July 26, 1960
L E. GARDNER EI‘AL
2,946,738
HYDROCRACKING A'GAS OILWITH A PRESULFIDED CATALYST
CONSISTING OF OXIDES OF'VANADIUM, COBALT
AND MOLYBDENUM ON GAMMA ALUMINA
Filed July 1, 1957
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NOT PIRESULFIDED (750 F)
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_
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INVENTORS
F/G' 3'
L. E. GARDNER
-
1w. HOGAN
BY 2
A TTORNEVS
United States Patent 0 F
. Patented vJuly 26,, 1960
2
1
_ pared as described in US. Patent 2,486,361). The im
2,946,133
pregnated vanadia-alumina is drained, dried, and calcined
so as to convert the metal compounds to oxides.
HYDROCRACKING A GAS’ on. wrrn A PRESUL-I'
FIDED CATALYST CONSISTING' 0F OXIDES OF
oxides on vanadia-alumina is then partially‘ reduced by
- treatment with hydrogen at an elevated temperature and
‘I GAMMA ALUMINA ,
' the partially reduced composite is sul?ded, preferably by
and E. Gardner and Robert J. Hogan, Bartlesville,‘
contacting the same with hydrogen sul?de at a temperature
in the range of about 600 to‘ 900°‘ F. or higher. - A pre-,
vOkla, assignorsto Phillips {Petroleum Company, a cor
.
The
calcined composite containing cobalt and molybdenum
VANADIUM,‘ COBALT AND'MOLYBDENUM ON
I poration of Delaware
‘2,946,738
10
ferred methodv is to reduce the composite in hydrogen
7 at a temperature in the rangeof 600 to 1100" F. and
Filed July 1, 1951, Ser. No. 669,350
thereafter subject the reduced composite to contact with
hydrogen sul?de admixed withhydrogen at an elevated’
sul?ding temperature. It is also feasible to simultaneously.
This invention relates to an improved hydrocarbon con 15 contact the mixed oxides composite with a mixture of hy-.
drogen and hydrogen sul?de under reducing and sul?ding
version catalyst.
I
-
18 Claims. '1 (c1. zos-nz)
conditions,yparticularly at a temperature in the range of
A speci?c aspect of the invention is concerned with a
method of preparing an improved hydrocarbon con
600 to 900° F.
'
'
A preferred method of sul?ding comprises passingv a'
version catalyst particularly suitedto the hydrocracking
of heavy gas oils.
20 gas containing from 5 to 10 volume percent of hydrogen‘
sul?de and 95 to 90 volume percent hydrogen through the
In the hydrocracking of gas oils, one of the problems
particulate catalyst‘ at a temperature in the range of ‘600
involved is that of developing a catalyst of high cracking
to 900° F. at moderate superatmospheric pressure and at
activity and low coke laydown characteristics. Generally
a space velocity between 5 and 500 and even higher
a catalyst of high cracking activity e?ects a substantial
amount of conversion to coke. In the hydrocracking of 25 volumes of gas per volume of catalyst per hour. About
100 ‘to 500 volumes of ‘gas per volume of catalyst is
gas oil, it is desirable to convert a substantial‘ amount
of the feed to ole?ns and avoid hydrogenation of the
suf?cient to- adequately activate the catalyst. The hy
drogen sul?de treatment is continued until this gas ap
It is also desirable
pears in the o?-gas. ‘The appearance of hydrogen sul?de.
that the catalyst have good desulfurization activity along
with high cracking activity and, low conversion to coke. 30 in the o?-gas may be determined by passing the o?-gas
through a bubble bottle charged with a solution of
We have developed a catalyst and a method of prepar
ing the same which has improved charactistics in the hy
cadmium chloride to which has been added a small‘amount ’
drocracking of heavy gas oils.
of sodium hydroxide.
.
.
.
