Note: Descriptions are shown in the official language in which they were submitted.
5~
The ilydrotreating of hydrocarbon or hydrocarbonaceous feedstocks,
including particularly heavy petroleum crudes and residua, is not new. In the
~ast, the lower molecular weight or gas oil portion of such feedstocks has been
catalytically converted and upgraded to high value fuels, while the heavy ends
or 1050 F.+ materials were split out, then generally used as low grade fuel or
as asphaltic materials. The 1050 F.+ material, often termed "the bottom of the
barrel," is of low commercial value, even less than an equivalent quantity of
raw crude.
Other related applications which describe new and improved
catalysts, and hydroconversion processes, or processes for cracking the 1050 F.+
hydrocarbon portion of heavy whole crudes and residua to yield therefrom
lighter boiling usable products, particularly from unconventional heavy crudes
and residua which contain appreciable amounts of sulfur and nitrogen, high
quantities of the so-called heavy metals, e.g., nic~el and vanadium, as well as
high "ConOcarbon," high carbon-to-hydrogen ratios, high asphaltenes, ash, sand,
scale and the like, are applications Nos. 219,484, 21~,496, 219,552 and 219,553
filed February 6, 1975.
Processes for the conversion of feeds containing 1050~.+
hydrocarbon materials to lower molecular weight hydrocarbons are known. For
exampley in one such known process, a hydrocarbon feed and gas are passed up-
wardly through an ebullating bed of particulate catalyt1c solids. The process
is thus conducted under conditions which establish a random motion of the
catalytic particles in the liquid without carrying the solids out of the reactor.
Based on the solid si~e and density of the catalyst particles, and liquid
density, velocity and viscosity, the mass of particulate solids is expanded
from about 10 pe~cent greater volume than the settled state of the mass to
perhaps two or three times the settled volume. While such process has been
found useful in the treatment of such feeds, it too has its limitations.
~' "
Thus, there are certain disadvantages associated with the activity of the
catalysts used in such process.
It is thus particularly difficult to treat crudes or residuas
which contain large amounts of 1050~.~ hydrocarbons and the hydroconversion
of 1050F.+ hydrocarbon materials to lower boiling and more useful hydrocarbons
presents an acutely difficult problem.
Supply and demand considerations, nonetheless, make it imperative
that new and improved methods be developed for the hydroconversion of new types
of heavy crudes and residua which contain great amounts of the 1050F.+ materials
which crudes and residua cannot be handled by present hydroconversion processes.
These so-called heavy crudes are different from conventional crudes in at least
four important aspects, each of which makes hydroconversion of such crudes by
present methods entirely unfeasible - viz., they have (1) very high Conradson
carbon (i.e., "Con. carbon") or carbon to hydrogen ratios (i.e., relatively
high carbon and low hydrogen content), (2) very high metals content, parti-
cularly as regards the amount o nickel and vanadium, (3) they are ultra-high
in their content of materials boiling above 1050~., e.g., asphaltenes~ and
even (4) contàin considerable amounts of sand and scale. Properties which
readily distinguish these new materials from conventional crudes are thus:
high metals, high asphaltenes, high carbon:hydrogen ratios, and a high volume
percent of hydrocarbons boiling above 1050~. The presence of the greater
amounts of metals and the higher carbon content of the heavy crudes9 in parti-
cular, makes any considerations regarding the processing of these materials most
difficult and expensive. The high "Con. carbon" and carbon:hydrogen ratios are
considerably higher than those o~ any presently usable hydrocarbon liquids.
It is an object of the present invention to provide new and
improved catalysts, particularly useful in hydrocarbon conversion reactions,
particularly reactions involving the hydroconversion of the 1050F.~ hydrocarbon --
portion of heavy crudes and residua.
~ 2 -
,. . . ~. ' ~ ' ~ :
A further object is to supply new and improved methods for the
preparation of such catalysts.
Another object is to provide a new and improved hydrocarbon
conversion process, or hydroconversion process useful in converting the 1050 F.+
hydrocarbon portion of feeds comprising heavy crudes and residua -to useful lower
boiling products while simultaneously producing appreciable Con. carbon reduction,
hydrodesulfuri~ation, hydrodenitrogenation and demetallization of the feeds.
These obJects and others are achieved in accordance with the
present invention which embodies
(a) novel catalysts which, although they possess certain common
characteristics 9 are of two distinct types as relates to an essential combina-
tion of properties regarding pore size ~or pore si~e distribution~, surface
area and pore volume, this enabling each to perform its function in a unique
manner, a first catalyst providing enhanced selectivity for conversion and
demetallization of whole heavy crudes and residua, in the presence of added
hydrogen, which contains relatively large quantities of 1050F.+ materials,
i.e., asphaltenes (C5 insoluble) and other large hydrocarbon molecules, which
are effectively converted to lower molecular weight products, and a second
catalyst particularly suitable for the efficient conversion, demetalli~ation
20 ~ and Con. carbon reduction of hydrocarbon materials, particularly of a feed of `
character similar to the product resultant from a hydroconversion process
utilizing said first catalyst. Conversion, as used herein, thus requires
chemical alteration of the 1050F.~ hydrocarbon molecules to form lower mole~
cular ~eight molecules boilin~ below 1050F. (i.e., 1050F.-) and it is measured
by the weight decrease in the amount of 1050F.~ hydrocarbons contained in the
original feed times I00, divided by the amount of 1050F.+ material originally
present in the feed. These catalysts in common comprise catalytically active
amounts of a hydrogenation component which includes a Group ~7IB or Group ~III
-- 3 --
,~ ".
- . - : . : i.: . . : : , .: - -
. . ~ .
'.
,. . ' ' ' ' ~ '. ' ' ',
~s~
metal (especially, a Group VIII nonnoble metal), or both (Periodic Table of
the Elements, E.H. Sargent and Co., Copyright 1962 Dyna-Slide Co.), particularly
molybdenum or tungsten of Group VIB, and cobalt or nickel of Group VIII, and
preferably a Group VI~ and Group VIII metal in admixture one metal with the
o~her, or with other metals, or both, particularly Group I~ metals, composited
with a refractory inorganic sup~ort, notably a porous, inorganic oxide support,
particularly alumina, or more particularly gamma alumina,
(i) said first catalyst, hereinafter termed "R-l"
catalyst for convenience, including a combination of
properties comprising, when the catalyst is of size
ranging up to 1/50 inch average particle size diameter,
at least about 20 percent, preferably at least about
25 percent, and more preferably a~ least about 70 percent
of its total pore volume of absolute diameter within the
the range of about 100~ (Angstrom units) to about 200~;
when the catalyst is of size ranging from about 1/50 inch
up to 1/25 inch a~erage particle size diameter, at least
about 15 percent, preferably at least about 20 percent,
and more preferably at least about 45 percent of its total
pore volume of absolute diameter within the range of about
15 ~ to about 250~; when the catalyst is of size ranging
from about 1/25 inch to about 1/8 inch average particle size
diameter, at least about 15 percent, preferably at least
about 20 percent, and more preferably at least about 30 per
cent of its total pore volume of absolute diameter within
the range of about 175~ to about 275~, wherein, in each o~
these catalysts of differing ranges of particle size distri-
butions, the pore ~olumes resultant from pores of 50~, and
~. : ,.. . . ..... . .
