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Патент USA US3026270

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March 20, 1962
c. H. WATKINS
3,026,260
THREE-STAGE HYDROCARBON HYDROCRACKING PROCESS
Filed April 25, 1960
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United States Patent 0 "
3,926,260
Patented Mar. 20, 1962
2
1
heavier hydrocarbon fractions results in a substantially
3,026,260
THREE-STAGE HYDROCARBON HYDRO
CRACKING PROCESS
Charles H. Watkins, Arlington Heights, 111., assignor to
Universal Oil Products Company, Des Plaines, 111., a
corporation of Delaware
Filed Apr. 25, 1960, Ser. No. 24,594
17 Claims. (Cl. 208-68)
increased yield of gasoline boiling range hydrocarbons;
that is, those hydrocarbons and hydrocarbon fractions
boiling within the range of from about 100° F. to about
400° F. or 450° F., containing iso and normal butanes,
as the particular case warrants. The necessity for hydro
cracking selectivity exists in order to avoid the decom
position of normally liquid hydrocarbons substantially
or completely into normally gaseous hydrocarbons, the
The present invention relates to a process for the con 10 latter being inclusive of methane, ethane and propane.
version of hydrocarbonaceous material into lower boil
ing hydrocarbon products, and, in one embodiment, is
The ultimate volumetric yield of normally liquid hydro
carbons, especially those boiling within the gasoline boil
directed toward a process for producing hydrocarbons
ing range, as an inherent result of the excessive produc
tion of normally gaseous hydrocarbons, can be decreased
ranges and substantially free ‘from nitrogenous com 15 to the extent Where the process is not economically
boiling within the gasoline and middle-distillate boiling
pounds, from hydrocarbons boiling at a temperature in
feasible.
excess of the middle-distillate boiling range, the latter
from controlled or selective hydrocracking in that the
being contaminated by substantial quantities of nitrog
latter involves the splitting of a higher-boiling hydro
carbon molecule into two hydrocarbon molecules, both
enous compounds.
Hydrocracking, or destructive hydrogenation, as dis
tinguished from the relatively simple addition of hydrogen
to unsaturated bonds between carbon atoms, e?ects
de?nite changes in the molecular structure of hydrocar
bons. Hydrocracking may, therefore, be designated as
cracking under hydrogenation conditions in such a man
ner that the lower-boiling hydrocarbon products resulting
therefrom are substantially more saturated than when
hydrogen, or material supplying the same, is not present.
As presently practiced, hydrocracking processes are most
Non-selective hydrocracking is distinguished
of which are normally liquid hydrocarbons. To a some
what lesser degree selective hydrocracking involves the
controlled removal of methyl, ethyl and propyl groups,
which, in the presence of hydrogen, are converted to
methane, ethane and propane, the latter being referred to
as “light para?inic hydrocarbons.” In selective hydro
cracking, the removal of the aforesaid radicals is con
trolled such that not more than one, or possibly two of
such radicals are removed from a given molecule. For
example, in the presence of hydrogen, and under selective
commonly employed for the destructive conversion of 30 hydrocracking conditions, normal decane may be reduced
various coals, tars and heavy residual oils for the purpose
to two pentane molecules, normal heptane reduced to
of producing substantial yields of low boiling, saturated
products; to some extent, there exists at least partial
hexane, and nonane reduced to octane or heptane, etc.
Conversely, uncontrolled or non-selective hydrocracking,
conversion to intermediates which are suitable for utiliza
will result in the decomposition of normally liquid hydro
tion as domestic fuels. In many instances, heavier gas 35 carbons into the aforesaid normally gaseous hydrocar
oil fractions, which ?nd utilization as lubricating material,
are also produced. Although many of these hydrocrack
ing processes, or destructive hydrogenation reactions, may
bons; for example, through the continuous demethylation
of normal heptane to produce seven methyl groups which,
in the presence of hydrogen, are converted to seven
be, and are, conducted on a strictly thermal basis, either
molecules of methane. Thus, hydrocracking reactions
in the absence, or presence, of hydrogen, the preferred 40 which are permitted to run rampant can be seen to effect
processing technique involves the utilization of a catalytic
seriously the economic considerations of a given process.
composite possessing a high degree of hydrocracking
Another disadvantage of non-selective or uncontrolled
activity. To assure effective catalytic action over an
hydrocracking is that such hydrocracking results in a
extended period of time, and from the standpoint of
more rapid formation of increased quantities of coke and
producing an increased yield of liquid product having im
proved physical aud/or chemical characteristics, con
other heavy carbonaceous material which becomes de
posited upon the catalytic composite employed, and de
trolled or selective cracking is desirable in virtually all
hydrocracking processes. For example, the lower mo
creases, or even destroys, the activity thereof to catalyze
the desired reactions in the desired manner. Such de
lecular weight products, consisting essentially of those
activation inherently results in a shorter processing cycle
or period, with the attendant necessity of more frequent
regeneration of the catalyst, or total replacement thereof
hydrocarbons boiling within the normal gasoline boiling 0
range, usually have an increased octane rating, and, as
with fresh catalyst. Gf further signi?cance, in regard to
the hydrocracking reaction, especially the economic con
siderations thereof, are the aspects of hydrogen produc
tion and consumption, the preservation of aromatic com
pounds which boil within the gasoline boiling range, and
from high molecular weight unsaturated hydrocarbons.
the production of a liquid product substantially free from
Selective hydrocracking is of particular importance
low molecular weight, unsaturated hydrocarbons. The
when processing hydrocarbons, and mixtures of hydro
deactivation of the catalyst, through the deposition of
carbons, having a boiling range in excess of the gasoline 60 coke and other ‘heavy carbonaceous material, or other
and middle-distillate boiling ranges; that is, hydrocarbons
means, appears to inhibit the hydrogenation activity to
and mixtures of hydrocarbons, as well as various hydro
the extent that a signi?cant proportion of the gasoline
carbon fractions, distillates and gas oils, having a boiling
boiling range hydrocarbons consists of unsaturated paraf
range indicating an initial boiling point of at least about
a'ins whereby the same is not highly suitable for subse
650° F. or 700° F., and an end boiling point as high as
' quent direct processing by catalytic reforming. On the
1000° F., or more. The controlled, or selective hydro
other hand, selective hydrocracking does not tend to ef
cracking of such hydrocarbon fractions results in greater
fect substantial hydrogenation, or saturation, of the aro~
yields of hydrocarbons boiling within the gasoline and
matic compounds boiling within the gasoline boiling
middle-distillate boiling range; that is, those hydrocarbons
range, or the destructive hydrogenation of low molecular
and hydrocabon fractions having a boiling range indicat
ing an end boiling point below about 650° F. to about 70 weight, straight or ‘branched-chain hydrocarbons into
700° F. Furthermore, the selective hydrocracking of such
normally gaseous hydrocarbons. Aromatic hydrocar
such, are extremely suitable for subsequent utilization in
catalytic reforming processes to further increase the
octane rating. Similarly, controlled or selective hydro
cracking results in an increased yield of middle-distillate
boiling range hydrocarbons which are substantially free
3,026,260
3
4
combine with the e?iuent vfrom said second reaction zone
bons, boiling within the gasoline boiling range, possess a
relatively high octane blending value, and are, therefore,
utilized to great advantage in increasing the anti-knock
characteristics of a given gasoline boiling range traction.
and hydrogen, prior to conversion thereof in said third
reaction zone.
The present invention is directed toward a three-stage
process for converting hydrocarbonaceous material hav
In addition, selective hydrocracking, although inhibiting
ing a boiling range of from about 700° F. to about 1000°
the saturation of aromatic compounds, does not neces
F., and containing nitrogenous compounds, into lower
boiling hydrocarbon products, which process comprises
initially fractionating said hydrocarbonaceous material to
produce a ?rst light fraction containing those hydrocar
sarily result in the production of an excessive quantity
of the lower molecular weight, unsaturated parat?nic hy
drocarbons.
Investigations have indicated that the relatively rapid 10
bons boiling below about 800° F. and a ?rst heavy frac
deactivation of a hydrocracking catalytic composite re
tion having an initial boiling point of about 800° F.,
cracking said ?rst heavy fraction in a ?rst reaction zone
containing a catalyst comprising at least one metallic
sults from the presence of nitrogen-containing compounds
within the hydrocracking charge stock. These nitroge
nous compounds, such as naturally-occurring, organic ni
trogenous compounds, examples of which include pyrroles,
15 component selected from the metals of groups VIA and
the iron-group of the periodic table, and mixtures thereof,
amines, indoles, and other classi?cations of organic com
pounds, result in the deactivation of the catalytically
separating the resultant e?'luent into a second light frac
tion and a second heavy fraction, the latter having an
initial boiling point of about 800° F., recycling said sec
ond heavy fraction to combine with said ?rst heavy frac
tion prior to conversion in said ?rst reaction zone, and
combining said second light fraction with said ?rst light
fraction; reacting the resultant light fraction mixture in
active metallic components, as well as the refractory in
organic oxide carrier material which acts as the acidic
component of a great variety of hydrocracking catalysts.
Such deactivation appears to result through the reaction
of the nitrogenous compounds with the various catalytic
components, the extent of such deactivation steadily in
a second reaction zone and in contact with a catalyst com
creasing as the process continues, and as the nitrogen
containing feed stock continues to contaminate the cata
lyst through contact therewith. It is believed that neu
prising from about 4% to about 45% by weight of molyb
traiization, occurring when the basicity of the nitrog
drocarbons from the resultant second zone e?luent, and
denum, removing ammonia and normally gaseous hy
passing the normally liquid hydrocarbons, along with
enous compound reacts with the acidic catalyst, result
additional hydrogen, into a third reaction zone maintained
ing in a neutralization of the latter, is a factor to be con
sidered in the deactivation of the catalyst, but is not the 30 at hydrocracking conditions; removing normally gaseous
hydrocarbons from the third reaction zone e?°luent and
predominating deactivating in?uence. The more predomi
catalyst deactivation, is believed to be the formation of
separating the normally liquid hydrocarbons into a ?rst
fraction having an end boiling point of about 400° F.
a nitrogen-containing complex, through inter-reaction with
the catalytically active metallic components, whereby the
to about 450° F., a second fraction having an initial
boiling point of about 400° F. to about 450° F. and an
active centers of the catalyst, normally available to the
hydrocarbon charge stock, are effectively shielded there
end boiling point of about 650° F. to about 700° F., and
nating e?ect, having the greatest in?uence in regard to
from.
a third fraction boiling at a temperature in excess of
about 650° F. to about 700° F., recycling at least a por
tion of said third fraction to combine with said hydrogen
Deactivation of this nature is not believed to be
a simple reversible phenomenon which may be easily
recti?ed by merely heating the catalyst in the presence
of hydrogen vfor the purpose of decomposing the nitro
gen-containing complexes.
40
and the normally liquid hydrocarbons from said second
reaction zone, prior to conversion thereof in said third
reaction zone.