It is an object of our invention to provide an improved‘
Various types of active alumina from anumber of
catalyst and process for preparing the same. ‘Another ob; 35 sources may be usedfor the alumina base of the catalyst.’
ject is to provide an improved hydrocracking catalyst‘
Synthetic alumina gel, partially dehydrated naturally oc
ole?ns to saturated hydrocarbons.
which has high cracking and desulfurization activity with
' curringvhydrous alumina, as well as precipitated alumina
low conversion to coke. A further object is to provide
an improved process for the conversion of vhydrocarbon
to more valuable ?uid hydrocarbons. It is also an object, 40
of the invention to provide an improved process for hy
'
drocracking a heavy gas oil. Other objects ‘of the in
'
"
'_ Our improved catalyst comprises cobalt molybdate on'
vanadia-alumina, which has been pretreated with hydrogen’
a variety of ways other than the manner speci?cally de
scribed herein. The impregnation mayv be e?ected from
a solution containing all three added metal compound
vention [will become apparent from a consideration of
the accompanying disclosure.
trihydrate properly dehydrated ‘so as "to maintain the
alumina, at least in part, in the gamma form may be used
as the support for the other constituents of the catalyst.
Itis also feasible to impregnate the alumina base in
promoters, such as from an‘ aqueous solutionvof am?
45
m‘onium vanadate, ammonium inolybdate,‘ and cobalt
the process of the invention has increased ‘cracking activ-'
‘nitrate; or the‘ impregnation may be by successive im-‘
pregnation with separate individual solutions ofthe three‘
ityflow coke laydown, and good‘ desu-lfurization activity
metal compounds followed by-calcination‘after-each im
pregnation. Another variation comprises successive im
This catalyst ‘ when made in accordance with‘,
at mild hydrocracking conditions. Our catalyst is '* also‘
unique in that a substantial proportion of the ole?ns pro
duced by cracking of the gas-oil components are not hy
w
pregnations of vanadia-alu'mina with an aqueous solution
of'the other two compounds, such as ammonium molyb
drogenated, although good desulfurization activity is main
tained during the hydrocracking. The catalyst comprises
date and cobalt nitrate, with calcination of thecomposite
between impregnations." Or the alumina support may be
a porous active gamma-alumina support or base having
impregnated by soaking same in or with a solution of
dispersed thereon- the voxides of vanadium, cobalt, and 55 all 'three metal compounds ‘followed by calcination and
repeating the soaking and calcination steps one or more
molybedenum. The composite is pretreated by partially
times to obtain. the desired concentration of the metals
reducing the oxides and sul?ding the partially reduced
on' the support.
_
1
1
‘ '
composite. "The amount of'the vanadium, cobalt, and
- The reduction of the mixed oxides’ in H2 at elevated tem4
molybdenum inithe catalystmaylrange from 1 ,toplO pe'r- ~
cent, calculated as metal, the balancebeing- alumina; 60 peratures (600—1100° F.) reduces the vanadium and
molybdenum oxides to the lower oxide forms and reduces
however, it is preferred that thevanadium-he in the, range ‘
most vof the cobalt oxide tothe metal. .The sul?ding
of 2 to 3 weight percent of the catalyst, the cobalt in the
treatment with H28 produces an elfective amount of metal
range of 2. to 4 weight. percent, and themolybdenum in the
sul?de in the. catalyst but theexact .form of .the sul?ded
range of3 to 6percent.
_
' ' j
' j
'
i
composite is not known. Hence the‘ terms; “reducing”
65
In preparing the catalysts of the invention, an active
and “sul?ding” as usedherein are. to‘be'linterp’re'ted in
porous, aluminum oxide having substantial pore’ volume
this light and anyone familiar with, the catalyst art ‘will
is impregnated with an aqueous solution of ammonium
understand what isw'meantgby a “reduced and sul?ded
vanadate followed by draining, drying, and calcining the
mixed oxides?’ vcomprosite catalyst. 1 This sul?ded catalyst
impregnated support; thereafter the calcined depositis 70 is an’ improved catalyst for hydrocracking of heavy gas.v
impregnated with a solution of, a mixture of cobalt nitrate . ' oils. Increased cracking activity and low .coke'lay».
and ammonium molybdate. (This solution may be pre
down is maintained using this catalyst at mild hydro
9,946,738
3
'_
r
p
I.
.
.
_.
’
Comparisons of the cracking activities of the catalyst
of Example 'I withcobalt molybdate alumina and with
cracking conditions. The range of operating condition
for hydrocracking using this catalyst are:
4
-
vanadia on alumina are shown in Table I.