- . . , ~,
, ~
~5~
smaller, i.e., 50~-, are ininimized; and preferably, while
in catalyst average particle size below 1/50 inch, the pore
volume resultant from pores of diameter above 300~, i.e.,
300~+, is minimized9 and in catalysts of average particle
size above 1/50 inch, the pore volume resultant from pores
above 350~, i.e., 350~+, is minimized; the surface areas and
pore volumes of the catalysts being interrelated with particle
size, and pore size distributions, surface areas ranging at
least about 200 m2/g to about 600 m2/g, and preferably at
least about 250 m2/g to about 450 m /g, with pore volumes
ranging from about 0.8~to about 3.0 cc/g, and preferably
from about 1.1 to about 2.3 cc/g (B.E.T.):
(ii) said second catalyst, hereinafter termed "R-2"
catalyst for conyenience, over the spectrum of particle
sizes ranging to l/8 inch average particle size diameter,
is one including a combination of properties comprising at
least about 55 percent, and preferably at least about 70 per-
cent of its total pore volume of absolute diameter within the
range of about 100~ to about 200~; less than 10 percent,
preferably less than 1 percent of the pore volume results
from pores of diameters 50~~; less than about 25 percent,
and preferably less than 1 percent of the total pore volume
resuIts from po~es of diameters ranging 300~+; surface areas
ranging from about 200 m2/g to about 600 m2/g, preferably from
about 250 m2/g to about 350 m2/g, and pore volumes ranging from
about 0.6 to about 1.5 cc/g, and preferably from about 0.9 to
about 1.3 cc/g ~B.E.T.):
~ :
,
- 5
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.: ', .' ," ' :"'' . ' :":, . '; '' ' ;., .: ' ~ ~
,, , ' , ; ,, :' ' , :: ' ' ' ' ' . : ~ ::
, : , .,: , ~ . . . ,.: , . . :
(b) a novel method for the preparation o e said R-l and R-2
catalysts from an aqueous or alcohol synthesis sol comprising dispersing an
aluminum halide in an aqueous or alcohol medium, and adding an organic reagent
which combines with the halide and removes the halide from solution as an
organic halide7 with control of water (or alcohol):aluminum salt ratios7 and
control and removal of hydrogen halide acid generated with reaction, preferably
with the additional incorporation of Group VIII noble metals or lanthanum or
lanthanum series metal salts, or both, to provide the selective pore si~e
distributions, particularly as relates to the formation of extrudates, with
concurrent optimization of surface area and pore volume, as required for the
production of R-l and R-2 catalysts; and
(c) a conversion process, conducted with said R-l catalyst, in
an initial or first reaction zone comprising one or more stages (and in one
or more reactors) wherein a hydrocarbon or hydrocarbonaceous feed, e.g., a
coal liquid, shale liquids, tar sands liquids, whole heavy crude or residua
feed, containing 1050F.~ materials, especially one having the ~ollowing
characteristics,
Operable Preferred
Range_ Range
Gravity, API-5 to 20 0-14
:~ 20 Heavy Metals
(Ni & V), ppm5-1000 200~600
- L050 F.+, Wt~%10-100 40-100
~ Asphaltenes ~C
: insolubles~, W~.% 5-50 15-30
` Con. Carbon, wt.% 5-50 10-30
is contacted, in the presence of hydrogen at severities sufficient to convert
at least about 30 percent by weight and preferably from about 40 percent to
about 60 percent of the 1050F.~ materials of the crude or residua present to
- 6 - ~:
- , '- ` : . ~. .. , ...., . ~ :
: . . . ,: . . . . .
: ... ' . . ': .~ ' .' .. ,
6~
1050F.- ma~erials, remove at least about 75 ~e~cent, and preferably from about
80 to about 95 percent, by weight oE the metals, preferably producing a product
having the following characteristics:
Operable Preferred
Range Range
Gravity, API 14-30 15-25
Heavy Metals
(Ni & V), ppm10-100 40-80
1050 F.~, Wt.%10-50 25-40
Asphaltenes (C
. insolubles), ~t.~ 3-20 5-15
Con. Carbon, wt.% 3-20 5-10
which product is suitable Eor further contact, in the presence oE hydrogen, in
a second or subsequent reaction zone comprising one or more stages (and in one
or more reactors) with said R-2 catalyst at severities sufficient to convert at
least about 50 percent, and preferably from about 60 percent to about 75 percent
of the 1050 F.~ materials of the crude or residua to 1050 F.- materials, remove
at least about 90 percent, preferably from about 97 percent to about 100 per-
cent, by weight of the metals, and reduce Con. carbon from about 50 percent to
about 100 percent, and preferably from about 75 percent to about 90 percent,
especially to produce a product having the following characteristics
Operable Preferred
Range ~ang~
Gravity, API 18-30 20-28
Heavy Metals (Ni & C 50 < 5
V),ppm
1050F.+, Wt.% . 5-30 10-25
Asphaltenes (C
insolubles), ~t.% ~ 3 Cl
Con. Carbon~ Wt.% ~ 5 <3
~" ` : ,,
- 7 -
. . .
- : . . .. : . . : . . : .
~6~s~a~
In their optimum fo~ms, the absolute pore size diameter, of the
R-1 catalyst, dependent on particle size, is maximized within the 100-200~,
150-250~, and 175--275~ ranges, and the R-2 catalyst within the 100-200~ range,
respectively. It i5 not practical, of course, to eliminate the presence of all
pores of sizes which do not fall within these ranges, but metllods of preparation
are known, particularly methods of preparation according to this invention,
which do indeed make it practical to produce catalyst particles of absolute
pore size diameters highly concentrated within these desired ranges. The
following tabulations show the pore size distributions, as percent of total
pore volume, of marginal and preferred catalysts of this invention:
2~
. . . .: .
i6~
,~ o ~ o ~ o
h ~ ~ O ~`i
S~ ~ ~ o ~~ U~ ~4 ~r) 1~ U~ o~7 o U~ ) o
P~
n o a~ Lr ~ O
a) o . ,~ o
a~ o ~cr, o Ll~ O O ~ O`J O U~ n O
a) o ~ ~ ~ ~ ~
: .
~.