A more speci?c embodiment of the present invention
The primary object of the present invention is to pro
involves a process for converting nitrogen-contaminated
vide a ‘hydrocracking process which produces substantially
greater yields of hydrocarbons boiling within the gaso 45 hydrocarbonaceous material, having a boiling range of
from about 700° F. to about 1000° E, into lower boil
line and middle-distillate boiling ranges, without the at
ing hydrocarbon products substantially free from nitrog
tendant saturation of aromatic compounds and the uncon
enous compounds, which process comprises initially
trolled cracking of the low molecular weight hydrocar
stabilizing said hydrocarbonaceous material to produce
bons. A related object is to provide a process which
permits the utilization of petroleum hydrocarbon charge 50 a ?rst light fraction containing those hydrocarbons boil
ing below about 800° F., and a ?rst heavy fraction hav
stocks having an initial boiling point as high as about
ing an initial boiling point of about 800° F.; cracking
700°
to about 800° F. or more, which charge stocks
said ?rst heavy fraction in a ?rst reaction zone contain
contain residual nitrogenous compounds in excessive
ing a cracking catalyst comprising at least one metallic
quantities of the order of about 1000 ppm. to about 5000
component from the metals of groups VIA and the iron
p.p.rn., such concentrations otherwise resulting in the
group of the periodic table, and mixtures thereof, sepa
rapid deactivation of the catalytic composite employed.
rating the resultant e?iuent into a second light fraction
In one embodiment, the present invention relates to a
and a second heavy fraction containing hydrocarbons
process for converting hydrocarbonaceous material, hav
boiling in excess of a temperature of about 800° F., re
ing a boiling range in excess of the gasoline boiling range,
into lower boiling hydrocarbon products which comprises 60 cycling the second heavy fraction to combine with said
?rst heavy fraction prior to the conversion thereof in
cracking said hydrocarbonaceous material in a ?rst re
said ?rst reaction zone, and combining said second light
action zone, separating the resultant e?iuent into a light
fraction with said ?rst light fraction; reacting the re
fraction and a heavy fraction containing hydrocarbons
sulting light fraction mixture with hydrogen in a second
having an initial boiling point in excess of a temperature
of about 800° F.; reacting said light fraction with hy 65 reaction zone containing a catalyst comprising from about
4% to about 45 % by weight of molybdenum, removing
drogen in a second reaction zone, passing at least a por
ammonia and normally gaseous hydrocarbons from the
tion of the effluent therefrom, along with additional hy
resultant second zone e?luent, and passing the normally
drogen, into a third reaction zone maintained at hydro
cracking conditions; separating the resultant normally
liquid hydrocarbons, along with additional hydrogen, into
liquid hydrocarbons into a ?rst fraction having an end 70 a third reaction zone maintained at hydrocracking condi~
tions and containing a catalyst comprising from about
boiling point of about 400° F. to about 450° F., a sec
0.01% to about 5.0% by weight of palladium composited
ond fraction having an end boiling point of about 650°
with silica and from about 10% to about 90% by weight
F. to about 700° F., and a third fraction boiling at a tem
of alumina; removing normally gaseous hydrocarbons
perature in excess of about 650° F. to about 700° F.,
and recycling at least a portion of ‘said third fraction to 75 from the resultant third zone ei?uent and separating the
8,026,260
6
3
normally liquid hydrocarbons into a first fraction having
an end boiling point of about 400° F. to about 450° F.,
a second fraction having an initial boiling point of about
400° F. to about 450° F., and an end boiling point of
about 650° F., to about 700° F., and a third fraction 5
boiling at a temperature in excess of about 650° F. to
about 700° F., recycling at least a portion of said third
fraction to combine with the normally liquid hydrocar
bons from said second reaction Zone and hydrogen, prior
to conversion thereof in said third reaction zone.
carrier material, are zirconia, magnesia, thoria, boria, ti
tania, etc. The preferred hydrocracking catalyst com
ponent, for use in the third stage, comprises a composite
of silica and from about 10% to about 90% by weight
of alumina, and still more preferably, a composite of
silica and from about 25% to about 65% by weight of
alumina. As hereinabove stated, the process of the pres
ent invention involves the utilization of three separate,
distinct reaction zones, each of which contains a catalyst
10 Whose composition depends, at least in part, upon the
The three-stage process of the present invention may
function to be served within such reaction zone, and,
be more clearly illustrated and understood by initially de
therefore, these catalytic composites will hereinafter be
?ning several of the terms and phrases as employed Within
described in greater detail.
the present speci?cation and the appended claims. The
As hereinbefore set forth, one'embodiment of the
term, “hydrocarbons,” or “hydrocarbonaceous material,” 15 present invention involves a process for producing hydro
is intended to connote saturated hydrocarbons, straight
carbons which boil within the gasoline and middle-distil
chain and branched-chain hydrocarbons, unsaturated hy
late boiling range, from those hydrocarbons which boil
drocarbons, aromatic and naphthenic hydrocarbons, as
at a temperature in excess of the middle-distillate boiling
well as mixtures of various hydrocarbons such as hydro
range. The three-stage process of the present invention
carbon fractions and/ or hydrocarbon distillates, etc. The
encompasses at least one hydrocracking reaction zone,
phrase, “hydrocarbons boiling Within the gasoline boiling
which, in and of itself, has been considered generally
range,” or “gasoline boiling range hydrocarbons,” is in
applicable to processing petroleum-derived feed stocks of
tended to connote those hydrocarbons boiling at a tem
the middle-distillate boiling range and above. Suitable
perature of from about 100° F. to about 400° F. or 450°
charge stocks to hydrocracking processes are considered
F.; that is, hydrocarbon fractions having an initial boiling
to include kerosine fractions, gas oil fractions, lubricat
points (as determined by Standard ASTM distillation
ing oil and white oil stocks, cycle stocks, fuel oil stocks,
methods) of about 100° F., and an end boiling point
reduced crudes, the various high-boiling bottoms recov
within the range of about 400° F. to about 450° F.
ered from the fractionating columns generally integrated
“Gasoline boiling range hydrocarbons” is intended to in
within catalytic cracking operations, and referred to as
clude hydrocarbon mixtures having the aforesaid boiling 30 heavy recycle stock, and other sources of hydrocarbons
range, and inclusive of iso and normal butanes. The
having a depreciated market demand due to the high
term, “light para?inic hydrocarbons,” is intended to con
boiling points of these hydrocarbons, accompanied by
.note those hydrocarbons containing three or less carbon
the usual presence of asphaltic and other heavy hydro
atoms; that is, methane, ethane and propane. Therefore,
carbonaceous residues. The present invention is particu
“hydrocarbons boiling at a temperature in excess of the
larly directed toward processing the heavier of the afore
gasoline boiling range” is intended to connote those hy
mentioned hydrocarbon feed stocks, namely, vacuum gas
drocarbons and mixtures of hydrocarbons which possess
oil fractions, white oil stocks, heavy cycle stocks, fuel
an initial boiling point in excess of about 400° F. to
oil stocks, reduced crudes etc.; that is, those heavy hy
about 450° F. The term, “middle-distillate,” or “light
drocarbons having an initial boiling point of at least
gas oil,” refers to those hydrocarbon fractions having an 40 about 650° F. to about 700° F. and an end boiling point
initial boiling point within the range of about 400° F.
of about 1000° F. or more. Generally, all of these
to about 450° F. and an end boiling point within the
sources of hydrocarbon feed stocks contain high-boiling
range of about 650° F. to about 700° F. Similarly, in
nitrogenous compounds and sulfurous compounds as con
regard to the various catalytic composites employed within
taminants. Although the major proportion of such ni
the three individual reaction zones of the present process,
trogenous compounds may be removed by many known
and in one embodiment in two of the three reaction zones,
means, such as a hydrore?ning pretreatment, it is very
the term, “metallic component,” or “catalytically active
di?icult, if not virtually impossible, to remove the last
metallic component," is intended to encompass those com
few parts per million of nitrogen from the charge stock
ponents which are employed for their hydrocracking ac
prior to subjecting the same to the hydrocracking process.
tivity, or for their propensity for the destructive removal 50 For example, a hydrore?ning pretreatment, in which the
of nitrogenous compounds, as the case may be. In this
feed stock is subjected to the action of a catalyst, at re
manner, the “catalytically active metallic components” are
action conditions, will result in the conversion of the
distinguished from those components which are employed
nitrogenous, organically-bound components into am
as the solid support, or carrier material, or the acidic
monia and the corresponding hydrocarbon residue. Al
cracking component. As hereinafter set forth in greater
though the structure of the hydrocarbon components are
detail, the process of the present invention consists of
not substantially altered, the resulting hydrocarbon charge
three integrated, but separate, stages. Each stage utilizes
stock will, in all probability, contain a relatively minor
a distinct catalytic composite, di?erent, in most applica
amount of nitrogenous compounds, as compared to the
tions of the present invention, from the catalytic com
excessive quantity originally present. Notwithstanding
posites employed in the other stages. The various cata 60 such quantities, these organic nitrogen compounds will
lytic composites will hereinafter be described in detail with
eventually result in the deactivation of hydrocracking
reference to the particular stage in which employed, and
catalyst, and particularly catalysts consisting of metals
also in regard to the function to be served.
The particular catalytically active metallic component,
or components, regardless of the stage in which employed,
are composited with a suitable, solid carrier material,
which may be either naturally-occurring, or synthetically
prepared. Naturally-occurring carrier materials, include
various aluminum silicates, particularly when acid-treated
to increase the activity thereof, various alumina-contain
ing clays, earths, sand, and the like; synthetically-prepared
carrier material generally includes at least a portion of
both silica and alumina. Other suitable carrier material
components which may, in particular instances, be com
bined in an integral portion of the synthetically-prepared
from groups VI and VIII of the periodic table. For ex
ample, I have found that a catalyst comprising at least
one platinum-group metallic component, impregnated
upon a silica-alumina carrier material, is a very effective
catalyst for the hydrocracking of gas oils boiling below
about 800° F. However, these catalysts are virtually im
mediately poisoned by either sulfurous or nitrogenous
compounds, and particularly by the latter. The con
taminants, and particularly organically-bound nitrogen
ous compounds, are very di?icult, if not impossible, to
remove from hydrocarbon fractions boiling above about
800° ‘F., whereas virtually complete removal may be ef
fected from hydrocarbons boiling below about 800° F.