The cobalt
molybdate catalyst is a commercially available catalyst
Preferred
Temperature, "F ............................ __
.Broad
700-800
100-1, 000
5 used by a number of oil companies in large scale hy
drotreating. It contained 1L6 percent Co and 5.5 per
cent M0 (‘by weight) and the balance active alumina and
had a surface area of 167 sq. m/g.
0 . 1-10
100-1 0, 000
being active alumina. It was made by impregnating the
Gas oils having a boiling range of 350 to 1100° F.'
are suitable feeds for the hydrocracking catalyst of the
invention. Such feeds usually contain up to about three
weight percent sulfur.
In the drawing, Figure 1 is a graph showing the effect
of temperature and of presul?ding of the catalyst of the
invention on conversion of gas oil; Figure 2 is a graph
showing a comparison of the volume percent of ole?ns
in the (Ts-400° F. gasoline fraction of a conversion
ef?uent from hydrocracking a gas oil with the presul
?ded catalyst of the invention and with a non-pres-ul
The vanadia on‘
alumina catalyst had a surface area of 177 sq. m./_g.
10 and contained 6.4 Weight percent vanadium, the balance
porous alumina support with ammonium vanadate ‘dis
solved in aqueous ethanolamine solution followed b
calcination at 1000" F.
15
>
Table I
FRACTIONATION OF LIQUID PRODUCTS
‘
20
Charge
Weight percent to-
Oil
'
?ded catalyst of corresponding composition; and Figure
04's and lighter; .......... ..
O5 to 400° F ................ __
400 F + .................... ._
3v is a graph showing the percent of sulfur removal from
a, gas~oil feed by a presul?ded catalyst and one of cor
Cobalt
Vanadla
Catalyst
Molybdate
on
of Ex
on Alumina Alumina ample I
0. 4
9. 4
90.2
0.0
6. 6
93. 4
0. 4
10.0
89.6
0. 9
27.8
71. 3
25
responding composition not presul?ded.
The mass spectroanalysis of the reactor gaseous ef~
The following speci?c examples are presented to- il
?uent is given in Table II.
lustrate the invention but are not to be'construed as
unnecessarily limiting the same.
-
Table II
EXAMPLE‘ I.--PREPARATION OF THE CATALYST
_' Active aluminum oxide obtained from Harshaw Chemi
cal Company was dried at 1000" F. and usedv as the
base. The pore volume of the aluminum oxide was 40
cc. per 100 grams. Twenty-eight and four tenths grams
‘of ammonium vanadate (NH4VO-3) was dissolved in 250
ml. water. One hundred eighty grams of dried alu
minum oxide was impregnated with this ammonium
vanada't'e' solution. vThe aluminum oxide was drained
free of the solution and dried at about 230° F. The
30
.
.
-
CoMoOr
Composition, M01 percent
’
‘
on
v
Alumina
p
Hrs."
V205 on
_ Alumina
________ _.
35 Para?ins-Crs and lighter
_
Ole?ns-Cgs-and lighter_._- ........ __‘_._
.
Catalyst
of Ex
ample I
92. s
95. 9
4.15
2.1
3.1
2.7
0. 1
2.0
0.0
’
s3. 1
10. 8
21-4
Desulfurization activities of the catalysts were: cobalt
molybdate on alumina-90 percent; vanadia on alu
dried material was calcined at 1000? F. to convert the 40
mina-60 percent and thecatalyst of this invention'—70
ammonium vanadate to vanadium oxide. A 250 ml.
percent. Coke laydown on the catalyst were low for all
solution containing 69.3 grams cobalt nitrate
three catalysts.
tce(No,)',;6H,o1
' EXAMPLE'I'llr-EFFECT OF TEMPERATURE'AND
45
and 41.5 grams of ammonium molybdate
V
l:
'
6MO'7O24.4H2O‘]
.
,
OF
PRESULFIDING
~
, A‘Wafra gas oil, boiling range 350 to 1 100° F., API
of 28.5, 2.17 weight percent sulfur was, hydrocr-acked
was. prepared as described in US. Patent 2,486,361.
under conditions of 7.50‘? F. and 800° F., 500 p.s.i,g., l
The vanadia-alumina was ‘impregnated with this solu
tion. The vanadia-alumina was drained free of the so 50 L-HSV and 1000 cu. ft. H2 per‘bbl. oil using batch No.