1--n ~ o :'
. u~ O
O O Ooo O O ~~ c~ o ~ o
. O ~ ~ ~ ~ ~ `~ `;I'
:~1 o trl
~ ~ .
,
.
_~
~ _~ ~ I ~ ~ 0~ ~ . . .
~J ''-o ~`1 _ ~1 _~ c~
o u~ ~ -- E~ -
U~ ~ ~) ~ V . ...
O ~ ~O'C ^ nJ _O¢ td ~ ¢
1 OO¢ Oa) ~ o¢ o a~ o c¢ u) a~
o o~ ~ oO ~ E~ ~ OO l_
~ ~ ~~ ¢ vI C`~o¢ ~ ~ ~u~ ~ ¢,~ ~i
u~ ,~ ~o o o o ~ ~ o o oo ~ ~ O u~ o o a~
~ ~ ~ o op t~ :~ U~ ~1 p t~ ~ 1~ U~ p U ' ' ` '
¢ ~ ~ o~a) ~ o~ ~ ~ -i ~ (d
H ~ i u) ~ ~ hC~ h 1i
¢ ~1 0 O :3 O j O :~
~ ~ ~ &1 U~ _ ~ P~
~:
. , .
_, 9 _ .
.
. ' ' ' .' ' ' . . . ' . . . ' ' ' ''. ' . "' ' " . " ' . .' ."" ' . ' ' . ' '. . ' ' ' . ' ' ' ' ~ ~ ' . ' . " " . '' . ' ' ' I . . ' ' ' .
~56~
U~
~ D
U~
CO ~o o
,R~
0~ 00
O
O O ~(
~ ~ O~ ~
a\ ~~ ~ a~ d R
h O _~ O ~ ~ c~ o
a
S~
P~
~ ~
~ a) .
,D ~ U ~
'C R
O ~i t~
~ O
p,i g ' .
a ~
o~ V h
o ~ a~ o
h ~rl ~I tQ
h a ~ ~ ~0 a
a~ ~ ~ o
U) U~
~ ~ u~ a ~ ~
h ~ rl a
~, ~,~ O ,a 4~
a a~ h o
aJ ~ V
rC ^ I a) a
O ~ ~ o
~rl ~ O U~
R ~ ~ a
O ^ al ,~ rl rl
rl g ~,a-l a
h ~ ~ rl ~rl
O ~
a ~, J
~ ~ ~d
~ o~ ~oo a
_
_ rl h ~ o ~ ~1
o oO a U~ ~æ
a h :-- >~ O a
O q? O¢ ~ U~ O Cq ~d
~1 ~ oo~C o a) ~ ,~
E~ v ~ ~o o + ~ ~ ~ u ~ a
cn ~ ~ ~I I ~ ~ o
p~ ~ ~ ~o O o
h ~ O O U~ .C a
: ~ ~ O ~ ~ a
~ ~ 1 u~ X E~ ~1 H
C) ~ O
~I Pl ~ .
~1 ~ .
- 10 -
' . ~ ' . , i :' ~ : , ., ' ' ' . , ' . : ' ` ~. . , . : ,' ' ' ' ',
The R-1 and R-2 catalysts can be the same or different as regards
their specific chemical composition, qualitatively or quantitatively, though
certain different forms of these catalysts have been found to provide better
results when used in the different and preferred process modes--viz. when R-l -
is used in an initial or first reaction zone to process heavy crudes or residua,
hereinafter referred to as "R-1 service," and when R-2 is used in a second or
subsequent reaction zone to process, e.g. the product of said initial or first
reaction zone (or feed of similar nature), hereinafter referred to as "R-2
service." In general, however, both the R-l and R-2 catalysts can comprise a
composite of a refractory inorganic support material, preferably a porous in-
organic oxide support with a metal or compound of a metal, or metals, selected
from Group VIB or Group VIII, or both, the metals generally existing as oxides,
sulfides, reduced forms of the metal or as mixtures of these and other forms.
Suitably, the composition of the catalysts comprises from about 5 to about 50
percent, preferably from about 15 to about 25 percent ~as the o~ide) of the
Group VIB metal, and from about 1 to about 12 percent, preferably from about 4
to about 8 percent (as the oxide) of the Group VIII metal, based on the total
weight (dry basls) of the composition. The preferred active metallic components,
and forms thereof, comprise an o~ide or sulfide of molybdenum and tungsten of
Group VIB, an oxide or sulfide of nickel or cobalt of Group VIII, preferably a
mixture of one of said Group VIB and one of said Group VIII metals, admixed one
with the other and inclusive of third metal components of Groups VIB, VIII and
other metals, particularly Group IVA metals. The preferred R-l and R-2 catalysts
are constituted of an admixture of cobalt and molybdenum, but in some cases the
preferred R~2 catalysts may be comprised of ni.ckel and molybdenum. The nickel-
molybdenum catalyst in R-2 service possesses very high hydrogenation activity
and is particularly effective in reducing Con. carbon. Other suitable Group VIB
and VIII metals include, for example, chromium, platinum, palladium, iridium,
. ,: .. : . ~ . . ...... .. . ' . . . . : .
., ,. ::,, .... .: ' ',,, . , ,',,',,, ' ~ '.: ' ' ' ' ' :'
:, , :. . , :,: .. .
' ' . .' . " ' ' ..... ' ' .,' :. . ~ :
~.~56~
osmium, ruthenium, rhodium, and the li~e. The lnorganic oxide supports suitably
comprise alumina, silica, ~irconia, magnesia, boria, phosphate, titania, ceria,
thoria and the like. The preEerred support is alumina, preferably gamma alumina,
which in R-2 service is preferably stabilized with silica in concentration
ranging from about 0.1 to about 20 percent, preferably from about 10 to about
20 percent, based on the total weight (dry basis~ alumina-silica composition
(inclusive of metal components). The catalyst composition can be in the form
of beads, aggregates of various particle sizes, extrudates, tablets or pellets,
depending upon the type of process and conditions to which the catalyst is to
be exposed.
Particularly preferred catalysts are composites of nickel or
cobalt oxide with molybdenun~, used in the following approximate proportions:
from about 1 to about 12 weight percent, preferably from about 4 to about 8
weight percent of nickel or cobalt oxides; and from about 5 to about 50 weight
percent, preferably from about 15 to about 25 weight percent of molybdenum oxide
on a suitable suppoxt, such as alumina. A particularly preferred support for
R-2 catalyst comprises alumina containing ~rom about 10 to about 20 percent
silica. The catalyst is sulfided to form the most active species.
