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Патент USA US3079343

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United States Patent 0 ””
3,079,327
Patented Feb. 26,‘ 1953
1
2
3,079,327
with little tendency to deactivate as far as conversion is
concerned.
PRGCESS FOR CONVERTING AN ASPHALT CQN
TAINENG PETRQLEUM RE§IDUAL GEL BY CAT
ALYTIC HYDROCRA?KING
The catalyst of the present invention can be prepared
by providing an acid-treated halloysite clay with catalytic
Carl D. Keith, Summit, N.J., and Henry Erickson, Park
Forest, Ill, assignors, by mesne assignments, to Sin
ciair Research, lino, New York, N.Y., a corporation of
amounts of cobalt and molybdena and calcining the com
posite.
Calcination temperatures employed are those
known in the art, for example, about 600 to 1300° F. or
more. Ordinarily the cobalt and molybdena will be pres
N0 Drawing. Fiied Apr. 7, 1960, §er. No. 20,532
ent in catalytic amounts of about 1.0 to 10.0 percent co
5 Claims. (£1. 208-48)
10 balt and about 6.0 to 20.0 percent molybdena. The com
The present invention relates to the conversion of
bination of cobalt and molybdenum on a catalyst calcined
asphalt-containing petroleum residual fractions to provide
after these components are added to the catalyst base as
improved reforming feedstocks, heating oils and cracking
in the present invention is sometimes referred to as cobalt
Deiaware
‘
stocks.
molybdate. The acid-treated clay may contain in addi
In the prior art processes for the conversion of asphalt 15 tion to that naturally present minor amounts, preferably
containing residual fractions, the fractions are generally
less than about 25 weight percent, of alumina.
?rst hydrogenated in the presence of a suitable catalyst
The hydrocracking step of our process generally em
under conditions of temperature and pressure which re
ploys elevated pressure conditions, for instance within the
_sult in cracking as well as hydrogenation. When this is,
range of about 500 to 5000 p.s.i.g., preferably about 2200
done, however, the catalysts commonly employed promote
to 2700 p.s.i.g. The temperature used in the hydrocrack
hydrogenation of both the lower boiling components in
ing step is usually about 600 to 900° F., preferably about
the feed, for, instance, those in the 950° F.—— boiling
780m 800° F. The free hydrogen employed is generally
range and the higher boiling components, for instance,
about 1000 to 6000 or more cubic feet per barrel of fresh
the 950° F.+ fraction with the result that relatively
residual feed and it is convenient to provide most of the
25
high hydrogen consumption occurs. Consequently large
hydrogen by recycle of gas. Make-up hydrogen can be
amounts of hydrogen are “los-t”- by way of hydrogenation
added as needed at a hydrogen consumption rate of about
to what is generally considered the less desirable frac
100 to 600 cubic feet per barrel of feed. The weight hour
tion, that is the high boiling component for instance, the
ly space velocity (WHSV) , weight units of feed introduced
950° F.+ fractions. Subsequent hydro-treating oper
into the reaction zone per weight unit catalyst per hour,
ations to which the lower boiling components are often 30 will usually be within the range of about 0.3 to 2.
subjected will require yet more hydrogen. Moreover, the
The product from the hydrocracking operation can be
catalysts commonly employed rapidly deactivate particu
separated into the heavier and lighter material fractions
larly as far as conversion is concerned; the conversion rate
by any convenient means known to the art, preferably
quickly decreasing after a short period of time.
under high pressure. Although the separation point can
In accordance with the present invention we have dis~
be varied, ordinarily a separation is made within the vicin
covered a new and improved process for the conversion
ity of about 800 to 1000” P. so that the heavier fraction
of asphalt-containing petroleum residual fractions to pro
will generally constitute a material having an initial boil
vide upgraded reforming feedstock, heating oils, and crack
ing point within the range of about 800 to 1000° F. and
ing stock which process includes a hydrocracking oper— 40 the lighter material an end boiling point in the range of
ation wherein the hydrogen consumed is primarily by the
about 800 to 1000° F. A preferred separation point is
about 950° F.
more desirable fraction i.e. the lower boiling components,
In the second stage of our process the lighter fraction
for instance, the 950° F. minus fraction; the total hydro
is hydrotreated under hydrogenation conditions and in the
gen consumption consequently being relatively small.