2. of the catalyst prepared as rdescribedinrExample I.
lution and dried at about 230° F. The dried material
The veffect of temperature and of presul?ding oncon~v
was calcined at 1000° F. to convert the cobalt and
molybdenum compounds to the oxides.
.Two batches were prepared according ‘to-this pro
cedure. Batch No. 1 analyzed 2 weight percent cobalt,
Elv weight percent molybdenum and 2 weight percent
version is shown in Table III‘ and plotted inFigure' 1.~
as
Tablb 111' . e
A
‘
V
CONVERSION OF 500° F. (+)
vanadium on the alumina. Batch No. 2 ‘analyzed 3.6
weight percent cobalt, 5.1 weight percent molybdenum
and- 2.4 weight percent vanadium on the alumina. The
surface area. of batch No. 1 was 208 sq. meters per gram
and of ‘batch’ No. 2 was 171 sq. meters per gram.
'
Nof. Pre.
60
.Presul?ded Catalyst
sul?ded
Hours on Stream
'
-
Catalyst
run' at
7
run at
,
run at
750° F.
750° F.
800° F
These catalysts were reduced in one atmosphere hy
drogen at 850° F. followed bypreasul?ding in one at
mosphere: of hydrogen-hydrogen sul?de containing 5 to
1.0 volume percent hydrogen sul?de. Approximately
100-to 500 volume of ‘gas was required per volume.
of catalyst.
EXAMPLE'II.-+HYDROCRACKING OF GAS 011
A Wafra gas oil, boiling range 350 to 1050° 'F., API
of 28.5, 2.17 weight percent sulfur and. 0.1 weight per
cent’ nitrogen was, hydrocrack'ed under conditions of
750°‘ F., 500 p.s.i.g;, 1 LHSV, and 1000 cu. ft. vHz per
bbl. oil, using batch No. 1 of the catalyst prepared as
described
Example I.
‘
p
The volume‘ percent ole?ns in the C5400“ F". gasoline
75 fraction are given in Table IV and ‘plotted in'Figu're 2.
2,946,738
8. A process for preparing a catalyst comprising im
Table IV
pregnating a porous active alumina support with aque
ous solution of compounds, convertible to the oxide form
VOLUME PERCENT OLEF’INS, IN C5~400° F. GASOLINE
Hours on Stream
Not Pre~
sul?ded
Presul?ded Catalyst
Catalyst
7
run at
run at
run at
750° F.
750° F.
800° F.
by calcination ,of the’metals cobalt, molybdenum, and
vanadium so as to deposit in the support an amount of
each said metal in the range of 1 to 10 weight percent;
drying the support, and calcining same so as to convert
the metal compound to metal oxide; heating the resulting
2. 9
metal oxide composite in a hydrogen ambient to a re
2.6
5. 5
ducing temperature; and thereafter sul?ding the resulting
composite.
26. 5
__________ -_
23. 8
__________ __
9. The process of claim 8 wherein the sul?ding step is
5.0
effected by contacting said resulting composite with HES
4. 0
28.1
__________ __
25. 9
__________ _.
3. 9 15
at a temperature in the range of 600 to 900° F.
10. The process of claim 9 wherein the sul?ding gas
comprises hydrogen containing H28 in the range of 5
to 10 volume percent.
11. A process for preparing a catalyst comprising im
pregnating porous active alumina particles with an aque
The percent sulfur removal from the oil feed are
given in Table V and plotted in Figure 3.
20 ous solution of ammonium vanadate; calcining the im
pregnated alumina so as to convert the vanadium to the
Table V
oxide form; thereafter impregnating the calcined com
SULFUR REMOVAL 7
posite with aqueous solution of cobalt nitrate and am
15.8
Not Pre-
Presul?ded Catalyst
sul?ded
Hours on Stream
__________ __
'
monium molybdate; calcining the resulting impregnated
V25
Catalyst
run at
run at
run at
750° F.
750° F
800° F
__________ _.
93
89
______________________ __
92
______________________ -.
______________________ _
__________ __
86
12. The process of claim 11 wherein the reducing step
is effected in hydrogen at a temperature above 600° F.
95
91
90
30
taining gas at a temperature in the range of 600 to 900° F.