The Group ~IB and Group VIII metal components, admi~ed one
component with the other or with a third or greater number of metal components,
can be composited or intimately associated with the porous inorganic oxide
support or carrier by Yarious techniques known to the art, such as by impregna-
tion of a support with the metals9 ion exchange, coprecipitation of the metals
with the alumina in the sol or gel form, and the like. For example, a pre-
formed alumina support can be impregnated by an "incipient wetness" technique,
or technique wherein a metal, or metals, is contained in a solution in measured
amount and the entire solution is absorbed into the support which is then dried,
calcined, etc., to form the catalyst. Also, for example, ~he catalyst composite
- 12 -
,. ~ .
~6~
can be formed from a cogel by adding together suitable reagents such as salts
of the Group VIB or Group VIII metals, or both, and ammonium hydroxide or
ammonium carbonate, and a salt of aluminum such as aluminum chloride or aluminum
sulfate to form aluminum hydroxide. The aluminum hydroxide containing the salts
of the Groups VIB or Group VIII metals, or both, and additional metals if
desired can then be heated, dried, formed into pellets, or extruded, and then
calcined in nitrogen or o~her generally inert atmosphere. Catalysts formed from
cogels do not possess pore size distributions as uniform as those formed by
impregnati.on me~hods.
The catalysts can be used in the reaction zones as fixed beds,
ebullating beds or in slurry form within beds. When used in the form of fixed
beds, the particle size diameter oE the catalysts generally ranges from about
1/32 to about 1/8 inch, preferably about 1/16 inch. When used as ebullating
beds the catalyst generally range about 1/32 inch diameter and smaller, and
when used as slurry beds the particle sizes generally range from about 100 to
about 400 microns. The bul~ density oE the R-l catalyst generally ranges from
about 0.2 to about 0.6 g/cc, preferably from about 0.2 to about 0.5 g/cc~,
depending on particle size, and that o the R~2 catalyst ranges from about 0.3
to about 0.8 g/cc, preferably rom about 0.35 to about 0.55 g/cc.
The catalysts oE this inventlon further comprise a metal, or
metalsj of Group IVA, or compounds thereof. The catalysts will thus comprise
germanium, tin, or lead, or admixture of such metals with each other or with
other metals, or both, in combination with the Group VIB or Group VIII metals,
or admixture thereof. Tlle Group IVA metals act as promoters for R-l and R-2
catalysts in enhancing the rate of demetallization of a feed. Of the Group IV~ -
metals, germanium is particularly preferred. Suitably, the Group IVA metal
compxises from about 0.01 to about 10 percent, preferably Erom about 2.0 to
about 5 percent of the catalyst, based on the total weight (dry basis) of the
;
- 13 - -:
, . .
,, " .. , ~ ,, ~, .... . .... . . . ... .. . . .. .
: " ~ ' : '' ' ' i ' ` " ' ' `
~C~56~
composition. The Group IV~ metals ~ust be incorporated within the catalyst
by impregnation.
A feature of both the R-l and R-2 catalysts is that each is of
very high surface area and co~tains ultra-high pore volume, this providing an
extremely great nllmber of active metal sites. This, in combination with the
selected pore size distributions of the R-1 and R-2 catalysts, provides catalysts
admirably suitable for the demetallization and hydroconversion of ~eeds oE the
characteristics described, which feeds usually contain additional high concen-
trations of sulfur and nitrogen. In R-l service, in utilizing R-l catalyst in
its most preferred form, the number of pores ranging between about 100-2752
absolute pore size diameter is maximized, dependent on particle size, as is
surface area and pore volume consistent with practical catalyst preparation
procedures and with regard to the particle crush strength requirements of the
process. Moreover, the number of pores which are smaller than 50~, and pre-
ferably those greater than about 300~, or about 350~ when the average particle
size diameter exceeds about 1/50 inch, are minimized. R-l catalyst of such
character has thus proven outstanding, even under the stringent requirements of
R-l service, in retaining considerable quantities of heavy metals while yet
remaining active over extraordinarily long periods. For example, the R-l
catalyst, when operated at a 700F. start-of-run temperature ~SOR), has been
shown suitable for maintaining 1050 F.+ conversion levels ranging from about
20 to about 40 percent, and higher, ~or periods ranging up to about~70 days,
and longer. In fact, this catalyst, at the end oE such period, has been found ~-
to retain over 150 percent of its own weight of heavy metals from whole heavy
crudes and residua feeds. Moreover, while accomplishing this, the R-l catalyst
also effectlvely removes much o~ the sulfur and nitrogen in hydrodesulfurization
and hydrodenitrogenation reactions. For example, whole heavy crudes and residua
of the type characterized often contain from about 2 to about 7 weight percent,
.: - 1~ -
, : . - , :, . . .: . ~ .: :.: . ,: .- ~ : .
- ~ . :: . . .
.. ". ..... . . ... . .
'. , , ~ " '' . . '. ' "' . ' ~'"`'. ' ', ,. . . ' ' :. .' .' ' ~ ' ' '. ''. ,, '' ' ' -, .
~q~5~8~
usually from about 3 to about 6 percen~ sulfur, and often from about 0.2 to about
0.8 percent, usually from about 0.3 to about 0.7 percent nitrogen. Generally,
from about 75 to about 95 percent of the sulfur, and from about 25 to about 60
percent of the nitrogen can be effectively removed from such heavy crudes and
residua in ~-1 service while obtainin~ high conversion. The product of such
reaction, unlike the original feed processed over the R-l catalyst, is now
suitable as feed to a coker to provide greater yields of C3 liquid product
than would otherwise have been possible by coking the original feed, and the
coke product is less sour and less contaminated by heavy metals. For example,
it has been found that by operating the R-l catalyst at a start-of-run ~SOR)
temperature of about 700~. at a low space velocity of about 0.25-0.50 Y/~l/V,
a product is obtained which is highly suitable for coking. Compared to coking
of the raw whole crude or residuum, the C3~ liquid product yield is increased
from 86 to 97 vol. % and the coke yield is decreased some 70%. The product
coke contains only 2.5 wt. % sulfur compared to 5.9% sulfur coke from coking
of the raw feed.
The product of the reaction conducted at a space velocity of
0.25 V/Hr./V is also highly suited for process~ng in a resid catalytic cracking
operation. The raw feed contains too much heavy metals and Con.carbon for con-
ventional catalytic crackingO The product, on the other hand, is lo~ enough inheavy metals and Con. carbon to be converted in a resid catalytic cracking
operation Hence, ~he hydroconverted product is fed directly to a fluid
catalytic cracker operating on a cheap amorphous catalyst at low once-through
430 F. conversion (ca. 25%) but at high 950 F. conversion (ca. 95%). The
result is that a 97% yield (C3+) of a synthetic crude suitable for further
processing in conventional refinery equipment is obtained. Coke yield, produced
on the cracking catalyst, is 7.5 wt. %.