presence of a hydrogenation catalyst to remove sulfur
Moreover the conversion level of catalyst activity does
and saturate the ole?ns contained in the light fraction.
not quickly decrease after a short period of time. The
Examples of suitable catalyst ingredients are any of the
process of the present invention involves passing the
hydrogenation catalysts such as molybdenum, tungsten,
asphalt-containing residual together with hydrogen into
vanadium, tin, chromium, the group VIII metals, for
contact with a particular catalyst under hydrocracking
instance, iron, cobalt, nickel, platinum group metals, and
conditions, separating the product into a lighter fraction 50 their
oxides and sul?des. Mixtures of these materials or
and a heavier fraction, hydrotreating the lighter fraction
compounds or two or more of the oxides can be employed.
in the presence of a hydrogenation catalyst and recovering
Minor catalytic amounts, e.g. usually less than about 10
one or more fractions which can serve ‘as reforming stock,
heating oil or cracking stock.
The asphalt and sulfur-containing petroleum residual
or 20%, of these ingredients can be dispersed on or car
55 ried as promoters by other materials such as oxides, sili
cates or mixtures of the oxides and silicates. The com
feed of the present invention is generally heavy residual
crude material that contains asphaltenes and maltenes, as
for example, penetration range asphalts having a penetra
posite is then calcined after the promoting metal is added.
Synthetic catalysts of this type are generally the activated
oxides of aluminum and the like, mixtures of oxides of
tion of about 250 or less at 77° F. The particular catalyst 60 silica with oxides of magnesium, boron, aluminum, titani
um, and zirconium. Speci?c examples of suitable hydro
employed in the hydrocracking step is comprised of co
genation catalysts are cobalt~molybdena-on-alumina,
balt and molybdena on acid-treated halloysite clay, for
nickel-tungsten oxide-on-alumina, nickel-tungsten sul?de
example, mineral acid, such as sulfuric acid, treated hal—
on-alumina, and cobalt-molybdena-on-silica-alumina. The
loysite clay. It has been found that use of this catalyst
in the hydrocracking operation of the present invention,
unlike other commonly employed hydrogenation catalysts,
unexpectedly pro-motes hydrogenation of the lower boil~
65
hydrogenation conditions employed generally will fall
within the following ranges: temperature, about 550 to
800° F.; pressure, about 200 to 800 p.s.i.g.; weight hourly
space
velocity 1 to 8; hydrogen recycle, about 500 to
ing or lighter fractions with little hydrogenation of the
5000 standard cubic feet per barrel of feed. The hydro
heavier fractions. Thus good yields of the lighter frac
tions are gained with relatively small hydrogen consump 70 treated light fraction from the second stage of our process
can be sent to a fractionator to obtain a reforming frac
tion. At the same time the catalyst exhibits good activity
tion, e.g. a fraction boiling in the gasoline range and
3,079,827
heavy fractions such as heating oil and catalytic cracking stock.
The following examples illustrate the invention.
EXAMPLE II
Io demonstrate the advantages of using cobalt molyb
denum acid-treated halloysite clay catalyst in the hydro
.EXAMPLE I
cracking stage of the present invention, comparative runs
‘
‘
5
were made under conditions similar to Example I but
_’I:o ayelma asphalt produced as bottoms 1n thevacuum
employing in {he hydrograckjng Stage the following cat.
dlstlll?iwn ‘of'crud? Petroleum 011 (22% based 01'! Crude)
alysts: cobalt-molybdena-on-alumina and cobalt-molyb
hydrogen gas was?dded-a?d at-therateof ‘WOO-Standard
dena-on-silica-alumina. The results of tests‘ on the '950"
cubic feet P51‘ barrel of asphalt feed- The mixture Was
F. minus and950° Fsplus liquid products are alsoshown
then introduced into a hydrocracking reactor. Reactor 10 in Table I.
7
Table No. 1
Run No. R46
C01\I00t+A1z03
ooMo04+s1orAn0=
017M001 + Acid-Treated
+ Trihydrate A1202
Halloysite Clay
0-3
48-54
64-30
0-8
32-43
64-30.