3,026,260
7
present invention, particularly when processing hydro
in particular processing schemes, a ?uid catalytic cracking
carbon charge stocks boiling above about 700° F, to
about 1000° F. or more, it is possible to produce high
unit operating in the absence of added hydrogen. It is
understood that the precise conversion means, illustrated
in the drawing as cracking zone 9, by which those hydro
volumetric yields of gasoline boiling range hydrocarbons
while simultaneously maximizing the yield of middle
distillate hydrocarbons which are substantially free from
nitrogenous compounds. A substantial increase in the
overall yield of gasoline boiling range hydrocarbons may
then be obtained by further processing nitrogen-free, mid
carbons boiling at a temperature in excess of about
800° F, are converted to hydrocarbons boiling below
about 800° F., is not considered to be a limiting feature
10 of the present invention. 1 have found that the nitrog
dle-distillate material simultaneously produced by the pres
ent process. The ?exibility of the present process permits
the withdrawal to storage of the middle-distillate hydro
carbon product for subsequent conversion to gasoline
boiling range hydrocarbons when the marketability of the 15
latter so requires.
The present three-stage process may be more clearly
8
VIA metal such as molybdenum, chromium and/ or tung
sten. The ?rst reaction zone, cracking zone 9, may be,
Through the utilization of the threestage process of the
enous compounds, contaminating the hydrocarbon charge
stock entering line 1, are extremely di?icult to re
move from the heavier hydrocarbons, that is, those
hydrocarbons boiling in excess of 800° F ., whereas these
nitrogenous compounds are readily susceptible to removal
from those hydrocarbons boiling below about 800° F.,
especially through the utilization of a particular catalytic
It is not
composite as hereinafter set forth. In any event, the
total effluent from cracking zone 9 passes through line
intended, however, to unduly limit the present process to
the particular embodiments indicated in the drawing.
drocarbons are removed via line 13 into fractionator 14.
understood through reference to the accompanying draw
ing which illustrates one embodiment thereof.
10 into separator 11 from which the normally liquid hy
Separator 11 serves to remove light para?inic hydro
carbons, such as methahe, ethane and propane, and other
overhead re?ux condensers, pumps, compressors, heaters,
various gaseous components from the total ef?uent enter
knockout pots, etc., have been eliminated, or greatly re
duced, as not being essential to the complete understand 25 ing through line 10, providing thereby a normally liquid
hydrocarbon stream in line 13. The light para?inic hy_
ing of the present process. The utilization of these, and
drocarbons are indicated as leaving separator 11 via line
other miscellaneous appurtenances will immediately be
12. Other gaseous components are removed from the
recognized by one possessing skill in the art of petroleum
normally liquid hydrocarbons in separator 11, and in
processing; it is not intended that such modi?cations re
move the process beyond the scope and spirit of the ap 30 clude carbon monoxide, carbon dioxide, hydrogen sul?de,
ammonia, sulfur dioxide, and various oxides of nitrogen.
pended claims. Referring now to the drawing, the hy
Various modi?cations may be made to the separating
drocarbon change stock, contaminated by a substantial
means illustrated by separator 11, whereby the overall
quantity of nitrogenous compounds, of the order of
?ow pattern therein is changed, but the function to be
about 1000 p.p.m. to about 5000 p.p.m., and sulfurous
compounds as high as about 3.0% to about 5.0% by 35 served, as well as the end result, remains the same. For
example, the total gaseous phase, illustrated as leaving
weight, enters the process through line 1 into stabilizer 2.
via line 12, may be passed through a suitable absorbent
To illustrate a particularly preferred embodiment of the
material, whereby the light paraf?nic hydrocarbons are
present invention, the charge stock in line 1 is indicated
recovered substantially free from hydrogen sul?de, am
as having an initial boiling point of about 700° F. and
monia, carbon dioxide, and the various oxides of nitrogen
an end boiling point of about 1000° F., as determined by
and sulfur. Similarly, vwater may be injected into line
standard ASTM distillation. However, it is understood
10, the mixture entering a suitable liquid-liquid separat
that the charge stock may be any of the heavy hydro
ing zone whereby the ammonia is adsorbed in, and re
carbonaceous material previously described; for exampie,
moved with the water phase, the light para?inic hydro
a reduced crude consisting entirely of hydrocarbons boil
carbons and other gaseous components being removed as
ing at a temperature in excess of 800° F. to 1000“ F. or
indicated by line 12, and the normally liquid hydrocar
more. The total liquid charge stock entering stabilizer
bons removed via line 13. Various other modi?cations,
'2 is separated into a ?rst light fraction having an end boil
in regard to the separating means illustrated by separator
ing point of about 800° F., shown as leaving stabilizer 2
11, as well as those separating means hereinafter de
via line 3, and a ?rst heavy fraction having an initial
boiling point of about 800° F., indicated as vleaving sta- I scribed, and illustrated by separators 21 and 30, will be
immediately recognized by those possessing skill in the
bilizer 2 via line 4. This ?rst heavy fraction is combined
art
of petroleum processing. It is not intended that these
with a second heavy fraction, containing hydrocarbons
modi?cations, and those above set forth, remove the re
boiling in excess of about 800° F., the mixture being
sulting flow from within the broad scope of the present
passed through heater 6 and line 8 into cracking zone 9.
invention. As illustrated, one of the essential features
The primary function, to be served by cracking zone 9,
of the present invention is the initial preparation of a
is the conversion of those hydrocarbons boiling in excess
stream of normally liquid hydrocarbons boiling below
of a temperature of 800° F. into lower boiling hydrocar
about 800° F ., and which pass through line 13 into frac
bon products which boil below about 800° F. Thus,
Various flow valves, control valves, coolers, condensers,
tionator 14. Fractionator 14 is maintained under suit
cracking zone 9 may be a common thermal-cracking reac
tion zone of the single-coil or double-coil type, in which 60 able operating conditions, of temperature and pressure,
instance the total liquid charge thereto is raised to the
such that the normally liquid hydrocarbons entering via
desired thermal cracking temperature in heater 6, prior
line 13 are separated into a second heavy fraction, con
taining those unreacted hydrocarbons boiling at a tem
perature in excess of 800° F. and a second light fraction
to entering cracking zone 9 through line 8. In another
embodiment, cracking zone 9 may comprise a catalytic
hydrocracking unit, in which event the total liquid charge
in line 4 is admixed with the requisite quantity of hydro
gen entering via line 5, the mixture being raised to the
operating temperature in heater 6, passing through line 8
into cracking zone 9. In this latter instance, cracking
zone 9 will contain a suitable hydrocracking catalyst
which may be an iron-group metallic component com
posited with a siliceous carrier material such as alumina
and silica. Or, the hydrocracking catalyst may comprise
an iron-group metallic component promoted by a Group
containing those hydrocarbons having an end boiling
point of about 800° F. The second heavy fraction is
removed from fractionator 14 via line 7 and is combined
With the ?rst heavy fraction in line 4 leaving stabilizer
2. The second light fraction is removed from frac
tionator 14 via line 15, and is admixed with the ?rst light
fraction leaving stabilizer 2 in line 3. The resulting light
fraction mixture is admixed with hydrogen, entering the
system via line 16, and the total charge is raised to the
desired operating temperature, within the range of about
8,026,260
9
10
500° F. to about 1000° F., in heater 17. The heated
From the foregoing description of the embodiment
mixture of hydrogen and the light fractions from stabilizer
illustrated in the accompanying drawing, it is readily as
2 and fractionator 14 are passed via line 18 into clean-up
certained that the process is, in effect, a three-stage proc
reaction zone 19. Clean-up zone 19 has disposed therein
ess for producing hydrocarbons boiling within the gaso
a catalytic composite comprising from about 4% to about 5 line boiling range, and simultaneously for producing in
45% by weight of molybdenum, calculated as the ele
creased yields of middle- istillate boiling range hydro
ment. The reaction zone is maintained under operating
carbons, the latter being extremely suitable for direct
conditions such that the substantially complete destruc
processing to produce additional gasoline boiling range
tion of the nitrogenous compounds, as well as the sul
hydrocarbons. Various modi?cations may be made to
furous compounds, contained within the charge stock, the 10 the illustrated embodiment by those possessing skill
latter now consisting essentially of hydrocarbons boiling
within the art of petroleum processing, and it is not in
below about a temperature of 800° F., is effected. In
tended that such modi?cations remove the process from
the scope and spirit of the appended claims. For ex
addition, as hereinafter set forth, through the careful
selection of both catalyst and operating conditions, there
ample, as hereinabove stated in regard to separators 11,
21 and 30, changes may be made whereby a somewhat
will be e?ected, in clean-up zone 19, a substantial degree
of hydrocarbon conversion whereby the heavier hydro
di?erent ?ow pattern and apparatus setup results. It is
carbons, those boiling within the range of from about
evident, however, that such a ?ow pattern will merely
650° F. to 800° F., are converted into hydrocarbons
accomplish the same object resulting from the flow pat
boiling below about 650° F., without experiencing the
tern illustrated within the drawing. An essential feature
excessive production of light .parai?nic hydrocarbons, 20 of the process of the present invention involves the three
stage reaction zone system, whereby each stage individ
methane, ethane and propane. Furthermore, since the
ually performs a particular function in a particular man
catalyst in clean-up zone 19 is selected for its nitrogen
insensitivity, the rapid deactivation of the catalyst, other
ner, the combinative effect being the production of gaso
wise resulting when hydrocracking ‘such nitrogen-contain
line and middle-distillate boiling range hydrocarbons
ing charge stocks, is not experienced. The total e?luent 25 from those hydrocarbons boiling in excess of a tempera
ture of about 700° F., the latter contaminated by substan
from reaction zone 19 is passed via line 20 into separator
tial quantities of nitrogenous compounds of the order of
21. As previously described With reference to separator
about 1000 ppm. to about 5000 ppm.
11, separator 21 is employed to illustrate a separating
means whereby the normally liquid hydrocarbons are
As hereinbefore set forth, the process ‘of the present
recovered in line 23 substantially completely free from 30 invention is particularly directed to the processing of
light para?inic hydrocarbons and other gaseous material,
hydrocarbons and mixtures of hydrocarbons boiling at
indicated as leaving separator 21 through line 22. In
addition, as a result of the catalyst and operating con
temperatures in excess of the "gasoline boiling range.
However, it is most advantageously applied to petroleum
derived feed stocks, particularly those stocks commonly
ditions ‘of clean-up :zone 19, substantial quantities of hy
drogen sul?de and ammonia are removed in separator 21.
considered as being heavier than middle-distillate frac
The normally liquid‘ hydrocarbons in line 23 enter line
tions. Such charge stocks include gas ‘oil fractions, ‘heavy
24, are admixed with hydrogen entering the system via
line 25, the entire mixture passing into heater 26, and
vacuum gas oils, reduced cr'udes, lubricating ‘oils, and
white oil stocks, as well as high-boiling bottoms recovered
from various catalytic cracking operations. Therefore,
thereafter through line 27 into hydrocra'cking zone 28.
The total charge to hydrocracking zone 28 will be raised 40 although the charge stock to the present three stage proc~
ess may have an initial boiling point of about 400° F. to
to a temperature, in heater 26, within the range of about
about 450° F., and an end boiling ‘point of about 1000° F.