- 15 -
': . , ' . ": ' ,, "~,-, ' '
.. , ,, ., ~ , ' ' .
s~
By operating the reactor, or reactors, containing the R-1
catalyst at a start of-run temperature of about 750F. and at a space velocity
of about 0.5 V/Hr./V, a product is made that is suitable for use in a catalytic
cracker employing zeolite cracking catalyst. By operating at about an 80%
430 F. conversion, a C3 yield of 107 volume percent and a coke-on-catalyst
yield of 7.5 wt. % can be obtained. However, the preEerred mode of operation
is to remove 90% of the metals from the raw feed with the R-l catalyst at a SOR
temperature of about 750 F. and a high space velocity of about 1.0 V/Hr./~.
This product is now suitable for R-2 service to provide feeds which can be used
directly in con~entional commercial petroleum operations, especially in con-
ventional hydrocracking and catalytic cracking operations for the production
of gasoline and other light distillates. The product from R-2 should contain
about 2 ppm heavy metals, or less, with a Con. carbon of about 3.3 wt. %. This
material, when converted in a catalytic cracker employing zeolite catalyst at a
catalyst makeup rate of 0.4 lb.tBbl~ at about 80% 430F. conversion, will
produce a yield of 110 vol. % C3~ and 6.7 wt. % co~e on catalyst.
In the preferred mode of operation (i.e., 750F. SOR and
1 V/Hr./~), this catalyst will have removed up to 90~ and more of the metals in
the raw feed after an operation of 27 or more days, the catalyst retaining over
about 95% of its weight of metals from whole heavy crudes and residuum feeds.
The amount of sulfur and nltrogen that is removed is comparable to that pre-
sented in the preceding paragraph.
In utilizing R-2 catalyst, in its most preferred form, the
number of pores ranglng between about 100-200~ absolute pore size diameter is
maximized, as is the surface area and pore volume consistent with practical
catalyst preparation procedures and with regard to the crush strength require-
ments of the process. This means, of course, that the number of pores of
d~ameter which are smaller than 100~ (especially 50~-) or greater than about
- 16 -
- , , . ~ , , , . ,:
' , ~ ' ' ' . ..
~.~s~
200~ are minimized, especially the 300~ pores. ~-2 catalyst of such character
has thus proven outstanding in R~2 service which, while not as stringent as R-l
service, is nonetheless rather severe, the R-2 catalyst retaining considerable
quantities of heavy metals while yet remaining active for Con. carbon conversion
over long periods. Moreover, the R-2 catalyst accomplishes this while achieving
high hydrodesulfurization and hydrodenitrogenation of the feed. For example,
operating at 650 F. SOR temperature and at a space velocity of 0.5 V/Hr./V,
the R-2 catalyst reduces the metals content of the ~-l product from a level of
about 60 ppm to about 5 ppm, representing about 99% metals removal based on
total feed. ~t the same time, asphaltenes are reduced to near 1 wt. ~ which is
necessary for obtaining Con. carbon levels of 2-3 wt. %, based on product.
Sulfur level reaches about 0.3 wt. %, representing over 90% removal of sulfur
based on the raw feed. The catalyst is also effective for effecting 1050 F.
conversions, and conversion levels (based on raw feed) of 60% and higher have
been obtained. The product of ~-2 service is suitable as feeds for conventional
~petroleum processing operations, particularly hydrocracking and catalytic crack-
ing operations.
In a preferred method for the preparation of these novel cata-
lysts, catalysts which at least meet the marginal requirements of R-l and R-2
catalysts às regards desired pore size distribution are prepared from alumina
in a synthesis reaction, as gels or cogels wherein certain critical conditions
must be observed as regards the concentration of reactants in the synthesis
solution, the acidity of the synthesis solution, and the temperature of ~he
synthesis reaction. Gel preparation without added metals, of course, requires
subsequent incorporation, e.g., impregnation9 of metals whereas in cogel pre-
paration the metals are added at the time of gel formation. In such preparations,
an aluminum halide, e.g., aluminum chloride, is first dispersed or slurried in
water or alcohol in certain critical proportions, de~ined for convenience in
- 17 -
~ : :~ .
' . ~' :. ~ ' ' , ' ~.', ,' . ; '
0~
terms of the molar ratio of water (or alcohol):aluminum halide dependent on
whether it is desired to produce an R-l or R-2 catalyst. The temperature of the
aluminum halide-~ater (or alcohol) slurry, to which the desired Group ~IB and
Group VIII metals and other metals, can be added as may be desired as in forming
of a cogel, is then lowered. Normally, water is used as the solvent, but
alcohols such as methanol can be used, though pore sizes tend towards the
smaller diameters with alcohol solvents. It is also essential in the reaction
to add a reagent which will remove the halide from solution while maintaining
pH in the range of 5-8, this being preferably accomplished by addition of an
olefin oxide, e.g., ethylene oxide, propylene oxide, and the like, which forms
a halohydrin. The reaction is necessarily carried out at relatively low temper-
ature, preferably from about 30F. to about 100F., and more preferably from
about 32 F. to about 60 F. The olefin o~ide is added in at least stoichiometric
quantities in relation to the amount of halide to be removed from the solution,
and preferably is added in molar excess to the solution. In the preparation of
catalyst which at least meets the marginal pore size distribution required of
R-l catalyst, the molar ratio of olefin oxide:halide ranges from about 1.5:1 to
about 2.0:1 and preferably from about 1.5:1 to about 1.7:1, while the molar
ratio of wate~ (or alcohol):aluminum halide is maintained within a range of
f~om about 15:1 to about 30:1, and preferably from about 18:1 to about 27:1.
In the preparation of catalyst which at least meets t~le marginal pore size
distribution required of R-2 catalyst, the molar ratio of olefin oxide:chloride
ranges from about 0.3:1 to about 1.5:1, and preferably from about 1.0:1 to about
1.2:1, while the molar ratio of water (or alcohol):aluminum halide is maintained
within a range of from about 22:1 to about 30:1, and preferably from about 26:1
to about 28:1. Failure to remove most of the halide, e.g., chloride, from the
reaction results in a failure to obtain the deslred crystal growth, failure to
obtain the required pore size dls-tributions, or failure to produce a crystal
- 18 -
: . . : : :
: . :. . : : .: : .::
- ~05680~ -
sufficiently stable to retain such desired pore size distrlbutions throughout
subsequent steps required in completing the formation of the catalyst. It is
believed that the required crystalline structure which shall ultimately be
produced from the sol is of a nature of boehmite, termed for convenience
"pseudo-boehmite," and that excessive halide concentration and high pH ad-
versely affect the proper formation of such aluminum oxy hydroxide crystallinestructure.