0-3
32-43
1.3
7.3
1.2
4.3
1.7
3.4
1.5
6.3
1.7
5.9
2.3
4.6
1.8
5.3
‘1.7
5.5
17. 0
11. 6
14. 2
17. 6
15.8
15. 2
13. s
.13. 7
5.0
14.0
29. 0
35. 3
3.9
856
10. 6
62. 2.
0.2
.505
19. 2
57. 0
25. 7
43. 0
0.1
495:
22.1
41. 0
4.0
300
25.3:
47. 0
__
Hz Consump. s.c.f.lb‘ol ________ ._
0.2
650
0.2
420
' 14. 4
55. 7v
3.7
540.
.13. 5
57. 3
0.2
245
.19. 0
56.1
0.2
320
Conversion to 950° 1*‘. minus. .'..ic‘s?smt’ )3‘. '“API______________ .-
60. 8
52.0
:37. 6‘
52.4
‘12.79
55. 2
.55. 0
5410'
52. 8
54. s
.51. 8
53.0
.39. 6.
“52.3
42. 5.
50.6
;
.
1
i
;
1
7. 3
14. 3;
19. 0
20.1
. 6. 5‘
17. 0
9.8
6;‘9'
13. s;
10. 7
'
Bromine'No__.__
Percent Sulfur __________ __
___
>
1.6
2e. 7
36. s,
12. 3‘
13: 5‘
V
'
49. 2
51. 5
46. 3
45. 4'
7.3
30.2
19.0
13. 9
20. 1
24. 2
5. 5
34. 0
12.3.
10.5
3.9
14.1
35. 1
33.6-
32.2
32 ‘a
22.91
123.0
22.5
0.461
0.59
0.13
0.14
0. 36.
Nes
20.2:
‘
0. 52‘
3.0
1. 52
23.- 4‘
.
133
0. 01
2017
0. 79
037
0.06
20. 4
0. 33
v0. 38
7. 4
1. 39
9.3
)0. 93
2L 5
=3. 7_
1. 46.
6. 7.
1. 32
2-4
2.26
22- 6
0. 02
r19. 81
0. 75,
0= 89
7_. 3»
1-52
24- 1v
23. 61
'23. 7
"122
241
55
120
100'
.2001
‘120
330:
115'
.255:
Carbon Residue'DlSQ ......... _.
0. 03
GEO-950° F. Parr. _____________ __
Nes,
Percent Sulfur
Carbon Residue ______________________ -v1950" 13‘. + Btms. °API ........ _3-5
Percent Sulfur ________________ __
1.18
"Carbon‘Residue ______________ __
23.5v
vMetals by ES:
N10, p.p.m__.'- .__ -.____
94
V505. p.p.m.--_ _-
21. 9
'11. 1;
l
64-80
2053
253
~43.
53;
40.
10;
I
.46. 2
42. 4
43. 0
41.
.
>21. 921. 7,
25.7
13; 7
' as. a‘
10.3
40.
-. 9.
p
10.2
12.2
34. 9
34. 3
32. 3‘
‘32. 4V
33.
11.71‘ 19:5
v22.7
29.3
33.71
.33.
0.51
1.11‘
1.22
1.2
0.02
19.53
0. 91
0. 70
0. 05
19. 0;
1.‘ 31
0.‘ 56
0. 01
1s. 9.
1. 52
1.33
'33. 4
0; 0
.-13.3
1.69
‘1.37
0.7
2.40
‘36:0
218
.350
'250
740
9.9 .
3.