450° F. to about 950° F; that is, the operating tempera
or higher, the process affords additional bene?ts, and is
ture of hydrocracking zone 28 will be at least about 50° F.
particularly directed toward the processing of hydrocar
lower than the operating temperature of clean-up zone
19. The total effluent, including butanes, normally liquid
45
hydrocarbons boiling within the range of from about
100° F. to about 800° F., carbon monoxide, carbon diox
bon charge stocks ‘having significantly higher initial boil
ing points, that is, of the order ‘of at least about 650° F.
to about 700° F. In further describing the ‘process of the
present invention, and the various limitations imposed
ide, light para?inic hydrocarbons, etc., are passed through
thereupon, the process will be divided, in the interest of
line 29 into separator 30. The normally liquid hydro
carbons, including butanes, are removed from separator 50 simplicity, into its three separate, distinctly individual
stages.
30" via line 32, and passed to side-cut fractionator 33 at a
Essentially, the ?rst stage comprises a stabilizing
point below centerwell 34. The light para?inic hydro
column, heater and reaction zone, suitable liquid-gas
carbons entering separator 30 are removed via line 31,
separating means, and a fractionator,'the ‘latter employed
and, as hereinbefore described, various other gaseous
for the purpose of separating the total normally liquid
components are removed therefrom, such that only nor
product e?’luent into a light fraction having an end boil
mally liquid hydrocarbons, but including butanes, are
ing point of about 800° F., and a heavy fraction having
passed into side-cut fractionator 33.
an initial boiling point of about 800° F. The various
Fractionator 33 is maintained at suitable conditions of
components of the ?rst stage are utilized in such a man
temperature and pressure whereby the butanes and nor
mally liquid hydrocarbons having an initial boiling point
60 ner, and under such conditions ‘as ‘to result in the sub
of about 100° F. and an end boiling point of about
400° F., and containing less than about 0.1 'p.p.m. of ni
trogen, are removed via line 36. A second fraction, con
taining less than about 3.0 ppm. of nitrogen, is removed
from a point above centerwell 34, via line 35. This sec
ond fraction contains those hydrocarbons boiling within
the middle-distillate boiling range, that is, having an ini
tial boiling point of about 400° F. and an end boiling
point of about 650° F. A third fraction, containing
those unreacted hydrocarbons boiling within the range of
from about 650° F. to about 800° F., are passed through
line 24, combined, at least in part, With‘th'e total normally
liquid hydrocarbon effluent in line 23, further admixed
with hydrogen in line 25, and recycled to the system
through heater 26 and line 27 into hydrocracking zone 28. 75
stantially complete conversion of the charge stock into
hydrocarbons boiling below 800° F. Although at least
a portion of the charge stock is converted, in this ?rst
stage, to hydrocarbons ‘boiling Within the gasoline boil
ing range, the greater proportion of the charge stock will
be converted to hydrocarbons boiling within the range of
from about 400° F. or 450° F. to about 800° F., the
lighter fractions serving as the charge stock to the second
stage of the entire process. Brie?y, therefore, the heavy
hydrocarbon charge stock, for example, a heavy vacuum
gas oil having a boiling range of from about 700° F. to
about 1000° F., or higher, and contaminated by ‘nitroge
nous compounds of the order of from about 1000 ppm.
'to about 5000 p.p.n1., and sulfurous compounds as high
as about 3.0% to about 5.0% by ‘weight, is introduced
3,028,280
11
12
into a stabilizing column for the purpose of removing
initial stabilizing step, thereby forming the total liquid
those hydrocarbons having an end boiling point of about
charge to this ?rst reaction zone.
Similarly, the second-stage of the present process com
800° F. Therremainder of the vacuum gas oil charge is
admixed with hydrogen in an amount of from about
3000 to about 10,000 standard cubic feet per barrel of
such hydrocarbon charge, in those instances wherein the
?rst-stage of the process comprises a hydrocracking re
prises at least a heater, reaction zone, and separating
means similar to that described in regard to the ?rst stage
production of light para?inic hydrocarbons, normally re
of the process. The total liquid charge to the second stage
of the process, now consisting essentially of hydrocarbons
boiling below a temperature of about 800° F., is admixed
with hydrogen in an amount of from about 1000 to about
8000 Standard cubic feet per barrel. The mixture of hy
drogen and liquid hydrocarbons is raised to a tempera
ture of from about 500° F. to about 1000° R, and passed
sulting from a thermal cracking unit, or ?uid catalytic
into the second reaction zone, maintained under an im
action zone. As hereinbefore set forth, the reaction zone
comprising this ?rst stage may be a thermal-cracking
unit of the single-coil or double-coil type. It is preferred,
however, in order to avoid the unnecessary, excessive
posed pressure of about 300 to about 3000 pounds per
the ?rst stage of the process. In the latter instance, the 15 square inch, the catalyst in which second reaction zone
serves a particular dual function. The liquid charge rate
mixture of hydrogen and those hydrocarbons boiling
is equivalent to a liquid hourly space velocity of about 0.1
above about 800° F., is heated to the desired operating
to about 10.0. Thas is, the catalyst is nonsensitive to the
temperature, of from about 500° F. to about 1500“ F.,
presence of substantial quantities of both nitrogenous
and thereafter passed into the ?rst reaction zone. The
cracking unit, to employ catalytic hydrocracking within
reaction zone will be maintained under an imposed pres 20 compounds and sulfurous compounds, while effecting the
destructive removal thereof, and also effects a signi?cant
sure within the range of from about 5 pounds to about
degree of conversion of those hydrocarbons boiling at a
3000 pounds per square inch, and at a temperature within
temperature in excess of about 650° F. into those hydro
the aforesaid range; the precise operating conditions will
carbons boiling within the gasoline and middle-distillate
be dependent upon the various physical and/ or chemical
characteristics of the particular heavy hydrocarbon charge 25 boiling ranges. I have found that a catalyst comprising
relatively large quantities of molybdenum, calculated as
being processed, and upon the type of cracking unit em
the element, and composited with a suitable carrier ma
ployed. Higher pressures appear to favor the destructive
terial such as alumina, is particularly e?icient in carrying
conversion of those hydrocarbons boiling in excess of
out the desired dual operation of the second reaction zone.
about 800° F., and are, therefore, preferred; thus, the
?rst reaction zone will preferably operate under an im 30 A particularly preferred catalytic composite, for utiliza
tion in this ?rst reaction zone, comprises from about 4.0%
posed pressure within the range of about 100 to about
to about 45.0% by weight of molybdenum, and utilizes
3000 pounds per square inch. When utilized as a hydro
alumina as the sole refractory inorganic oxide within the
cracking zone, as distinguished from a simple thermal
carrier material. It is preferred to utilize alumina in
cracking zone, the ?rst reaction zone will contain a hydro
cracking catalyst comprising at least ‘one metallic com 35 the absence of other refractory inorganic oxides, such as
silica, zirconia, magnesia, titania, thoria, boria, etc. Al
ponent from the metals of groups VIA and the iron-group
though these refractory inorganic oxides may be employed
of the periodic table, and mixtures thereof. Thus, the
in relatively minor quantities, with respect to the amount
catalyst will comprise one or more of the following: chro
mium, molybdenum, tungsten, iron, cobalt, and nickel.
of alumina, they appear to impart additional cracking
Regardless of the component, or components, they are 40 activity to the catalyst Within the second reaction zone,
such that those hydrocarbons boiling in excess of about
composited with a suitable carrier material, and prefer
650° F. are subjected to non-selective cracking whereby
ably one which contains substantial quantities of silica.
Thus, the hydrocracking catalyst employed in the ?rst
reaction zone may comprise from about 10% to about
excessive quantities of light paraf?nic hydrocarbons are
produced therefrom. In addition to the aforementioned
50% by weight of nickel, and a composite of alumina and 45 major proportion of molybdenum, minor quantities of
nickel, iron and/or cobalt, from about 0.2% to about
from about 65% to about 95% by weight of silica.
6.0% may be employed. The precise composition of the
Lesser quantities of the group VIA metallic components
catalytic composite employed in the second reaction zone
will be employed, and will lie within the range of from
will, of course, depend to a great extent upon the physical
about 2.0% to about 20.0% by weight thereof. In any
and chemical characteristics of the liquid charge there
event, the hydrocarbon charge stock will contact the
through.
particular catalyst employed at a liquid hourly space
The gaseous ammonia and hydrogen sul?de, resulting
velocity within the range of from about 0.3 to about 10.0;
from the destructive removal of nitrogenous and sul
a relatively lower range of liquid hourly space velocity
furous compound-s within the second reaction zone, are
is preferred, that is, from about 0.3 to about 3.0. Al
though the ?rst reaction zone is designed to serve a single
function, that of converting (those hydrocarbons boiling
above about 800° ‘F. into hydrocarbons boiling below
about 800° F., there will be effected at least partial re
removed from the total e?iuent in any suitable manner.
For example, the total effluent may be admixed with
Water, and thereafter subjected to separation such that the
ammonia is adsorbed within the water-phase. Or, the
total reaction zone e?luent may be passed into a separa
moval of the sulfurous and nitrogenous compounds. The
tion zone, countercurrently to a liquid adsorbent, whereby
resulting ammonia and hydrogen sul?de, in addition to
the ammonia, hydrogen sul?de, and other gaseous com
light para?inic hydrocarbons, carbon monoxide and car
ponents are e?ectively completely removed therefrom.
bon dioxide, and the normally liquid hydrocarbons in
In addition to the removal of hydrogen sul?de and am
cluding butanes, are passed into a suitable separating
monia, it is desired that the few light para?inic hydro
means whereby the bu-tanes and normally liquid hydro
carbons,
methane, ethane, and propane, resulting from
carbons are recovered substantially free from the light 65 the hydrocarbon conversion within the second reaction
para?inic hydrocarbons and the aforementioned gaseous
zone, are also removed from the total e?luent therefrom.
products. The normally liquid hydrocarbons are then
Therefore, the separating zone may comprise a low-tem
perature ?ash chamber whereby the ammonia, hydrogen
subjected to fractionation to provide a light fraction com
prising the material boiling below about 800° F., which 70 sul?de and light para?nic hydrocarbons are removed as
a gas phase. In any event, the normally liquid hydro
light fraction is combined with the initial light fraction
from the initial stabilizing procedure, thereby forming the
carbons, which may or may not include butanes, sub
stantially completely free from nitrogenous compounds,
charge to the second stage of the process. Those hydro
are utilized as the liquid charge to the third stage of the
carbons which boil above a temperature of about 800° F.
are recycled to combine with the heavy fraction from the 75 present process.
3,026,260
13
1%
The third stage of the present process is designed to
convert the now nitrogen and sulfur free hydrocarbons
boiling within the range of from about 650° F. to about
about 650° F. to about 800° F. are removed from the
bottom portion of the side-cut fractionator, and are re
.