After completion of the reaction, the temperature of the gel is
raised to from about ambient to about 180~. to form a sol. Preferably, the
sol is formed at essentially ambient temperature, ranging generally from about
70 F. to about 80F. and, on proper aging, pseudo-boehmite is produced. It is
essential to age the gel at such temperature for at least about 6 hours, and
preferably for about 24 hours to about 72 hours while the gel is in contact
with its syneresis liquid. Lesser periods of aging results in reducing the
uniformity o pore siæes, and significantly longer periods, particularly periods
in excess of 6 days, often produces bimodal distribution of the pores. Failure
to properly age the gel, while it is in contact with the syneresis liquid, also
produces a crystal structure which is not sufficiently stable to retain the
desired particle size distributions in the subsequent and necessary steps of
washing, drying and calcination.
It has been discovered that Group VIII noble metals and lanthanum
and lanthanum series metals, or compounds thereof, are admirably suitable as
promoters for providing narrow pore size distributions and, in conjunction with
control of the concentration of the reactants employed in the synthesis, the
eemperature, and particularly the acidity of the synthesis solution, these
promoters can be used to provide R-l and R-2 catalysts of optimum pore siæe
di~tributions Catalysts which meet even the preferred specifications of R~
and R-2 catalysts can thus be made by incorporation o~ small amounts of Group IIIB
`
- 19 -
metals of Atomic Numbe~- 57 and greate~, and Grou~ VIII noble metals, or both,
or compounds or salts thereo~, wlthin the solution during the synthesis.
Exemplary of the former are such ~etals as lanthanum, and the rare earth metals
of the lanthanum series such as cerium, praseodymium, neodymium, promethium,
samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,
ytterbiunl and lutetium. Exemplary of the Group VIII noble metals are ruthenium,
rhodium, palladium, osmium, iridium, and platinum, which metals are less pre-
ferred than the lan-thanum series metals because of their greater cost. Suitably,
such metals, or compounds thereof, are added to the solution, for preparation
of R-1 and R-2 catalysts, in molar ratios of promoter metals:aluminum halide
ranging from about 0.001:1 to about 0.06:1, and preferably from about 0.01:1
to about 0.03:1. The reason for t~e effectiveness of these metals, particularly
the lanthanum metals, generally added as soluble salts, e.g., as halides,
acetates, nitrates, sulfates, etc., in producing the high unirormity of pores
sizes in the desired ranges, when employed at the conditions defined, is not
understood.
The syneresis liquid, after the aging step, is poured off of the
gel or cogel. In the case of a gel, the gel can next be crushed to the desired
particle size, air dried, then thoroughly washed. It is particularly preferred
to wash the gel or cogel with alcohol, to remove contaminants, after which the
catalyst is air dried at room temperature, and then dried at mild temperatures,
e.g., at about 175-225F. for about 3 to 6 hours, then calcined, e.g., by heat-
ing at about 800-llO0 F. for about 1 to 4 hours, and, the gel, then impregnated
with a predeterminéd amount of the desired metal, or metals. The washing step
is critical in the formation of the desired pore size distribution. Gènerally,
isopropanol or one of the intermediate alcohols, e.g., n-propyl isobutyl and
the like promotes th~ formation of the desired pore sizes. Methanol, on the
other hand, forms smaller pores generalIy, e.g., 0-100~, and hexyl alcohol forms
- 20 -
,-. . :
. ,,, . , . . , . , . . , .. , ,,, . . . ~ .. ,. . . .. , ~ , . , ,. .. , . . . - .
, .,. . .,:. .. , ~ ,. : , : . . . ..
~56~
larger pores, e.g., 30 ~ . ~ixtures o-~ water and intermediate alcohols also
favor the formation of 0-100~ pores.
Impregnation of the alumina can be done prior or subsequent to
the calcination step. If subsequent to the calcination step, it is best to
allow the calcined alumina to equilibrate with the moisture in the air for 4-6
hours prior to impregnation to avoid damage to the pore structure. I- is
imperative that the impregnation be done with a non-aqueous solution, e.g.,
alcohol, rather than water solu-tion. If water solutions are used, the pore
structure wlll readily shrink to the 0-100~ pore diameter range during sub-
sequent drying and calcinationO The catalytic metals, e.g., Co and Mo, are
dissolved in alcohol, e.g., methanol, and preferably isopropanol, and the
solution imbibed into the alumina. Drying for 16-24 hours in air at ambient
conditions, then drying for about 3-6 hours at 175-225 F., and then calcining
at ~00-1100F. for 1-4 hours, will preserve the desired pore structure. The
catalyst is then crushed and screened to the desired particle size for testing,
usually 1~-35 mesh (Tyler).
Extrudates of outstanding strength and quality, which meet the
require~ents of both R-l and R-2 catalysts, can be prepared in accordance with
a preferred and novel method o~ this invention which embodies extrusion of a
gel or cogel of preselected pore size distributions falling within the R-l and
R-2 catalyst ranges, or which contains pores of size distribution sufficiently
large that when the gel is subjected to extrusion at the required conditions
the reduction in the size of the pores caused by the extrusion and aging steps
will reduce the pore sizes such as to cause them to fall within the R-l and R~2
catalyst ranges. The gel or cogel, at the time of extrusion, is of critical
liquids-solids content (generally produced by drying), it has been previously
aged within syneresis liquid for preselected periods at conditions involving
critical time, temperature, or time-temperature relationships and, aftes
- 21 -
, . .,, . I .,: . . , ~ ~ , , : - .
: ' ,'' '' ';'' ' '' ' '"' :'' ',;' " '''' ~ ~ ' ; " '' ' ' '"
~S68~
extrusion, the extrudate is dried to provide a critical liquid solids content
and, in a preferred embodiment, then returned to syneresis liquid, without
washing, and again aged for specific critical periods at conditions involving
critical time, temperature, or time-temperature relationships.
