Note: Descriptions are shown in the official language in which they were submitted.
1~8~S~
Canadian ~atent application No. 220,643 relates to a process
for the catalytic hydrode~ulphurization without catalyst replenishment
cf vanadium and nickel-containine residual hydrocarbon oils. According
to the ~aid Canadian patent application the desulphurization i~
carried out by contacting the oil at elevated temperature and
pressure and in the presence of hydrogen successively with two
different catalyst~, each of these t~o catalyst~ having a porosity
and a particle size within specified limits depending on the poro~ity
and particle size of the other catalyst in the combination and
on the hydroeen partial pressure applied, while the two catalysts
are applied in a specified v~lume ratio. As i8 shown in the said
Canadian patent application, the life of 8 certain quantity by
volume of such a catalyst combination in maintsining a certain
desulphurization level is longer than that of an equal quantity
by volume of either of the catalyst~ applied separately. It was
already observed in the said Canadian patent application that
the deactivation of the desulphurization catalyst combination
can be suppressed and consequently its life prolonged, by preceding
the desulphurization by Q cata~ytic demetallization. This observation
implies that, if a feed that has previously been catalytically
demetallized is processed over a certain quantity by volume of
the catalyst combination, the life of the catalyst combination
will be loneer than when the non-demetallized feed is processed
over the same qu~1tity by volume of the catalyst combination.
Therefore, upon application of a catalytic demetallization as
referred to hereinbefore, the feed wiIl be contacted with a larger
quantity by volume of catalyst than when no demetallization i8
applied, since in the former case, besides a specific quantity
by volume of the desulphurization catalyst combination, which
is the same in both cases, a certain quantity by volume of demetallization
catalyst i~ used in addition.
~, :
-- 3 --
Upon contination of the studies concerning the catalytic
hydrodemetallization of vanadium and nickel-containing residual
hydrocarbon oils followed by catalytic hydrodesulphurization of
the demetallized oil using a combination of two desulphurization
catalysts according to the said Canadian patent application, it
WQS found that the life of the desulphurization catalyst combination
in maintaining a certain desulp~ urization level can be considerably
prolonged, while keeping the total quantity by volume of catalyst
constant, when part Or the desulphurization catalyst combination
is replaced by a demetallization catalyst and when, in addition,
the ~ollowing requirements are met,
1) The desulphuriz~tion catalyst combination, which according
to the said Canadian patent application comprises a catalyst
I containing one or more catalysts and a single catalyst
II, is in the present patent application tsken to comprise
only two single desulphurization cstalysts, of which the
rirst is indicated as catalyst I and the second as catalyst
II.
2) The residual hydrocarbon oil that is used as the feed has
a total vanadium and nickel content above 120 ppmw.
3) The demetallization catalyst, indicated as catalyst 0, meets
: the following requirements
a) the catalyst comprises one or more metals having
hydrogenation activity on a carrier,
b) p/d>3.5-0.02 v, in which v is the percentage of the
total pore volume that consists of pores with a dia-
meter larger than 100 nm,
c) the total pore volume is larger than 0.40 ml/g,
d) the specific surface area i8 larger than 100 m /g,
but in cases where the catalyst has such a p and
.
- , : , , , . : :
d that the quotient p/d is larger than 3.5-0.02 v, hut at most 10-0.15 v,
the catalyst has to meet the following additional requirements: e) the
nitrogen pore volume is larger than 0.60 ml/g, f) the specific surface area
is larger than 150 m /g, and g) p is larger than 5nm.
4. Catalyst 0 has a larger total pore volu~e than catalyst I.
5. Catalyst 0 and catalyst I have such a p, d and v that the following
relation is met
~ cat.o~l 2X~ ~/(d) ] cat I-~.8(vo~vI))
6. l'he percentage of the joint cata]yst volume of catalysts 0, I and
II that is occupied by catalyst 0 amo-mts to at least 10 %v.
The catalytic hydrodemetallization of residual hydrocarbon oils
using a catalyst which meets the requirements given hereinbefole under a) to
g) is described in Canadian patent applications No.'s ]72,04n, 212,547,
212,563 and 232,027.
The present inventioll therefore relates to an improved process for
the catalytic hydrodesulphurization of vanadium and nic~el containing resid-
ual hydrocarbon oils having a vanadium and nic~el content above 120 ppmw
utilizing a desulphurization catalyst system comprising a single catalyst I
and a single catalyst II, which catalysts meet the following requirements:
(a) both catalysts have a total pore volume larger than 0.30 ml/g of which
the percentage (v) that consists of pores with a diameter larger than 100
nm is less than 10, (b) catalyst II has such a specific average pore diameter
(p) and a specific average particle diameter (d) that the quotient p/(d)0 9
meets the requirement
0.6x]0 4x(P~1 )2~ p/(d)0 9 cat II~3+6xlO x(P}I )
- (c) the percentage of the joint catalyst volume of catalysts I and II that
is occupied by catalyst II (~OV cat. II) lies between 10 and 90% and meets
the requirement
~Ox( rS rxlnO~2x(P}I )-2~ov cat. II~300x( ~ 100)2x(PIl )-2,
~ .