800° F., into hydrocarbons boiling within the gasoline
and middle-distillate boiling ranges. The charge to the
third stage, being the total normally liquid hydrocarbons,
cycled to combine with the normally liquid hydrocarbon
effluent from the second reaction zone, thereby forming
the total liquid charge to the third stage of the present
process. The gasoline boiling range hydrocarbons, re
including butanes, discharging from the second-stage sep
covered from the present process as a liquid product, are
arating means, is admixed with hydrogen in an amount
of from about 1000 to about 6000 standard cubic feet per
virtually completely free from nitrogenous and sulfurous
compounds, and, therefore, are extremely well suited for
barrel of total liquid charge. The quantity of hydrogen, 10 direct utilization as the charge to a catalytic reforming
employed within the ‘third reaction zone, may be less
unit. The middle-distillate liquid product, those hydro
than that required in either of the two preceding zones.
This is due to the physical and chemical characteristics of
the charge stock, whereby such charge stock readily lends
itself to comparatively mild hydrocracking conditions
within the third stage of the process. Therefore, although
carbons boiling within the range of about 400° F. to
about 650° F., contain less than about 5 .0 ppm. of nitro
gen, and more often from about 1.0 to about 3.0 ppm.
This middle-distillate fraction may be subjected to fur
ther processing, for example, in still another ihydrocrack
the third stage may operate acceptably at an imposed pres
ing reaction zone, and due to the physical and chemical
sure within the range of from about 1000 to about 3000
characteristics thereof, under extremely mild hydrocrack
pounds per square inch, excellent results may be achieved
ing conditions whereby there is virtually total recovery
through the utilization of lower pressures, within the 20 therefrom of those hydrocarbons boiling within the gaso
range of from about 500 to about 1500 pounds per square
line boiling range. The middle-distillate hydrocarbon
inch. Similarly, the temperature at which the third re
fraction is also well suited for subsequent utilization as
action zone is maintained, may be signi?cantly less than
fuel oil. During the operation of the three stage process
the temperature in either of the two preceding zones. For
of the present invention, it may be found that the middle
example, as hereinbefore stated, the second reaction zone 25 distillate boiling range hydrocarbons are recovered con
is maintained at a temperature within the range of about
taining more than about 5.0 ppm. of nitrogen. In
500 to about 1000° F. The third reaction zone operates
this event, the heavier hydrocarbons recovered from the
at a temperature at least about 50° F. lower than the
bottom portion of the side-cut fractionator, that is, those
aforesaid range; it is not uncommon, in the process of the
hydrocarbons boiling within the range of about 650° F.
present invention, to permit the third reaction zone to 30 to about 800° F., may be recycled to combine with the
operate at a temperature level as much as 100° F. to
charge to the second-stage, or clean-up reaction zone of
200° F. lower than that in the second reaction zone.
the present process.
Thus, the third reaction zone may be maintained under
From the foregoing description, it is seen that the proc
the relatively mild hydrocracking conditions of from
ess of the present invention will utilize at least two cata
about 400° F. to about 800° F. Similarly, the liquid 35 lytic composites, and three in those instances where the
hourly space velocity through the third reaction zone may
be signi?cantly higher, within the range of from about
?rst reaction zone is designed to function as a hydro
cracking reaction zone. In those instances where the
1.0 to about 10.0.
heavy hydrocarbonaceous material, to be processed with
The catalyst employed within the third reaction zone
in the three stages of the present invention, possesses
compri es at least one metallic component selected from 40 physical and/ or chemical characteristics which warrant
the metals of groups VIA and VHI of the periodic table.
the utilization of a severe hydrocracking reaction zone as
The metallic component of the catalyst utilized within the
third stage of the present process may comprise mix
the ?rst stage, any suitable acidic-type cracking catalyst
may be employed. Generally, suitable hydrocracking
tures of two or more of such metals. Thus, the catalyst
catalysts have been shown to consist essentially of sub
employed in the third reaction zone may consist of chro 45 stantially large quantities of chromium, tungsten, molyb
mium, molybdenum, tungsten, iron, cobalt, nickel, pal
ladium, platinum, ruthenium, rhodium, osmium, iridium,
and mixtures of two or more including nickel-molyb
denum, nickel-chromium, molybdenum-platinum, cobalt
nickel-molybdenum, molybdenum-palladium, chromium
platinum, chromium-palladium, molybdenum-nickel-pal
ladium, etc. The active metallic components are gener
ally employed in an amount of from about 0.01% to
denum, nickel, iron, cobalt, and mixtures thereof. For
example, kieselguhr, composited with about 10% to about
50% by weight of nickel, and preferably, 30% to 50%
by weight, is a suitable catalyst for utilization under
50 severe hydrocracking conditions.
On the other hand, an
acidic carrier material, comprising about 75% by weight
of silica and 25% by Weight of alumina, may be com
posited with about 25% to about 50% by weight of
about 20.0% by weight of the total catalyst. In those
chromium and/ or tungsten. In accordance with the proc
instances Where the hydrocracking catalytic composite in 55 ess of the present invention, it is preferred that the ?rst
the third reaction zone comprises both a group VIII and
reaction zone contain a hydrocracking catalyst compris
‘a group VLA metallic component, these will be present
ing at least one metallic component from the metals of
in a weight ratio, of the group VIII metal to the group
group VIA and the iron-group of the periodic table, and
VIA metal, within the range of from about 0.05:1 to
mixtures thereof. Thus, a preferred catalytic composite
about 5.021. The total e?luent from the hydrocracking 60 of the present invention would comprise a carrier mate
zone is passed into suitable separating means whereby
rial of silica and alumina composited with about 10%
the light para?inic ‘hydrocarbons, and other various gas
eous products are removed. The resulting normally
liquid hydrocarbons are subjected to distillation in a side
to about 50% by weight of nickel, and promoted by lesser
quantities of chromium, tungsten and molybdenum, with
in the range of about 2% to about 20% by weight. In
cut fractionator under such conditions as will yield a 65 any event, the catalytic composite, for utilization in the
heart-cut having a boiling range of about 400° F. to about
?rst reaction zone, may be manufactured by any suitable
650° F., which heart-cut fraction is substantially free
from nitrogenous compounds, containing less than about
5.0 ppm. thereof. Those hydrocarbons boiling below
manner.
A particularly advantageous procedure, from
the standpoint of manufacturing, employs one or more
impregnating techniques. Thus, where the catalyst is to
about 400° F., including butanes, are removed from the 70 contain both nickel and tungsten, the impregnation
upper portion of the side-cut fractionator, and may be
method of preparation involves ?rst preparing the suit
transmitted to storage pending further use either as charge
able carrier material, for example a composite of 75 %
to a catalytic reforming unit, or as gasoline blending
by weight of silica and 25 % by Weight of alumina, and
subsequently forming an aqueous solution of water
components. The comparatively minor quantity of those
soluble compounds of the desired metals, such as nickel
unreacted hydrocarbons boiling within the range of from
3,026,260
15
16
fractory' inorganic oxide material.’ The use of such mate
nitrate, nickel carbonate, tungsten chloride hydrate, etc.
The alumina-silica particles, serving as the acidic carrier
material, are commingled with the aforementioned aque
ous solutions, and subsequently dried at a temperature of
about 200° F. The dried composite is then subsequently
oxidized in an oxidizing atmosphere such as air, for the
purpose of permanently affixing the metallic components
Within and throughout the carrier material. The high
temperature oxidizing procedure is effected at an elevated
temperature of about 1100° F. to about 1700° F., and 10
rial, for example, magnesia, Zirconia, thoria, boria, and
especially silica, even in relatively minor quantities, has
the tendency to increase the hydrocracking activity of the
catalyst, ‘whereby the conversion reactions result in the
unnecessary production of light, straight-chain paraf?nic
hydrocarbons. Therefore, although the catalyst employed
in the ?rst stage of the process utilizes a composite of
alumina and large quantities of silica, the catalyst within
the second stage of the process preferably employs alu
mine. in a substantially pure state. The normally liquid
for a period of from about 2 to about 8 hours or more.
hydrocarbons leaving the second-stage of the present proc
It is understood that the impregnating technique may be
ess, will generally be contaminated with less than about
elfected in any suitable, desired manner; thus, the carrier
10.0 ppm. of nitrogen. Through careful selection of
material may be impregnated ?rst with a nickel-contain
ing solution, dried and oxidized, and thereafter impreg 15 the operating conditions and catalyst within the second
nated with a tungsten-containing solution.
stage, the normally liquid hydrocarbons may be produced
The second
to contain less than about 5.0 parts per million of nitro
gen. In any event, when compared to the quantity of
impregnating step will then be vfollowed by subsequent
drying and high-temperature oxidation procedures. On
nitrogen contained within the original heavy hydrocar
the other hand, the two aqueous solutions may be inti
bonaceous material, the charge stock to the third-stage
mately commingled with each other, and the carrier mate
of the present process may be considered substantially
rial impregnated in a single step. The particular means
completely free from nitrogenous compounds. This is
by which the catalyst, for utilization Within the ?rst stage
due, at least in- part, to the method of concentrating such
of the present process, is prepared, is not considered to
nitrogenous compounds Within a hydrocarbon fraction
be limiting upon the present invention. The primary func
tion, or object, of the ?rst stage of the present process, is 25 boiling below about 800° F., and processing such frac~
tion within the second stage of the present process.
to elfect the substantially complete conversion of those
The third stage of the present process is designed to
hydrocarbons boiling in excess of 800° E, into hydro
convert the now substantially nitrogen-free hydrocarbon
carbons boiling below about 800° F., and this is, in part,
fraction boiling in excess of the middle-distillate boiling
accomplished by means of intra-stage recycle of those
range, into hydrocarbons boiling within both the middle
30
unreacted hydrocarbons boiling in excess of about 800° F.
distillate and gasoline boiling ranges; in addition, the
As hereinbefore set forth, virtually all heavy hydro
utilization of a selective catalyst within the third stage of
carbonaceous material boiling in excess of about 800° F.
the present process will effect substantial conversion of
contains substantial quantities of nitrogenous and sul
the middle-distillate boiling range hydrocarbons into
furous compounds which are di?icult to remove from the
gasoline boiling range hydrocarbons without the usual
higher boiling components. Therefore, as the function of 35 attendant
conversion to light para?inic hydrocarbons
the ?rst stage of the present process is to convert the
such
as
methane,
ethane and propane. In view of the
higher boiling components into material boiling below
fact that the total hydrocarbon charge to this third reac
about 800° F., the function of the second stage of the
tion zone may contain from about 3.0 to about 5 .0 ppm.
present process is to e?iect the substantially complete
of nitrogen, it is to great advantage to utilize certain
destructive removal of those nitrogenous and sulfurous
catalytic composites therein, and which composites are
compounds now boiling below about 800° F. Therefore,
most effective for the mild hydrocracking of hydrocar
the second stage of the present process, referred to as the
bons boiling within the range of 650° to about 800° F.,
clean-up zone, contains a nitrogen-insensitive catalyst
although containing these residual nitrogenous com
comprising at least about 4.0% by Weight of molyb
pounds. By the same token, as hereinabove described,
denum, calculated as the element thereof. The catalyst 45 the catalyst is selected to effect substantial conversion of
may be further promoted by including therein relatively
middle-distillate hydrocarbons into gasoline boiling range
minor quantities of iron-group metals, such as cobalt,
hydrocarbons. To illustrate, alumina, containing rela
nickel and iron.