In tle preparation of an extrudate, a gel or cogel is initially
prepared from a sol, preferably one containing a Group VIII noble metal, or
metals, or lanthanum and lanthanum series metals, or admixtures thereof, in the
range of proportions previously described, by varying the molar ratios of water
(or alcohol):aluminum halide andiolefin oxide: halide, and also within the ranges
described consistent with the requirements of producing an R-l catalyst, if an
R-l catalyst is desired, or with the requirements of producing an R-2 catalyst,
if an R-2 catalyst is desired. Subsequent to formation of a gel or cogel of
the required properties, the gel or cogel is initially aged in syneresis liquid
at critical time, temperature~ or time-temperature relationships sufficient to
increase the crush strength of the finished particle and -to provide the desired
pore size distribution of the gel or cogel, or to preserve such pore size
distribution sufficiently that when subjected to extrusion and further aging at
the required conditions the reduction in size of the pores caused by the extru-
sion will produce pore size distributions falling within the R-l and R-2 catalyst
ranges. This is accomplished in part by the presence of the Group VIII noble
metals or lanthanum series metals, or both, which inhibits or tends to inhibit
the normal tendency to reduce the sizes of the pores during the necessary step,
or steps, of aging. The crush strength is increased, and pore size distribution
preserved by aging the gel or cogel prior to extrusion, preferably containing
the Group VIII or lanthanum series metals, or both, in syneresis liquid (1) for
an initial time period ranging at least 6 hours, and up to about 30 days, or
longer? preferably for a period of from about 1 day to about 6 days, and more
preferably from about 24 hours to about 72 hours, at generally ambient temperatures,
- 22 -
.: : : : ' ,, . ., :. . : .: . - : : . : .: :
i.e., about 50E. to about 80 ~., o~ by aging (2~ at elevated tempe~atures
ranging from about 80F. to about 180F., preferably from about 100F. to about
160F., or by aging (3) at a combination of time-temperature relationships
within these ranges of express conditions. It is preferred, however, to subject
the gel or cogel to an initial aging for a rather short period, (a) preferably
from about 1 to 3 days or, more preferably, from about 24 hours to about 30
hours, at ambient conditions, or Cb) at higher ~emperatures ranging from about
80F. to about 180F., preferably 100F. to about 160F. for shorter periods,
preferably ranging from about 10 hours to about 2~ hours, and more preferably
from about i5 hours to about 20 hours, and then to extrude, dry the extrudate
to a critical liquid-solids content, and thereafter again subject the extrudate
to a subsequent aging in syneresis liquid.
The gel or cogel, after the initial aging period, is separated
from the syneresis ]iquid and partially dried by standard teclmiques, e.g., as
described, to produce a gel or cogel containing from about 12 percent to about
40 percent, and preferably from about 15 percent to about 25 percent solids
content, based on the total weight of the gel or cogel with its occluded liquid.
The gel or cogel is preferably crushed to less than 10 mesh ~Tyler series)
particle sizes and then extruded through a die to produce extrudates of desired
diameter, and the extrudates are then cut into desired lengths. Efforts, on
the one hand, to extrude a gel or cogel having too low a solids content generally
prove unsuccessful or, if successful, the extrudates will be of poor quality
and may even deteriorate and crumble on subsequent aging in syneresis liquid.
Extrusion of a gel of too high solids content adversely affects the pore size
distribution previously developed in the gellation, the crush strength and the
larger pores generally being substantially reduced in size. After extrusion,
and formation of the extrudate, the extrudate must again be dried to a solids
content of ~ 25 wt. %. If the extrudate is to be subsequently aged, as preferred,
_ 23 -
:- . - . ~ . . . .
,, . ~ I
~,, . . ::
- :.
',. :, ' ;,, . ~ ' ' : '
~,'.' ~' ', . :
.
~ 6~
the extrudate, after drying, ls then directly trans~erred, without washing, to
the syneresis liquid. In the subsequent aging in syneresis liquid, the extru-
date is again treated at critical time, temperature, or time-temperature
relationships to preserve the required R-] and R-2 pore size distributions.
Suitably, this is accomplished by aging the extrudate in the syneresi~ liquid
(1) for a period ranging at least 6 hours, and up to about 30 days, or longer,
preferably for a period ranging from abou, 1 day to about 6 days, and more
preferably from about 24 to about 72 hours at ambient conditions, or by aging
(2) at elevated temperatures ranging from about 80F. to about 180F., pre~
ferably from about 100F. to about 160~., for periods ranging from about 10
hours to abou~ 24 hours, preferably from about lS hours to about 20 hours, or
by aging (3) at a combination of time-temperature relationships within these
express conditions. The extrudate is then again necessarily dried to provide a
solids content of ,25 wt. %, and then washed, preferably wlth alcohol. Failure
to dry the gel to the required solids content can produce disintegration of the
particles in washing. A gel or cogel properly aged, properly dried to the
required liquids-solids content, properly extnlded, without washing, and then
again dried to the required solids content, the extrudate subsequently aged for
the required period, and then dried to the required ~olids content prior to
Z0 washing will provide extrudates of superior strength and quality.
A low torque extruder, ~odel 0.810 Research Extruder manufactured
by Welding Engineers of King of Prussia, Pennsylvania, has been found to produce
extrudates of outstanding quality when produced pursuant to these specifications.
Extrudates of superior crush strength can be formed in producing both R-l and
R-2 types of catalysts. After passage through a die to provide shapes of pre~
determined selected diameter, particularly for use in ebullating and fixed beds,
the extrudates can be cut in the desired lengths, dried to critical solids
content, aged in the syneresis liquid and again dried to control solids content9
- 24 -
.. . i , , .. ,, . . , . . . ; .
washed, preferably in alcohol as previously described, again drie~, calcined
and, where desired, the so-formed extrudate then impregnated with the desired
metal, or metals, or with an additional metalg or metals.
The metals-con-taining catalyst, whether formed as a gel or cogel,
can then be contacted with hydrogen and hydrogen sulfide, or hydrogen sulfide
precursor, or both, in situ or ex situ, in a subsequent step, or steps, to
reduce and sulfide all or part of the metal salts and activate the catalyst.
The sulfiding is generally carried out by passing hydrogen sulfide in admixture
with hydrogen through a zone of contact with the catalyst. The temperature of
sulfiding is not especially critical, but is generally carried out in the range
of about 500 to about 900F., preferably from about 6~0F. to about 750~.
The time required for the sulfiding of the metals is generally short and not
more than an hour, or at least no more than one to four hours is generally
required to complete the sulfiding. Typically~ in sulfiding the catalyst, the
catalyst is contacted with a dilute gaseous solution, e.g., about 5 to about
15 percent, yreferably from about 8 to about 12 percent, of hydrogen sulfide in
hydrogen, or hydrogen plus other nonreactive gases, and the contacting is con-
tinued until hydrogen sulfide is detected in the effluent gas. Such treatment
converts the metals on the catalyst to the sul:eide form. Sulfur-containing
hydrocarbons, such as gas oils and the like, may be used as hydrogen sulfide
precursors.
