higher compared to the traditional y-Al203 and SiO 2 supported systems. The effect of surface area of the support and of the catalyst composition on their cata-.
React. Kinet. Catal. Lett., Vol. 36, No. 1, 65-70 /1988)
CARBON-SUPPORTED
SULFIDE BIMETALLIC
CATALYSTS
FOR HYDROr
DESULFURIZATION [Yu.I. Yermakov[ , A.N. M.S. Institute All-Union
Startsev,
Tsekhanovich
Shkuropat,
and V.F.
of Catalysis,
Research
S.A.
Institute
G.V.
Plaksin,
Surovikin
Novosibirsk
630090,
USSR
of Technical
Carbon,
Omsk,
USSR
Received December 4, 1986 Accepted April 9, 1987
It has been e s t a b l i s h e d ported
sulfide Ni-Mo,
higher c o m p a r e d supported
that the activity of c a r b o n - s u p -
N i - W and Co-Mo catalysts
to the traditional y-Al203
systems.
~OKa3aHO~
T@nb C y ~ b ~ H ~ H ~ X Ni-Mo,
HOBepXHOCTH
A traditional drodemetallization catalysts
to similar
[2-6].
BnH~HHe
HOCHTenH H COCTaBa K a T a n H 3 a T O p O B
support of c a t a l y s ~ for h y d r o r e f i n i n g is y-Al203.
For recent years,
sulfide
systems on u
catalysts
however,
into the c o m p o s i t i o n
supports
of the t e c h n o l o g y
permits
and hythese
[i-6].
The
can be higher
[4-6], because most of of the active
It has been noted p r e v i o u s l y
cation of carbon fication
H3yqeHO
cy-
HaHeceH-
have also been p r e p a r e d on carbon supports
the cobalt enter phase"
CHCTeM,
HOCH-
CBOHCTBa.
a c t i v i t y of c a r b o n - s u p p o r t e d compared
Tpa~H~HOHH~X
H OKHCb anmMHHH~.
Ha HX K a T a ~ H T H q e C K H e
Ha y F H e p o ~ H ~
N i - W H Co-Mo K a T a H H 3 a T 0 p O B
B~me aKTHBHOCTH
HMX Ha CHnHKaPenb y~enbHo~
on their cata-
has been studied.
qTO aKTHBHOCTb H a H e C e H H ~ X
~eCTBeHHO
and SiO 2
The effect of surface area of the
support and of the c a t a l y s t c o m p o s i t i o n lytic p r o p e r t i e s
is much
"Co-Mo-S
[5] that the appli-
to achieve
to extract metals
the utmost simplifrom e x h a u s t e d
Akad~miai Kiadd, Budapest
YERMAKOV et al. : H Y D R O D E S U L F U R I Z A T I O N
catalysts
for hydrorefining
ports.
But carbon
hardly
compete
described
supports
of activated
charcoal
due to their
low mechanical
of narrow pores.
Material
Besides,
type Sibunit whose
previously
Here we present pare sulfide
out their
with oxides
and the high portion ash content.
by simply burning
[7], is free
the results
catalysts
type,
supcan strength
they have high
properties
have been
from these disadvantages.
of applying
for thiophene
this material
to pre-
hydrogenolysis.
EXPERIMENTAL Carbon material used as a support and Si02-supported spectively,
were
catalysts
were prepared
Catalysts aqueous
commercial
of W(Mo)
analytical
(NH4)6Mo7024.4H20.
and treated
with
a trap at T = -70 ~ sulfurization without
the model
in Table
reaction
and T = 300 ~
RESULTS
Chemical
Parent
sealed
i. Catalyst
of thiophene
Co(NO3)2"6H20;
calcined
were
products
vessels
composition
activities
circula-
degassed
in reaction
samples
in air at 400
out sulfurization
Chemical
compounds
catalyst
for 1 h in a static samples
with
and stored
of catalyst
were compared
hydrogenolysis
in
at the
is in
at PH2 = 2 MPa
[8].