-- 4 --
lOl~llSl
in which SF is the sulphur content of the feed and Sp is the desired sulphur
content of the desulphurized product (p in nm, d in mm, PH in bar, Sp and
SF in %w, the improvement comprising prolonging the life of the desulphur-
ization catalyst system by first hydrodemetallizing said vanadium and
nickel containing residual hydrocarbon oil utilizing processing parameters
compatible with and substantially identical to those for said hydrode-
sulphurization step so that said catalytic hydrodemetallization step and said
hydrodesulphurization step are conducted sequentially and continuously and
utilizing a hydrodemetallization catalyst 0, providing the requirements
given hereinbefore under 3) to 6) are met.
The present invention also provides in an apparatus for the
hydrocracking of residual oil having a vanadium and nickel content of at
least 120 ppmw and a sulphur content of about 2% w the improvement com-
prising the use of a series of catalysts in the following order from the
output to the infeed of the apparatus: (1) hydrodesulphurization catalysts
comprising a single catalyst I and a single catalyst II, which catalysts ~
meet the following requirements: (a) both catalysts have a total pore volume ;
larger than 0.30 ml/g of which the percentage (v) that consists of pores
with a diameter larger than 100 nm is less than 10, (b) catalysts II has such
a specific average pore diameter (p) and a specific average particle diameter
(d) that the quotient pt(d)0'9 meets the requirement
(PH2) ~ ~/(d) ~cat II~3t6X10 4X(PH )2
(c) the percentage of the joint catalyst volume of catalysts I and II that
is occupied by catalyst II (%v cat.II) lies between 10 and 90% and meets the
requirement
40x~ xlO0) x~PH ) ~%v cat.II~300x( ~ H2
in which SF is the sulphur content of the feed and Sp is the desired sulphur
content of the desulphurized product (p in nm, d in mm, PH in bar, Sp and
SF in %w.
,, ~
.
~ ~ - 5 _
1~81151
As demetallization catalysts preference is given to the catalysts
described in above-ementioned Canadian patent applications No~s 172,040,
212,547, 212,563 and 232,027.
The invention will now be elucidated with the aid of the following
example,
EXAMPLE
Catalysts combinations consisting of a demetallization catalyst
(catalysts 1,11 and 40), a first desulphurization catalyst (catalyst A) and
a second desulphurization catalyst (catalyst D) were employed for hydrode-
metallization followed by hydrodesulphurization without catalyst replenish-
ment of two vanadium and nickel-containing residual hydrocarbon oils (oils D
and F). Moreover, catalyst combinations consisting of the two desulphur-
ization catalysts A and D and also each of these two catalysts separately
were employed for the hydrodesulphurization without catalyst replenishment ~ :
of the two oils.
, - 5a -
~llSl
-- 6 --
Demetallization/desulphurization or only desulphurization of the
oils was carried out by passing the oils together with hydrogen
downwards through three cylindrical vertically disposed fixed
catalyst beds at elevated temperature and pressure.
The experiments were carried out four by four. In each set
of four experiments the same oil was desulphurized under the same
conditions and with the same volume Or catalyst, down to the same
sulphur content in the product. (In all the experiments Sp was
0.5 %w). In one of the four experiments the first catalyst bed
contained the demetallization catalyst indicated hereinarter as
catalyst 0, the second catalyst bed the desulphurization catalyst
indicated hereinafter as catalyst I and the third catalyst bed
the desulphurization catalyst indicated hereinafter ss catalyst
II. In the three remaining experiments the three catalyst beds
contained either a combination of catalyst I and catalyst II
successively or catalyst I exclusively or catalyst II exclusively.
The desulphurization experiments were carried out at an initial
temperature of 36015C, a space velocity of 0.7 kg.l .h , a
gas rate of 600 NlH2.kg and a hydrogen partial pressure of 100
or 150 bar. For the preparation of a product having constant sulphur
content the temperature had to be gradually increased during the
experiments. The desulphurization experiments were ended when ~ -
a temperature of 420C had to be applied to prepare a product
having the desired sulphur content.
The demetallization was carried out at a constant temperature
Or 420 C and a hydrogen partial pressure and eas rate correspondine
with those applied in the desulphurization. In case of demetallization
followed by desulphurization the space velocity throuehout the
catalyst system amounted to 0.7 kg.l .h
Composition and properties Or the catalysts which were ap~lied
in the form Or their ~ulphi~er. are aiven in Tables ~ and 13. For
lV~llS~
-- 7 --
information concerning the preparation of catalysts A and D reference
is made to Canadian patent applicstion No. 220,643 and for information
about the preparation Or cataly~ts 1 and 11 to Canadian patent
~pplication No. 172040 in which the preparation of these catalysts
is described in detail. Catalyst 40 is a demetallization catalyst
within the scope of Canadian patent application No. 172040, which
catalyst was prepared by co-impre¢nation of an alumina carrier
with an aqueous solution containing vanadyl oxalate and nickel
nitrate, followed by drying and calcination of the composition.