When these latter metals are utilized
tively minor quantities of silica (approximately 12% by
in conjunction with the large quantities of molybdenum,
weight) possesses a high degree of activity in regard to
the destructive removal of nitrogenous compounds. Like
wise, silica is a good hydrocracking catalyst when con
taining a relatively minor quantity of alumina, while on
they will be employed in an amount within the range of
about 0.2% to about 6.0% by weight thereof. In the
presence of the molybdenum-containing catalyst, and
under the operating conditions hereinbefore set forth, the
the other hand, is not a good nitrogen remover. Sim
organically~bound, nitrogen compounds are separated at
ilarly, the metallic components of the catalyst disposed
55
the nitrogen-hydrogen bonds to ‘form ammonia which is
within the third stage, or hydrocracking reaction zone,
released in a free form from the reaction media. Simi
Will exhibit similar propensities. For example, as indi
larly, any sulfurous compounds, such as mercaptans, thio
cated in regard to the ?rst reaction zone, when the latter
phenes, etc., are converted into hydrogen sul?de and the
contains a suitable hydrocracking catalyst, large quantities
corresponding sulfurafree hydrocarbon. In addition to
the effective clean-up of the hydrocarbon charge stock,
a signi?cant degree of hydrocarbon conversion occurs
whereby the heavier molecular weight hydrocarbons, boil
ing at a temperature within the range of about 650° F. to
60
of nickel exhibit high activity in regard to hydrocrack
ing, but do not possess a relatively high degree of activity
in regard to the removal of nitrogenous compounds. On
the other hand, molybdenum may be considered a good
nitrogen remover, but is not relatively active as either a
about 800° F., are converted, via highly selective crack 65 hydrocracking or hydrogenation catalyst.
ing reactions into hydrocarbons boiling below about
Similarly,
metals selected from the platinum-group of the periodic
650° F. It is understood, however, that such selective
table are considered excellent hydrogenation catalysts,
hydrocracking reactions are not necessarily complete in
and, although effecting hydrocracking to a certain degree,
the sense that all of the hydrocarbons boiling in excess
are not normally considered in the classi?cation of hydro
of 650°
are converted to lower boiling hydrocarbon 70 cracking catalysts. I have found that catalytic com
products. In order to maintain the high degree of selec—
posites which comprise at least one metallic component
I tive cracking, in this second-stage of the present proc
selected from groups VIA and VIII of the periodic table,
ess, it is preferred that the previously mentioned catalytic
and mixtures thereof, including platinum, palladium,
components be composited with a carrier material com
nickel and/or molybdenum, etc., and composited with
prising alumina without the addition thereto of other re 75
3,026,260
17
18
silica and from about 10% to about 90% by weight of
zone, is not considered to be a limiting feature of the
process of the present invention.
As hereinbefore set forth, the carrier material utilized
within the second stage is preferred to be alumina. Since
the primary function of this second stage is the destruc
tive removal of nitrogenous and sulfurous compounds, it
is considered advantageous to limit the conversion reac
alumina, constitute preferred hydrocracking catalysts for
utilization within the third stage of the process of the
present invention. Such catalysts have a relatively high
degree of activity in regard to the conversion of hydro
carbons boiling Within the middle-distillate boiling range,
and, more importantly, effect the substantially complete
conversion of those hydrocarbons boiling Within the
tions in a manner such that little or no light para?inic
range of 650° F. to about 800° F. It is signi?cant that
hydrocarbons are produced. The alumina may be pre
such activity is substantially unaffected even by the rela 10 pared by adding a reagent such as ammonium hydroxide,
tively minor quantities of nitrogen, less than about 5.0
ppm. contained within the charge to the third-stage re
action zone.
ammonium carbonate, etc., to a salt of aluminum such as
aluminum chloride, aluminum nitrate, aluminum acetate,
etc., in an amount to form aluminum hydroxide. Alu
The carrier material, for utilization within the cat
alyst employed in the ?rst stage of the present process, 15 minum chloride is generally preferred as the aluminum
salt to be employed, not only for convenience in sub
unless of course such stage comprises a thermal cracking
sequent washing and ?ltering procedures, but also it ap
unit of the single-coil or double-coil type, may be alumina,
pears to give the best results. The resulting precipitate
magnesia, fuller’s earth, montmorillonite, silica, kiesel
is, upon drying, converted to alumina. The alumina par
guhr, etc. A suitable carrier material may consist, for
example, of a major proportion of precipitated silica com 20 ticles may take the form of any desired shape such as
posited with one or more hydrated oxides such as hy
spheres, pills, pellets, cakes, extrudates, powder, gran
drated alumina, hydrated zirconia, and hydrated thoria.
ules, etc. A particularly preferred form of alumina is
the sphere, and these spheres may be continuously manu
factured by passing droplets of an alumina hydrosol into
When synthetically-produced, the solid carrier material
may be made in any suitable manner including separate,
successive or coprecipitation methods. For example,
silica may be prepared by commingling Water glass and
a mineral acid under such conditions as will precipitate
a silica hydrogel.
The silica hydrogel is subsequently
washed with Water containing a small amount of a suit
an oil bath which is maintained at an elevated tempera
ture, and retaining the droplets in said oil bath until the
same set into ?rm hydrogel spheroids. This particular
method, commonly referred to as the oil-drop method,
is described in detail in U.S. Patent No. 2,620,314, issued
able electrolyte for the purpose of removing sodium 30 to James Hoekstra.
ions.
The oxides of other compounds, when desired,
With respect to the carrier material employed as a
may be prepared by reacting a basic reagent such as am
part of the catalyst disposed Within the [third reaction
monium hydroxide, ammonium carbonate, etc., with an
zone, it is preferred to utilize at least tWo refractory in
acid salt solution of the metal, as for example, the chlo
organic oxides, and preferably alumina and silica. When
ride, sulfate, nitrate, etc., or by adding an acid to an 35 silica and alumina are employed in combination, the lat
alkaline salt of the metal such as, for example, commin
ter will be present within an amount of from about 10%
gling sulfuric acid with sodium aluminate, etc. When
to
about 90% by Weight. Thus, the carrier material
it is advantageous to prepare the carrier material in the
within the third-stage of the present process may com
form of particles of uniform size and shape, this may be
readily accomplished by grinding the partially dried oxide
cake, with a suitable lubricant such as stearic acid, resin,
graphite, etc., subsequently forming the particles in any
prise the following: 88% by weight of silica and 12% by
Weight of alumina, 75% by weight of silica and 25% by
weight of alumina, 88% by weight of alumina and 12%
by weight of silica. Following the formation of the
suitable pelleting or extrusion apparatus. The preferred
carrier material, the catalytically active metallic com
carrier material, for utilization in the ?rst stage of the
present invention, comprises at least two refractory in 45 ponents are composited therewith. The catalyst com
prises at least one metallic component selected from the
organic oxides, and such a composite may be prepared
metals of groups VIA and VIII of the periodic table, and
by the separate precipitation method, in which the oxides
are precipitated separately, and then mixed, preferably
includes the platinum-group metals, the iron-group
metals, molybdenum, tungsten, and chromium. These
in the wet state; when successive precipitation methods
are employed, the ?rst oxide is precipitated as previously 50 metallic components may be incorporated within the
set forth, and the wet slurry, either with or without prior
alumina-silica carrier material in any suitable manner.
impregnating techniques may be advantageously em
washing, is composited with a salt of the other component.
Thus, a precipitated, hydrated silica, substantially alkaline
ployed by ?rst forming an aqueous solution of a water
free, is suspended in an aqueous solution of aluminum
soluble compound of the desired metal such as platinum
chloride and zirconium chloride following which precipi 55 chloride, palladium chloride, chloroplatinic acid, chloro
tated hydrated alumina and precipitated hydrated zirconia
palladic acid, ammonia molybdate, nickel nitrate hexa
are deposited upon the silica gel by the addition of an
alkaline precipitant, such as ammonium hydroxide. The
resulting mass of hydrated oxide is water washed, dried
and calcined at about 1400° F. Another possible method 60
of manufacture consists of commingling an acid such as
hydrate, tungsten chloride, dinitrito-diamino platinum,
etc., and commingling the resulting solution with the
alumina-silica in a steam drier.
Other suitable metal
containing solutions which may be employed are colloidal
solutions or suspensions including the desired metal cy
hydrochloric acid, sulfuric acid, etc., with commercial
water glass under conditions to precipitate silica, washing
anides, metal hydrom'des, metal oxides, metal sul?des,
ponent may be formed by adding the aluminum and/or
zirconium salts together or separately. It is understood
that the particular means employed for the manufacture
of the hydrocracking catalyst, utilized in the ?rst reaction 75
Following the high-temperature oxidation procedure, the
etc. Where these solutions are not water-soluble at the
the precipitate with acidulated water or other means to
temperature employed, other suitable solvents such as
remove sodium ions, commingling with an aluminum salt 65 alcohols, ethers, etc., may be utilized. The ?nal cata
such as aluminum chloride, and/or some suitable zir
lytic composite, after all of the catalytic components are
conium salt, etc., and either adding a basic precipitant
present therein, is dried for a period of from about 2 to
such as ammonium hydroxide to precipitate alumina
about 8 hours or more, and subsequently oxidized in an
and/or zirconia, or forming the desired oxide or oxides
oxidizing atmosphere such as ‘air, at an elevated tem
through the thermal decomposition of the salt as the case 70 perature of about 1100° F. to about 1700° F., and for a
may permit. The silica-alumina-zirconia cracking com
period of from about one to about eight hours or more.
catalyst may be reduced for a period ranging from about
1/2 hour to about 1 hour in the presence of hydrogen, at a
temperature within the range of about 700° F. to about
3,026,260
19
20
stantial reduction in the quantity of light paraf?nic hydro
1000° F. Where convenient, the catalyst may be reduced
in situ, that is, by placing the catalyst within the third
carbons otherwise resulting from the non-selective single
stage hydrocracking of similar heavy hydro'carbonaceous
reaction zone, subjecting the same to an imposed hydro
gen purge of the system at a temperature of about 700° F.
The total quantity of metallic components of the cata
material. Furthermore, the process of the present in
vention results in a gasoline boiling range hydrocarbon
product substantially free from unsaturated paraf?nic hy
drocarbons; the gasoline boiling range product is, there
lyst disposed within the third reaction zone, is within the
range of from about 0.01% to about 20.0% by weight
fore, extremely well suited as charge stock to a catalytic
reforming unit for the purpose of further increasing the
within the range of from about 0.5% to about 10.0% by 10 octane rating thereof. Thus, through the utilization of
the process of the present invention, a hydrocarbon charge
weight of the catalyst. The group VIII metals, which
of the total catalyst.
