e r of magnitude lower t h a n the a c t i v i t y of t h e non-pre-
a u l f i d e d c a t a l y s t . Subsequent i n t r o d u c t i o n of Ni i n c a t a l y s t s c o n t a i n i n g t h e
same amount of Mo ( F I G . l a , c e n t r a l p a r t ) , shows a n o t h e r r a p i d d e c r e a s e i n a c t i -
v i t y a t very low c o n t e n t of Ni, followed by a slower decrease u n t i l N l = 5.59.
The r i g h t p a r t of F IG. 4a r e p o r t s t h e a c t i v i t y of c a t a l y s t s c o n t a i n i n g t h i s l a t -
ter amount of N i , but with decreasing amounts of HO. Below 3.79 of Mo, t h e ac-
t i v i t y remains c o n s t a n t and is equal t o t h e a c t i v i t y of s u l f i d e d N i / A 1 2 0 3 .
I t is i n t e r e s t i n g t o follow t h e v a r i a t i o n o f a c t i v i t y t o g e t h e r with t h e
d i f f e r e n t s e l e c t i v i t i e s roported i n FIG. 4b and 4c. When s u l f u r is added t o
l o oxide, t h e r e l a t i v e amount of hydrogenated C4 and C5 i n c r e a r o s immediately
t o reach t h e l e v e l observed a f t e r 2h30 of p r e s u l f i d a t i o n (FIG. 4 b ) . A t t h e
same time, t h e r a t i o c y c l C5/lin C 5 d e c r e a s e s r a p i d l y . W e have a l r e a d y shown
( 2 1 , 2 2 ) t h a t t h e i n c r e a s e of t h e hydrogenation a b i l i t y of t h e c a t a l y s t favours
t h e mechanism of formation of l i n C5 t o t h e p r e j u d i c e of c y c l . C5. On p a r t i a l -
l y reduced M o 0 3 / A 1 2 0 3 , o n l y h i g h l y reduced Mo atoms (degree $ I V ) a r e a b l e to
d i a s o c i a t o H 2 and t o perform hydrogenation. The amount of such sites depends
upon t h e c o n d i t i o n of reduction! XPS a t u d i e o i n our c o n d i t i o n r (23) show t h a t
most of t h e Mo atoms are a t i l l a t o x i d a t i o n degree V I o r V and o n l y few a t de-
g r e e I V o r less.
The formation of MoS2 reduces a l l Mo atoms t o degree IV and t h e s e a r e now
a b l e t o d i s s o c i a t e H2 and t o hydrogenate t h e aromatic amhe as w e l l a s t h e o l e -
f i n i c i n t e r m e d i a t e s formed by HDN.
Although both mechanismr are s t r o n g l y i n h i b i t e d by t h e s u l f i d a t i o n , t h e
r e l a t i v e i n c r e a s e of Cq + C1 t o t h e detriment of C5 molecules (FIG. 4c), i n d i -
cates t h a t t h i s s u l f i d a t i o n i n c r e a s e s s t r o n g l y t h e metallic c h a r a c t e r of t h e

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 r
1
FIG. &a. pyridino HDN, left p a r t , function of time of

1 .lo4

FIG. bb.
FIG. 4c.
p r c s u l f i b t i o n - c e n t r a l p a r t , function of
li concentration - r i g h t p a r t , function of
h concentration (&creasing mo u n t ) .
0 % s a t C5/ZC5, 0 % butane/rC&, A cycl.
Cg/lin.Cg.
0 % CL + C1 + MI3 i n a. % C5 + m3 in a.