94
88
87
93
92
88
89
__________ _.
88
91
.......... __
87
...................... -
88
...................... _.
88
13. The process of claim 12 wherein the reduced com
posite is sul?ded by contacting same with an HzS-con
14. Theprocess of claim 11 wherein the reducing and
______________________ _
88
89
composite so as to convert the cobalt and molybdenum
to the oxide form; thereafter reducing and sul?ding the
resulting composite to leave metal sul?des in the catalyst.
sul?ding steps are effected by contacting the composite
35 at a temperature above 600° F. with a mixture of hydro
__________ __
gen and H28.
‘
15. A process for the hydrocracking of ?uid hydrocar
bons boiling in the range of about 350 to 1100° F. to
more valuable hydrocarbons which comprises contact
Certain modi?cations of the invention will become
apparent to those skilled in the art and the illustrative 40 ing a ?uid hydrocarbon feed in admixture with hydrogen
details disclosed are not to be construed as imposing
unnecessary limitations on the invention.
,
We claim:
with a catalyst consisting essentially of porous active
alumina in major proportion admixed with a reduced
and sul?ded mixture of the oxides of vanadium, cobalt,
1. A catalyst consisting essentially of a reduced and 45 and molybdenum under hydrocracking conditions.
16. A process for hydrocracking a gas oil boiling in
sul?ded mixture of the oxides of vanadium, cobalt, and
the
range of about 350 to 1100° F. which comprises
molybdenum containing metal sul?des deposited on por
contacting said gas oil admixed with hydrogen under
ous active alumina.
hydrocracking conditions including a temperature in the
2. A catalyst of the composition of claim 1 having
been activated by treatment with a reducing and sul?d 50 range of 700 to 800° F. with a catalyst consisting es
sentially of porous active alumina having deposited there
ing gas at an elevated temperature above 600° F.
on a reduced, sul?ded mixture of the oxides of vanadium»,
3. A catalyst of the composition of claim 1 having
cobalt, and molybdenum.
been activated by treatment with an HZS-containing gas
17. The process of claim 16 wherein said catalyst con
at a temperature in the range of 600 to 900° F.
4. A catalyst of the composition of claim 1 wherein the 65 tains from 1 to 10 weight percent of each of the metals
V, Co, and Mo.
range of each of Co, Mo, and V is 1 to 10 percent by
weight of the catalyst and the balance comprises gamma
alumina.
5. A catalyst of the composition of claim 4 having
18. The process of claim 17 wherein said hydrocrack
ing conditions include a temperature in the range of 725
to 775°- F., pressure in the range of 100 to 1000 p.s.i.g.,
at least 100 s.c.f. of H2 per bbl. of liquid feed, ‘and 0.5
been sul?ded by contacting same with a stream of H2S 60 to
2.0 LH space velocity.
at a temperature in the range of 600 to 900° F. until'H2S
appears in the o?f-gas.
'
References Cited in the ?le of this patent
6. A catalyst consisting essentially of an active gamma
alumina support impregnated with the oxides of vanadi
um, cobalt, and molybdenum, the vanadium being in the 66
range of 2 to 3 weight percent, the cobalt 2 to 4 weight
percent, and the molybdenum 3 to 6 weight percent, sub
jected to reduction in H2 and sul?ding in H28 at temper
atures above 600° F. to leave metal sul?des in the cat
alyst.
7. A catalyst of the composition of claim 6 having
been reduced with hydrogen at a temperature in the range
of 600 to 1100° F. and thereafter sul?ded in HgS at a
temperature in the range of 600 to 900° F.
UNITED STATES PATENTS
2,365,029
2,428,692
2,487,466
2,656,302
2,687,983
2,761,815
2,761,817
2,769,756
Voorhies ____________ __ Dec. 12,
Voorhies _____________ __ Oct. 7,
Nahin ________________ __ Nov. 8,
Porter et a1 ___________ __ Oct. 20,
Garwood ____________ __ Aug. 31,
Hutchings ____________ __ Sept. 4,
Sweetser et al. ________ __ Sept. 4,
Porter et al. __________ __ Nov. 6,
1944
1947
1949
1953
1954
1956
1956
1956
2,793,170
2,804,426
Stiles et al ____________ __ May 21, 1957
Askey _______________ _.. Aug. 27, 1957