compositions
in different
with the atomic
ratio
and activities
carriers
component
activity
[8] is only
(M 1 = Ni, Co;
(per 1 g) activity
is almost maximum, sulfide
1.5 -2 times
are listed catalysts as highs
catalysts
and Carbon)
h = M I / M 1 + M 2) = 0.2 - 0.3
of Si02-supported
lic origin
of sulfide
(SiO2, 7-A1203
M 2 = Mo, W) at which the specific
66
re-
AND DISCUSSION
supported
active
salts.
impregnation,
(120 ~
freezing
with air.
impregnation
grade Ni(NO3)2"6H20; After
Sulfurized
temperature,
contact
represented
by one-step
in H2S at 400 ~
tion installation
7-A1203-
with SBE T = 200 and 240 m2/g,
and Ni(Co)
were dried by IR irradiation ~
traditional
[8].
were prepared
solutions
WO 3 and
type Sibunit with SBE T = 17-550 m2/g was
[7]. For comparison,
of the
in Table
i. The
of organometalas that of the
YERMAKOV et al. : HYDRODESULFURIZATION
Table Composition
and c a t a l y t i c
Composition of catalysts
properties
of b i m e t a l l i c
SBET f o r s u p p o r t s
catalysts.
No.
1
Support
sulfide
= 200-240 m2/g
Metal concentration (wt.%) Co or Ni
Activity at 300 UC mol thioph. g-at(Ml+M2)xSx
Mo or W
xl04 1
Ni-W
Sibunit
0.8
4.2
ii0
2
Ni-W
Sibunit
1.0
6.0
83
3
Ni-W
Sibunit
1.2
9.0
74
4
Ni-W
SiO 2
1.0
6.4
50
5
Ni-W
AI203
1.2
8.0
48
6
Ni-Mo
Sibunit
0.6
4.0
116
7
Ni-Mo
Sibunit
1.5
i0.0
92
8
Ni-Mo
SiO 2
0.8
2.3
30
9
Ni-Mo
AI203
1.8
6.0
30
10
Co-Mo
Sibunit
I.i
8.0
60
corresponding This
catalysts
fact can be a s c r i b e d
ported lysts
catalysts. supported
on c a r b o n
decrease
metals
increasing
with
is due to the rising
We b e l i e v e of the c a t a l y s t used
evidence
the
being
by i m p r e g n a t i o n
metal
in the m e a n
same r e a s o n
activity
coarse surface
particles
are c h a r a c t e r i z e d I g-at.
accounts
having
of m i x e d
is, a p p a r e n t l y ,
of s u p p o r t e d
Apparently,
size of s u l f i d e
this
particles
(Fig.
for the d e p e n d e n c e area of c a r b o n
material
I). The m e t a l
concen-
the c h a r a c t e r i s t i c
that on a c a r r i e r
the cata-
of metals.
on the surface
preparation
the same,
per
of c a r b o n - s u p -
systems,
concentration.
concentration
for the c a t a l y s t
tration
more
the
by i m p r e g n a t i o n .
organometallic
in the a c t i v i t y
increase
surface
on c a r b o n
to the high d i s p e r s i t y
But u n l i k e
by a s l i g h t
with
supported
curve
a low s u r f a c e
sulfides,
~nsufficient
since
is likely area
there
to form
in this case
to e n s u r e
the
"mono67
Y E R M A K O V et al. : HYDRODESULFURIZATION
~o so
p
~-, 4o
>
200
Fig.
i.
Ac~vity
400 600 SurfQce o r e a , m 2 9-1
of N i - M o
area of c a r b o n centration
catalysts
carriers
versus
the
at a c o n s t a n t
in the c a t a l y s t s
surface metal
(4% Mo and
O
con-
1.5% Ni)
O
x
800
z
120 ~ "6
0
-~ E
o-'
"6
0