c a t a l y s t . As seen p r e v i o u s l y , t h e formation
of small molecules by i n i t i a l metallic c r a c -
king needs a l a r g e s i t e (ensemble) composed
of many contiguous atoms i n a high degree of
I r e d u c t i o n . This e x p l a i n s why t h e HDN a c t i v l -
t y on o x i d i c N i M o i n c r e a s e s very r a p i d l y w i t h
N i c o n c e n t r a t i o n ; one can imagine t h a t t h e
s i z e of N i p a r t i c u l e s i n c r e a s e s w i t h t h e con-
I c e n t r a t i o n ( 1 9 ) . The a n i o n i c v a c a n c i e s o f
t h e edges of MoS2 c r i s t a l l i t e s can be consi-
dered a s an ensemble of atoms l a r g e enough
t o perform t h e C 4 + C1 + NH3 i n i t i a l c r a c k i n g ,
b u t n o t t h e 5 C1 + NH3 and C3 + 2 C1 + NH3
t h a t one can observe i n a d d i t i o n on pure N i
metal/A1203. On pure Mo/Al2O3 i n o x i d i c form,
the number of t h e s e ensembles is very small
and less t h a n 20% of t h e transformed p y r i d i n e
are o b t a i n e d through t h i s way, whereas about
55% a r e o b t a i n e d on MoS2. On FIG. 4c, C 3 + C 2
+ NH3 is n o t r e p o r t e d and follows C5 behaviour.
This minor mechanism of a c i d i c c h a r a c t e r has
a l r e a d y been e x p l a i n e d ( 2 1 1 .
However, t h e advantage o b t a i n e d on t h e
one hand by t h e h i g h e r hydrogenation a b i l i t y
o f t h e s u l f i d e phase (which favours t h e f i r s t
s t e p o f t h e Hofmann e l i m i n a t i o n and t h u s t h e
formation of C5 molecules ( 2 1 ) ) and on t h e
o t h e r hand by t h e increase of t h e metallic
c h a r a c t e r (which favours t h e formation o f
C4 + C1 + NH3) does n o t compensate t h e l o s s
of b a s i c i t y which is a consequence of t h e
s u b s t i t u t i o n of 0- by S-. T h i s b a s i c i t y is c r i t i c a l f o r t h e second s t e p of t h e
Hofmann e l i m i n a t i o n ( a b s t r a c t i o n of a p r o t o n i n 6 p o s i t i o n t o t h e N atom).
The a d d i t i o n of N i to XO i n s u l f i d i c form, i n c r e a s e s t h e metallic charac-
t e r of the mystem ( c e n t r a l p a r t , FIG. 4 c ) . I n f a c t , w e b e l i e v e t h a t N i i n c r e a -
ses the number of d e f e c t s , and thum of ensembles a b l e t o crack. This conclu-
s i o n is i n f u l l agreement w i t h V r i n a t and D e Mourgues (1) and P r a t t e t a1
(16)'s microscopic o b s e r v a t i o n on COMO and N i M o bulk c a t a l y s t s .
A t t h e same time, w e observe a s t r o n g d e c r e a s e o f t h e hydrogenating a b i l i -
t y of t h e c a t a l y s t (FIG. 4b, c e n t r a l p a r t ) , followed by a secondary maximum
corresponding t o t h e c o n c e n t r a t i o n o f the maximum promoting e f f e c t i n HDS. That
could be explained i f one admits t h a t t h e s t a b i l i z a t i o n e f f e c t of N i on d e f e c t s

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i r duo t o an e l e c t r o n i c t r a n a f e r t towards nos2. T h i s e i o c t r o n i c t r a n r f e r t ha8
been obaorvad i n XPS r t u d i e r on Co-no-S phare by T o p r k ' r group ( 9 ) . The mag-
n i t u d e of t h i r e l e c t r o n i c tranrfert would depend upon the naturo of t h e w t a l
p a i r (hore NiMo) and can oxplain t h o o b r e r v a t i o n r publirhed by C h i a n o l l i o t a 1
( 2 4 ) . The hydrogenating c a p a c i t y of nOS2 banal plan. murt t h u r be s t r o n g l y
affected by thir tranrfert. The rocondary m a x i m u m correspond. to a maximum of
defect8 w i t h MO a t 0 m Carrying a n i o n i c vacancier and thur l e a s a f f e c t e d by t h e
electronic tranrfert.
Tho recond decreare i n HDN a c t i v i t y (PIC. 4a) r e r u l t i n g f r o m the introduc-
t i o n of Ni would be duo t o the docreare of t h e hydrogenating a b i l i t y of t h e ca-
t a l y t i c ayrtem necerrary f o r tho f i r r t r t e p of tho HDN reaation.
F i n a l l y , t h e r i g h t p a r t of FIG. 4b shows t h e very poor hydrogenating a b i l i t y of
Ni s u l f i d e whon Mo concentration diminisher. The c y c l . C5 i n c r e a r e r when hydro-
genation diminisher; however when Mo9 i r below 5 9 , the t r e n d r o v e r r e s and a now
mechanism is probably involved. I n F I G . 4c, tho decreare of Mo concentration
shcmr a r e t u r n t o a moro acidic mechanism (C4 + C I L and C 5 ) ) . T h i s obrerva-
t i o n added t o t h e small increare of HDN a c t i v i t y t o a constant l e v e l for high
concentration of Ni r u l f i d o , can be explained by t h e i n t a r v e n t i o n of t h e acidic
p r o p e r t i e a of t h e alumina ( r u p p o r t ) , which is nogligeable for Mo concentrations
above 79. The Ni r u l f i d o c r y s t a l l i t e a are t h e hydrogenating c a n t e r s .