was provided ‘with a catalyst bed of a calcined cobalt 40 Examination of the data of Table I shows the ability
of the catalyst .of the .presentinventionto promote the
molybdena-on-acid treated halloysite clay. The catalyst
analyzed approximately 2.5% Co-and 8.5% M003. The
amount vof catalyst present in the reactor was such/that
the weight hourly space velocity was .8 based on the
total fresh feed. The temperature:in the hydrocra-cking
reactor was about 820° F. and the pressure about 1000
p.s.i1.-g. The product together_with the unconsumed hy
drogen was removed from the bottom of the reactor and
introducedv into a ?ash drum. Unconsumed hydrogen as
selective hydrocrackin-g reaction with relatively small con
sumption of hydrogen whereas other hydrocracking cat
alysts although aifording hydrocracking of. asphaltic feed
stocks cannot upgrade the asphaltic feed without sub
stantial consumption'of hydrogen, yet the API gravities
in the 950° F. minus fractions obtained by our hydro
cracking operation are good. The data also show that
the catalyst did not deactivate as far as conversion is
concerned over an 80'hour period and that the catalyst
well ascertain ‘volatile constituents of the product were
was
relatively clean. The low hydrogen consumption
50
recoveredoverhead'and passed to an absorber to purify
and perhaps other factors result in a.950° 'F.+ fraction
the hydrogen. The hydrogen from the absorber wasre
which is relatively unre?ned, i.e. as compared with that
cycledat -a rate of 4000 s.c.f./lb. to the hydrogen line
from the use of non-halloysite based catalysts, and the
and hence into the reactor. The liquid product was re
heavy fraction is high in sulfur, carbon residue and cat—
movedfrom the ?ash-drum and introduced into a super
atrnospheric fractionating'colurnn. In the fractionation 55 .alyst-poisoning metals and of low gravity. Thus the ?rst
step of the process is selective towards improving the
column the liquid product'was split into a 950° F. minus
more
valuable light products which are to 1be hydrogenated
tractionrand a 950°.F. plus fraction (based on atmospheric
in our second stage and hydrogen is vnot lost to the rela
pressure). Composites of tests of a series-of runs were
made to obtain‘product inspection from 0-8, 32-48,
48-64 and 64-80 hours on stream. Table 1 lists the re
sults of these tests.
The 950° F. minus fraction from each run is then
sent to a hydrogenation zone. The hydrogenation zone
is provided with a bed of cobalt-molybdena-on-alumina
' tively less desirable “950° ‘F.+ fraction.
We claim:
60
1. A process for the conversion of asphaltecontaining
petroleum residuals which comprises passing an asphalt
containing petroleum residual fraction and hydrogen
under hydrocracking conditions, including a temperature
catalyst and hydrogen gas at a rate of 3500 s.c.f./1b. The 65 from about 600 ‘to 900° F. and elevated pressure, into
contact ‘with a calcined catalyst consistingessentially of
catalytic amounts of cobalt and molybdena on acid
zone is’ operated eta temperature of ‘680° F. and a pres
treated halloysite clay, separating the resulting product
sure of ~500'p.s.i.g. The amountof ‘catalyst present was
at a separation point within the range .of about 800 to
such that the weight hourly-space velocity ‘based on'the
1000° F. into a heavierfraction and a lighter‘fraction,
70
totalfced-waslO. .The'hydrotreated (hydrogenated and
catalyst analyzes 2.5% cobalt and 6% molybdenum. The
hydrotreating the lighter fraction under hydrogenation
desuliurized) product then is sent to a fractionator. In
conditions and in the presence of a hydrogenation catalyst.
the. fractionator a reformingstock. having an end boiling
2. The process of claim 1 wherein the hydrocracking
pointof about 400° Rand a cracking stock and heating
conditions
include a temperature of about 780 to 800° F.
oil .having'aninitial boilingpoint of about 400° F. and
75 and a. pressure of about 2200 tov 27 00 p.s.i.g.
an end boiling point of about'950°
are obtained.
5
3,079,325’
3. The process of claim 1 wherein the lighter fraction
has an end boiling point of about 950° F.
4. The process of claim 1 wherein the hydrotreating
step is conducted in the presence of a hydrogenation cat
alyst at a temperature of about 550 to 800° 'F., ‘a pressure
of about 200 to 800 p.s.i.g.
5. The process of claim 4 wherein the hydrogenation
catalyst is cobalt molybdena on alumina.
6
References Cited in the ?le of this patent
UNITED STATES PATENTS
O?uit et a1. __________ _._ May 1,
Q,744,‘05 6
2,85 3,433
2,902,43 1
2,908,633
2,9 14,45 9
Keith ________________ __ Sept. ‘23,
Dinwidclie et ‘a1. _______ __ Sept. 1,
Reif et a1. ____________ __ Oct. 13,
Mills et a1. __________ __ Nov. 24,
1956
1956
1959
1959
1959
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