The group VIA metal, such as
chromium, molybdenum, or tungsten, is usually present
stock, having a boiling range of from about 700° F. to
about 1000” F. or higher, may be substantially completely
amount of from about 0.01% to about 10.0% by weight
converted into hydrocarbons boiling within the gasoline
of the total catalyst. When an iron sub-group metal,
such as iron, cobalt, or nickel, is employed, it is present 15 boiling range, notwithstanding the presence of exceedingly
excessive quantities of nitrogenous and sulfurous com
in an amount of from about 0.2% to about 10.0% by
pounds. Furthermore, these high volumetric yields are
weight, while, if a platinum-group metal such as plat
may be divided into two sub-groups, are present in an
obtained Without the usual exceedingly high yield loss
inum, palladium, iridium, etc., is employed, it is present
in an amount within the range of from about 0.01% to
due to the formation of an excessive quantity of light
it will contain metals of the above groups in a ratio of
from about 0.05:1 to about 5.0:1 of the group VIH
either a batch or a continuous-type operation.
third reaction zone, include, but are not considered to be
in their respective reaction zones, as ?xed beds, as il
about 5.0% by weight of the total catalyst. When the 20 paraf?nic hydrocarbons, and without experiencing the
rapid deactivation of the catalytic composite employed.
metallic component of the hydrocracking catalyst con
The process of the present invention may comprise
sists of both a group VIA metal and a ‘group VIII metal,
When
utilizing the continuous-type operation, which is the par
metal component to the group VIA metallic component. 25 ticularly preferred manner of e?ecting the present in
vention, the various catalytic composites may be disposed,
Therefore suitable catalysts for utilization within the
lustrated in the accompanying drawing, and maintained
under the desired operating conditions. The hydrocar
limited to, the following: 6.0% by weight of nickel and
0.2% by weight of molybdenum; 6.0% by weight of
nickel and 0.2% by weight of platinum; 0.4% by weight
of platinum; 6.0% by weight of nickel and 0.2% by
weight of palladium; 0.4% by weight of palladium, etc.
30 bons, and hydrogen, are continuously charged to the re
action zone, passing in downward ?ow through the cata
lyst, or, Where desired, either in upward ?ow or radial
?ow. The operation may be eifected as a moving-bed
type, or a suspensoid-type of operation, in which the
The catalyst employed within the third stage of the
process of the present invention is preferably disposed
within the reaction zone as a ?xed bed.
As a result of 35 catalyst and hydrocarbons are passed as a slurry through
the reaction zone.
the physical and chemical characteristics of the charge
The following examples are given to further illustrate
the process of the present invention, and to indicate the
bene?ts to be afforded through the utilization thereof.
ture at which the catalyst is maintained may be at least
about 50° F. less than the temperature employed within 40 It is understood that the examples are given for the sole
purpose of illustration, and are not intended to limit the
the second reaction zone. It is not unusual, in the process
generally broad scope and spirit of the appended claims.
of the present invention, to operate the third reaction
stock to the third stage, the operating conditions therein
are relatively mild. For example, the operating tempera
zone at a temperature which is as much as 150° F. lower
than the temperature within the second reaction zone.
Furthermore, there exists the requirement for a lesser 4.5
quantity of hydrogen within the third stage, and the
rate of liquid charge thereto may be substantially in
creased. The total e?tluent from the hydrocracking re
action zone may be passed to a suitable high-pressure,
low-temperature separation zone, from which a hydrogen
rich gas stream is withdrawn and recycled to supply at
least a portion of the hydrogen which is admixed with
the liquid hydrocarbon charge stock. It is understood
that the broad scope of the present invention is not to
be unduly limited to a particular catalyst, or to a par
ticular method of manufacturing the same. The utiliza
tion of any of the previously mentioned catalytic com
posites, whether in the ?rst, second or third reaction
zones, at operating conditions which vary within the
55
EXAMPLE I
A Mid-Continent vacuum gas oil, having a boiling
range indicating an initial boiling point of about 600° F.
and a 95% distillation point (ASTM Method D-86) of
950° F., the latter indicating an end point of about 1000°
F., was subjected to processing in accordance with the
description of the second-stage of the present process.
The gas oil was contaminated by 252 ppm. of nitrogen,
and contained 0.35% by weight of sulfur. The catalyst
employed consisted of an alumina-silica carrier material,
comprising 88% by weight of alumina, impregnated with
a single impregnating solution containing molybdic acid
and nickel nitrate hexahydrate in amounts to yield a ?nal
catalyst containing 6.4% by weight of molybdenum and
2.4% by Weight of nickel. The catalyst was maintained
at a temperature of 750° F., a pressure of 1500 pounds
limits hereinbefore set forth, do not necessarily yield 60 per square inch, and the liquid charge rate was equivalent
results which are equivalent to those obtained through
to 0.3 liquid hourly space velocity, in the presence of
the utilization of other catalytic composites or other
4500 standard cubic feet per barrel of hydrogen. Under
operating conditions. An essential feature of the present
these conditions, the normally liquid hydrocarbon product
invention is the separate, distinctly integrated three stages
contained nitrogen in an amount of 21 ppm.
within which the overall process is effected. Through the 65
To illustrate the function of the ?rst stage of the
utilization of the process of the present invention, greater
present process, whether utilizing a severe hydrocracking
concentrations of hydrocarbons boiling within the gaso
reaction zone, or a thermal cracking reaction zone, a Mid
line and middle-distillate boiling ranges are produced
Continent gas oil, containing no hydrocarbons boiling in
from those hydrocarbons which boil in excess of the 70 excess of 800° F., was processed in a like manner, again
middle-distillate boiling range. Furthermore, greater con
simulating the second-stage of the present process. The
centrations of gasoline boiling range hydrocarbons may
gas oil was contaminated with total nitrogen in an amount
be produced from those middle-distillate boiling range
of 252 ppm. and total sulfur in an amount of 0.35%
hydrocarbons withdrawn as a product from the third stage
by weight. These and other charge stock inspections
pf the process. The overall picture results in a. sub 75 are given in the following Table I.
3,026,260
22
Table 1
MID-CONTINEN’I‘
GAS OIL—CHARGE
PROPERTIES
AND
PRODUCT
90%
650
End point
688
Percent @ 400° F _____________________ __
Percent @ 650° F. ____________________ __
Charge
Product
45.0
90.0
5
Product distribution:1
Gravity, ° API @ 60° F _________________________ __
ASTM, 13-86 Distillation, ° F.:
IBP
Percent @ 650° F _____________ -_
32. 3
Butanes—
41. 0
180°
180°
400°
650°
536
11.8
46.1
40.3
8.9
Total volumetric yield _______________ .._ 107.1
.
Total Nitrogen, wt. ppm ........ __
Total Sulfur, Wt. Percent ________________________ __
F., E.P ______________________ __
F.-400° F., E.P. _____________ __
F.-650° F., E.P. _____________ __
F. and heavier _______________ __
1 C1-C3 light para?'inic hydrocarbons:1.64 wt. percent.
0.99
15
Product Distribution:l
Butanes
180° R, ER, vol. percent _______________ __
180° F.-400° F., E.P., vol. percent _______ __
As previously stated in regard to Example I, the indi
cated product distribution accounts for those butanes
inadvertently removed from the total reaction zone e?lu
ent while separating the light paraiiinic hydrocarbons
therefrom. The product distribution is, however, based
400° F.—650° F., E.P., vol. percent
650° F. and Heavier, vol. percent ________ __
20 upon an overall material balance of 99.9%.
Total Volumetric Yield ___________ __
It is again
signi?cant that the total light parai?nic hydrocarbon yield
was less than about 2.0% by weight of the total liquid
charge. In addition, the total volumetric yield was
signi?cantly in excess of 100%. Of greater signi?cance,
is the fact that only 8.9 volume percent of the total
liquid charge to the third stage of the present process
1 01-0; Light Para?inic Hydrocarbons=L80 wt. percent.
The total liquid product ef?uent, including butanes,
had a nitrogen content of slightly less than 1.0 ppm.
and a total sulfur content of 0.022 Wt. percent. These
data indicate that the nitrogenous and sulfurous com
was unreacted. As indicated in the product distribution,
pounds may be effectively completely removed from those
hydrocarbons boiling at a temperature less than about
800° F., whereas, these compounds, particularly the
there resulted 57.9% by weight of gasoline boiling range
hydrocarbons and 40.3% by volume of middle-distillate
nitrogenous compounds, are di?’icult to remove from 30 boiling range hydrocarbons.
The foregoing examples clearly indicate the method of
those hydrocarbon fractions boiling in excess of 800°
the present invention and the various bene?ts to be af
F. In addition to the rather effective clean-up of the
forded through the utilization thereof. The three-stage
charge to the second reaction zone, there is evidence of a
process of the present invention has been shown to result
considerable amount of selective hydrocracking taking
place as shown by the shift in boiling range. The prod 35 in exceedingly large volumetric yields of gasoline boiling
range hydrocarbons and middle-distillate hydrocarbons
uct distribution, as indicated in Table I, was obtained
while processing heavy hydrocarbonaceous material sev
by precise laboratory fractionation in a 30-plate distilla
crly contaminated by excessive quantities of both nitro
tion column, and includes the butanes removed along with
genous and sulfurous compounds.
the light para?inic hydrocarbons prior to the laboratory
distillation. It is signi?cant that the light para?inic hy 40 I claim as my invention:
1. A process for the conversion of hydrocarbon oil
drocarbon yield was less than 2.0% by weight of the
containing nitrogenous compounds and hydrocarbons boil
total charge, and that the total volumetric yield was in
ing above about 800° R, which comprises cracking said
excess of 100%.
oil to form hydrocarbons heavier than gasoline and boil
EXAMPLE H
ing below about 800° F., reacting the last-named hydro
The charge stock employed in this example (illustrat
carbons with hydrogen to convert nitrogenous compounds
ing the third stage), was the liquid hydrocarbon product
therein to ammonia, separating the ammonia from nor
resulting from the Mid-Continent gas oil utilized in Ex
mally liquid hydrocarbons, and hydrocracking at least
ample I (illustrating the operation of the second-stage
a portion of the latter in the presence of hydrogen and
of the process). The catalyst employed in this example
a hydrocracking catalyst.