The two re~idual oils used in the experiments are further
de~cribed hereinafter. The results of the experiments are eiven
in Table C.
OIL D
An oil havine a total vanadium and nickel content of 225
5 ppmw, and a sulphur content of 2.0 %w, which oil had been o~tained
as a residue in the atmospheric distillation of a Caribbean crude oil.
OIL F
An oil having a total vanadium and nickel content of 410
ppmw and a sulphur content of 2.0 %w, which oil had been obtained
as a residue in the atmospheric distillation of a Caribbean crude oil.
Table A
; Cat. Metal load, Carrier Pore Pore Specific % of % of v,% p,nm d,mm
No. pbw per 100 vol., volume surface the the
pbw of car- ml/g in pores area, pore pore
rier with a m2/g volume volume
~ co ho diameter in in
~0.7xp pores pores
and with with
~1.7xp, a dia- a dia-
ml/e meter meter
cO 7x~ >1.7x~
____ _____ ____ _______ ______ _______ _______ _:___ ______. .____ _____ ____
A 4,7 11,4 Al203 0,54 0,42 202 1~,7 5.f~ 1,3 14,1 1,5
3,8 9,5 Al203 0,50 0,47 303 2,8 3,2 ~,0 4,7 o,~
95_5~3~s~8-~53ns~3~s=~z=~===as==~3======55================-=-~5=======~==~
Table B
Cat Metal load, Carrier Pore Total Nitrogen v, ~ p, nm d, mm
No. pbw per 100 vol., pore pore
pbw of car- ml/z volume, volume,
rier ml/e ml/g
Nl V
____ _____ _____ _______ ______ ______ ________ ____ _____ _____1 _ 2,0 Al203 225 0,57 o,56 ~0,5 10,2 0,7
11 0,52,0SiO2 243 0,81 0,74 9 ~,0 2,2
40 0,52,0Al203 220 o,60 0,57 1,5 14,9 1,5
============================
Table C
~xp. Oil PK , Cat.O ~v Cat.O %v Cat.I %v Cat.II Cat.life of
No. No. 2 No. (Cat.No.A) (Cat.No.D) cat.or cat.
bar combination,
_______________ _____ ________ _________ _________ _:__________
XVI D 150 1 40 42 18 1400
XVI' D150 - - 70 30 1000
XVI" D150 - - 100 ~ 425
XVI"' D150 - - - 100 600
XVII D100 1 40 36 24 3000
XVII' D100 - - 60 40 2000
XVII" D100 - - 100 - 400
XVII"' D100 - - - 100 1300
XVIII F150 11 50 35 15 850
XVIII' F150 - - 70 30 550
XVIII" F150 - - 100 - 200
XVIII"' F150 - - ~ 100 250
XIX D 150 40 40 42 18 900
XIX' D150 - _ 7 30 1000
XIX" D150 - _ 100 _ 425
XIX"' D150 - - - 100 600
====.,._.=.. ========.... ====.. =.. ====================================
Of the experiments eiven in Table C only experiments XVI-XVIII
are demetsllization/desulphurization experiments accordine to
the present patent application. The other experiments have been
included in the table for comparison.
In experiments XVI-XVIII catalyst combinations were applied
in which each of the catalysts satisfied the requirements concerning
porosity and particle size; the other requirements according to
the present patent application were also satisfied in these experiments.
Comparison of the lives of each of the cntalyst combinations
: ' ' :
1~8~
O/I/II given in the last column of Table C and applied in experiments
XVI-XVIII with the lives of the catalyst combinations I/II applied
in the associated experiments XVI'-XVIII' clearly shows the gain
in catalyst life which is achieved upon a~plication of catalyst
combinations according to the present patent application.
It is true that a suitable cntalyst combination I/II was
applied in experiment XIX (and that this experiment therefore
falls within the scope of Canadian patent application No. 220,643 ,
but the quotient p/(d)-9 of the catalyst O applied was too low
to meet the requirements of the present patent application.
Experiments XVI'-XIX' are also experiments within the scope
of Canadian patent application No. 220,643
It is pointed out that experiments XVI', XVI" and XVI"'
given in Table C are identical with experiments XIX', XIX" and
~IX"' respectively, also in this table and that experiment~ XVI"',
XVII" and XVII"' in Table C are identical with experiments IX",
XIV' ~nd XIV" in Table B of C~adiun pateDt application 6'o. 220,643
.