CONCLUSION
Which kind of conclurion can be drawn from t h i a rtudy on the o r i g i n of t h o
promoting e f f e c t of Ni f o r HDS r e a c t i o n ?
The promotion affects the a t e p of r u l f u r removal and not the hydrogenation stop.
No v a r i a t i o n i n t h e HDS nuchaniam ( c o n s t a n t r e l e c t i v i t y ) har been observed whon
varying t h e Ni and Mo conoentrationa ( t h i s work), o r the prerrure ( 1 ) ; thir im-
p l i e r t h a t the n a t u r e of t h e mito i r not modified i n r p i t e of the presence of
tho promoting effect. The n i c k e l would have, thus, the e f f e c t of increasing
t h o numbor of rites, probably the a n i o n i c vacancior on th. edger of t h e nos2
c r y r t a l l i t e a . The role of a Ni-no-S phare (rimilar t o t h e Co-no-S described by
Toprde'a group ( 9 ) ) would be t o a t a b i l i z e a very d i r o r d e r e d nos2 phase by elec-
t r o n i c t r a n r f e r t and would not be a c t i v e ar a s i t e f o r the HDS r e a c t i o n . Tho
c o r r o l a t i o n found betwoen HDS a c t i v i t y and Co-Mo-6 9 (10) would be of aecondary
order a a c t i v i t y is proportional t o the number of miter which i r i n t u r n propor-
t i o n a l t o t h e 9 Co-Mo-8. I n a d d i t i o n , t h e p r e r e n t work doer not allow t o r u l e
o u t a porrible f i r s t o r d e r c o r r e l a t i o n betwoon HDS a c t i v i t y and t h e average
hoat of formation of th two s u l f i d e r , am reported by C h i a n e l l i e t a1 ( 2 4 ) .
I t is porrible t o imagine a double e f f e c t , namoly M i n c r e a r e of number of si-
ter ( r t a b i l i z e d by Ni) and an improvoment of t h o q u a l i t y of there rites by op-
t i m i z a t i o n of t h e o r b i t a l r t r u c t u r e and of the bond r t r e n g t h , according t o
Chianelli'r correlation. I t i r a l r o possible t h a t thir c o r r e l a t i o n would a l r o
be of rocondary order I a c t i v i t y would be proportional t o tho number of r i t e
and t h o numbor of s i t e would be i n t u r n proportional t o t h o Ni + Mo e l e c t r o n i c
t r a n r f o r t . T h i s Ni + Mo e l e c t r o n i c tranrfert would be d i r e c t l y related t o t h e
averago h e a t of formation of the two s u l f i d e s .

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ACXNOWLEDGPlEblT
T h i s p r o j e c t h a s been p o s s i b l e with t h e f i n a n c i a l assistance of t h e DRRT
(Action RBgionale no 83.5.0365).

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25.
whero ri is t h e a c t i v i t y of t h e c a t a l y a t i f rNi for Ni/A1203 w i t h 5.08% w.
of Ni, rMofor Mo/A1203 w i t h 7.13% w. o f no, x t h e % W. o f N i and y t h e %
w. o f Mo f o r t h e c a t a l y s t i.

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