50
consisted of a carrier material of 88% by weight of
2. A process for converting hydrocarbonaceous mate
silica and 12% by weight of alumina, impregnated with
rial containing nitrogenous compounds and hydrocar
sut?cient palladium chloride to result in a ?nal composite
bons boiling in the range of from about 700° F. to
containing 0.4% by weight of palladium. The operating
about 1000° E, into lower boiling hydrocarbon prod
conditions were, a pressure of 1500 pounds per square
ucts, which comprises cracking said hydrocarbonaceous
inch, a temperature of 575° F., a liquid hourly space 55 material in a ?rst reaction zone, removing light paraf
velocity of 1.0 and a hydrogen rate of 3000 standard
?nic hydrocarbons from the resultant e?luent, and there
,cubic feet per barrel of liquid charge. It should be noted
after separating the remaining normally liquid hydro
that these operating conditions are comparatively mild
carbons into a heavy fraction having an initial boiling
with respect to those normally encountered in single
point in excess of a temperature of about 800° F. and
stage hydrocracking processes. The product properties, 60 a light fraction heavier than gasoline and boiling below
and the product distribution, obtained on the total liquid
about 800° F., recycling said heavy fraction to combine
hydrocarbon e?iuent resulting from this simulation of
with said hydrocarbonaceous material; reacting said light
the third-stage of the present process, are indicated in
fraction with hydrogen in a second reaction zone to con
following Table 11.
65 vert nitrogenous compounds therein to ammonia, re
Table II
moving ammonia and normally gaseous hydrocarbons
MILD HYDROCRACKING, MID-CONTINENT GAS OIL
PRODUCT PROPERTIES
from the resultant second zone e?iuent, and passing
Gravity, ° API @ 60° F. __________________ ....
tional hydrogen, into a third reaction zone maintained at
156
70 hydrocracking conditions; removing normally gaseous
hydrocarbons from the resultant third zone e?luent and
ASTM, D-86 distillation, ° F.:
IBP
‘10%
30%
50%
70%
__._
the normally liquid ‘hydrocarbons, along with addi
49.1
220
305
445
560 75
separating the normally liquid hydrocarbons into a ?rst
fraction having an end boiling point of about 400° F. to
about 450° F., a second traction having an initial boil
ing point of about 400° F. to about 450° F. and an
8,026,260
23
'24
end boiling point of about 650° F. to about 700° F., and
that said platinum-group metallic component is pal
a third fraction boiling at a temperature in excess of
ladium.
11. The catalyst of claim 9 further characterized in
about 650° F. to about 700° F., and recycling at least
a portion of said third fraction to combine with said
hydrogen and the normally liquid hydrocarbons from
said second reaction zone, prior to conversion thereof in
said third reaction zone.
_
3. The process of claim 2 further characterized in
that said platinum-group metallic component is platinum.
12. A process for converting nitrogen-contaminated
hydrocarbonaceous material, having a boiling range of
from about 700° F. to about 1000° F., into lower boil
ing hyrocarbon products substantially free from nitro
genous compounds, which comprises initially stabilizing
that said hydrocarbonaceous material is initially sta
bilized to produce a light fraction having an end boiling 10 said hydrocarbonaceous material to produce a ?rst light
fraction containing those hydrocarbons boiling below
point below about 800° F., and a heavier fraction having
about 800° F., and a ?rst heavy fraction having an initial
an initial boiling point of about 800° F., said heavier
boiling point of about 800° F; cracking said ?rst heavy
fraction passing into said ?rst reaction zone.
fraction in a ?rst reaction zone containing a cracking
4. The process of claim 2 further characterized in
that said ?rst reaction zone is maintained at thermal 15 catalyst comprising at least one metallic component from
the metals of groups VIA and the iron-group of the pe
cracking conditions.
riodic table, and mixtures thereof, separating the re
5. The process of claim 2 further characterized in
sultant et?uent into a second light fraction comprising
that said ?rst reaction zone contains a hydrocracking
hydrocarbons heavier than gasoline and boiling below
catalyst comprising at least one metallic component
about 800° F. and a second heavy fraction containing
from the metals of groups VIA and the iron-group of
about 1000° F., and containing nitrogenous compounds,
hydrocarbons boiling in excess of a temperature of about
800° F., recycling the second heavy fraction to com
bine with said ?rst heavy fraction prior to the conversion
thereof in said ?rst reaction zone, and combining said
prises initially fractionating said hydrocarbonaceous ma
acting the resulting light fraction mixture with hydrogen
the periodic table, and mixtures thereof.
_
6. A process for converting hydrocarbonaceous mate‘
rial having a boiling range of from about 700° F. to
into lower boiling hydrocarbon products which com 25 second light fraction with said ?rst light fraction; re
in a second reaction zone containing a catalyst compris
terial to produce a ?rst light fraction containing those
ing from about 4% to about 45% by weight of molyb
hydrocarbons boiling below about 800° F., and a ?rst
denum to convert nitrogenous compounds therein to
heavy fraction having an initial boiling point of about
800° F., cracking said ?rst heavy fraction in a ?rst re 30 ammonia, removing ammonia and normally gaseous
hydrocarbons from the resultant second zone e?luent,
action zone, separating the resultant e?luent into a second
and passing the normally liquid hydrocarbons, along with
light fraction and a second heavy fraction, the former
additional hydrogen, into a third reaction zone main
tained at hydrocracking conditions and containing a
boiling point of about 800° F., recycling said second 35 catalyst comprising from about 0.01% to about 5.0%
comprising hydrocarbons heavier than gasoline and boil
ing below about 800° F. and the latter having an initial
heavy fraction to combine with said ?rst heavy fraction
by weight of platinum composited with silica and from
about 10% to about 90% by weight of alumina; re
moving normally gaseous hydrocarbons from the re
bining said second light fraction with said ?rst light
fraction; reacting the resultant light fraction mixture 40 sultant third zone e?luent and separating the normally
liquid hydrocarbons into a ?rst fraction having an end
with hydrogen in a second reaction zone to convert nitrog
boiling point of about 400° F. to about 450° F., a second
enous compounds therein to ammonia, removing am
fraction having an initial boiling point of about 400° F.
monia and normally gaseous hydrocarbons from the
to about 450° F. and an end boiling point of about 650°
resultant second zone e?iuent, and passing the normally
prior to conversion in said ?rst reaction zone, and com
F. to about 700° F., and a third fraction boiling at a
liquid hydrocarbons, along with additional hydrogen,
into a third reaction zone maintained at hydrocracking 45 temperature in excess of about 650° F. to about 700°
F., recycling at least a portion of said third fraction
conditions; removing normally gaseous hydrocarbons
to combine with the normally liquid hydrocarbons from
from the third reaction zone e?‘luent and separating the
said second reaction zone and hydrogen, prior to con
normally liquid hydrocarbons into a ?rst fraction hav
version thereof in said third reaction zone.
ing an end boiling point of about 400° F. to about 450°
13. The process of claim 12 further characterized in
F., a second fraction having an initial boiling point of 50
that said second reaction zone is maintained at a tem
about 400° F. to about 450° F. and an end boiling point
perature within the range of from about 500° F. to about
of about 650° F. to about 700° F., and a third fraction
1000° F. and said third reaction zone is maintained at
boiling at a temperature in excess of about 650° F. to
a temperature at least about 50° F. lower than the tem
about 700° F., recycling at least a portion of said third
fraction to combine with the normally liquid hydro 55 perature in said second reaction zone.
14. A process for converting nitrogen-contaminated
carbons from said second reaction zone and hydrogen,
hydrocarbonaceous material, having a boiling range of
prior to conversion thereof in said third reaction zone.
from about 700° F. to about 1000° F., into lower boil
7. The process of claim 6 further characterized in that
ing hydrocarbon products, substantially free from nitrog
said third reaction zone contains a catalyst comprising
at least one metallic component selected from the metals 60 enous compounds, which comprises initially stabilizing
said hydrocarbonaceous material to produce a ?rst light
of groups VIA and VIII of the periodic table, and mix
tures thereof.
fraction containing those hydrocarbons boiling below
.
8. The process of claim 6 further characterized in that
about 800° F., and a ?rst heavy fraction having an
initial boiling point of about 800° F.; cracking said ?rst
said third reaction zone contains a catalyst comprising a
65 heavy fraction in a ?rst reaction zone, separating the
group VIA and a group VIII metallic component, the
resultant effluent into a second light fraction compris
ratio of said group VIII metallic component to said
group VIA metallic component being within the range
of about 0.05:1 to about 57.021.
9. The process of claim 6 further characterized in
that said third reaction zone contains a catalyst compris
ing at least one platinum-group metallic component com
posited with silica and from about 10% to about 90%
by weight of alumina.
,
.
.
ing hydrocarbons heavier than gasoline and boiling be
low about 800° F. and a second heavy fraction contain
ing hydrocarbons boiling in excess of a temperature of
about 800° F., recycling the second heavy fraction to
combine with said ?rst heavy fraction prior to the crack
ing thereof in said ?rst reaction zone, and combining
said second light fraction with said ?rst light fraction;
10. The catalyst of claim 9 further characterized in 75 reacting the resulting‘ light fraction'mixture with hydro
m
a
3,026,260
25
26
gen in a second reaction zone containing a catalyst com
F. and said third reaction zone is maintained at a tem
prising alumina, from about 4% to about 45% by weight
of molybdenum to convert nitrogenous compounds there
ture in said second reaction zone.
in to ammonia, and from about 0.2% to about 6% by
perature at least about 50° F. lower than the tempera
weight of nickel; removing ammonia and normally gase
15. The process of claim 1 further characterized in
that said hydrocarbon oil has a boiling range of from
ous hydrocarbons from the resultant second zone e?iu
about 700° F. to about 1000° F.
ent, and passing the normally liquid hydrocarbons, along
with additional hydrogen, into a third reaction zone main
tained at hydrocracking conditions and containing a cata
16. The process of claim 1 further characterized in
that said oil is thermally cracked.
17. A process for the conversion of hydrocarbon oil
lyst comprising from about 0.01% to about 5.0% by
weight of palladium composited with silica and from
about 10% to about 90% by weight of alumina; remov
ing normally gaseous hydrocarbons from the resultant
third zone e?iuent and separating the normally liquid
boiling above and below about 800° R, which comprises
separating said oil into a light fraction boiling below
containing nitrogenous compounds and hydrocarbons
about 800° F. and a heavy fraction boiling above about
800° F., cracking said heavy fraction to form additional
hydrocarbons into a ?rst fraction having an end boiling 15 hydrocarbons heavier than gasoline and boiling below
point of about 400° F. to about 450° F., a second frac
about 800° R, combining the last-named hydrocarbons
tion having an initial boiling point of about 400° F.
with said light fraction, reacting the resultant mixture
to about 450° F. and an end boiling point of about
with hydrogen to convert nitrogenous compounds there
650° F. to about 700° F., and a third fraction having an
in to ammonia, separating the ammonia from normally
initial boiling point in excess of a temperature of about
liquid hydrocarbons, and hydrocracking at least a por
650° F. to about 700° F., recycling at least a portion
tion of the latter in the presence of hydrogen and a hy
of said third fraction to combine with the normally
drocracking catalyst.
liquid hydrocarbons from said second reaction zone and
hydrogen, prior to conversion thereof in said third re
References Cited in the ?le of this patent
action zone; the process further characterized in that 25
UNITED STATES PATENTS
said second reaction zone is maintained at a temperature
within the range of from about 500° F. to about 1000°
2,885,346
Kearby et a1. ________ __ May 5, 1959
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