In accordance with the present hydroconversion process, the
~-1 catalyst is contacted in a reaction zone with a hydrocarbon or hydro-
carbonaceous feed, e.g~, a liquid derived from coal by hydrogenation, shale or
tar sand liquids, a heavy crude or residua feed, in the presence of hydrogen,
at conditions of severity suEficient to achieve the desired conversion of the
- 25 -
" ` ' ` ' ' :
56~Z~D~
1050F.~ materials to lower molecular weightZZ or 1050 F.- materials, and
simultaneously to remove at least about 80 weight percent, and preferably from
about 85 weight percent to about 90 weight percent of the heavy metals, parti-
cularly vanadium and nickel, from the feedO Removal of the heavy metals is
enhanced by the combination of conditions, particularly that of temperature,
which enhances the conversion and results in some cleavage and reduction in
the size of the asphaltenes~ and the selective pore si7e distribution of the
R-1 catalyst, the 10C-275~ pore si~e openings accepting asphaltenes ranging
from small to relatively large size, with regard to whether or not such mole-
cules were originally of such size or reduced in size by the conditions ofreaction. The small to relatively large si2e asphaltenes readily diffuse, with
hydrogen, into the depths of the catalyst particles wherein hydroconversion
reaction egressing from the particle, along with unreacted materials, as more
highly hydrogenated lo~er boiling products.
In conducting the reaction, the R-l catalyst is generally
employed in one or more stages of a reactor, or reactors, aligned in series
(which can and usually does include one or more stand-by or swing reactors, as
desired). The R-l catalyst, after being reduced and sulfided generally in situ
~ithin the reactor, is operated under conditions, the majo~ variables of which
are tabulated for conveniencè, as Eollows:
Operable Preferred
Temperature, F., E.I~T.( )
Start-of-Run 700 750
End-of-Run 850 800
Pressure, psi 2000-10,000 2000-5000
Hydrogen Rate, SCF/B 3000-20,000 3000-10,000
Space ~elocity, LHS~ 0.25-5.0 0.5-1.0
(1) Equivalent Isothermal Temperature (E.I.T.)
- 26 -
,', . ' .
: ,, . ., . ~ .. ;, . . , ,:
.. , .~ ... ,. ~
:,
,' ~' ' : . ., ' ' ' ' ' " , , . .: ,
,
, , : ,, ,' , . ' , ' ~: ,
~613~
The hydrocarbon or hydrocarbonaceous feed, i.e., soal liquid,
shale or tar sand liquids, heavy crude or residua, is rendered by R-l service
more suitable as a feed for use in a coking process or a resid catalytic crack-
ing process. Preferably, however, the product of R-l service is rendered a
suitable grist for R-2 service, and thereby made suitable as a feed for use in
conventional petroleum refining processes, especially as a feed for a hydro-
cracking or catalytic cracking operation. The R-2 catalyst, as heretofore
suggested, is of pore size distribution selective of a range of asphaltene
molecules smaller than those accepted within the pores of the R-l catalyst.
The asphaltenes in the R-l product are generally smaller than those of the raw
feed and can quite readily diffuse into the pores of the R-2 catalyst. The R-2
reactor is specifically designed to remove the remaining metals such that the
procluct will contain ~ 5 ppm metals and ~2-3 wt. % Con. carbon. Conditions are
needed that favor the hydrogenation of the fused benzene rings of the asphaltenefragments followed by the cra~king and dealkylation of the satura-ted rings. In
this way, Con. carbon can be effectively reduced to the desired level. These
conditions also favor the removal of the very refractory remaining metals.
Corlditions favoring this type of reaction are low start-of-run temperature~ e.g.
650-700F.~ at high hydrogen partial pressure, e.g., 2000-5000 psig.
In contrast to tne R-l catalyst, the R-2 catalyst removes less
metals and Con. carbon on an absolute basis but percentage-wise it removes aboutthe same amount of the metals. This is also true of the sulfur and nitrogen
removal reactions. However, this catalyst is more effective on the most re-
fractory molecules a~d must be quite active to accomplish this reaction, espe-
cially at the low temperature required.
The R-2 catalyst, which differs from R-l catalyst, is effective
in the hydroconversion of smaller molecules, far more so than an R-l type
catalyst. ~lbeit it has pores maximized within a ranee of diameters smaller
- 27 -
,., . .. . . , . . ~,
-: . , , ' . 1
~3~S6~
than the R-l catalyst, it does not encounter d~ffusion problems with the con-
version material produced in R-l service. The smaller pores prevent the very
large asphaltene molecules from entering the pores which severely diminish the
much needed hydrogenation function of the catalys-t.
In R-2 service, the R-2 catalyst is generally employed in one
or more stages of a reactor, or reactors aligned in series. The R-2 catalyst,
after being reduced and sulfided generally in situ within the reactor, is
operated under conditions, the major variables of which are tabulated Eor con-
venience as follows:
Operable Preferred
Temperature, F., E.I.rr.
Start-of-Run 600 650
End-of-Run 850 775
Pressure, psi 2000-10,000 2000-5000
Hydrogen Rate, SCF/B 3000-20,000 3000-10,000
Space Velocity, LHSV 0.25-5 0.25-2.0
~ The invention will be more fully understood by reference to the
following selected nonlimiting examples and comparative data which illustrate
its more salient features. ~ll parts are given in terms of weight units except
as otherwise specified.
Examples 1-7, immediately following 9 describe preparation of a
series of R-l and R-2 catalysts, inclusive of gels and cogels, wherein pore
size distribution is controlled and set during gellation. Examples 1-4 thus
describe the preparation of gel type catalysts under varying conditions which
favor the formation of R-l or R-2 catalysts, respectively. Catalysts A and B
are thus R-l pre-catalysts, and Catalysts E and F are R-2 pre-catalysts. Example
5 describes preparation of R-1 catalysts, prepared from cogels, including Group
VIB and VIII metals. Examples 6-7 describe preparation of vastly improved gel
type catalysts of both the R-l and R-2 types.
- 28 -
" , . .. . ~ ., . ....... : : .
, ~ . .
Examples 1-4 (Preparat.ion of Gel-Type Catalysts ~B~E and F)
In a first series of preparations, 1160 gram portions of
A1C13.6H20 were weighed, transferred to large glass beakers, and then slurried
in portions of deionized water ranging from 15:1 to 27:1. The several portions
of slurried material were each then cooled to 35 F., and gaseous ethylene oxide
was then introduced at a rate of 12.5 grams per minute until sufficient ethylene
oxide had been added to provide molar ratios of C2H40/HCl ranging from l.l to
1.6.
The resulting clear solutions were then allowed to slowly warm
to an ambient temperature of 75F., a rigid gel having begun to form after about
1 hour. The gels were permitted to age at this temperature for periods ranging
24 to 72 hours, each in contact with its own syneresis liquid, the syneresis
liquid having become visible as a stratified layer above the blocks of solidified
gels and between the glass walls and side boundaries of the solidified gels
which shrink away from the glass and exude the syneresis liquid.
The gels, after the aging period, were each then separated from
its respective syneresis liquid by merely pouring off the liquid. The gels,
having the appearance of dry blocks of material, were then crushed into parti-
culate masses, and each then thoroughly washed with 5 gallons of isopropyl
alcohol containing 1000 cc NH40H in a column or by successive decantation. The
washing was continued in each instance until the effluent from the column was
free of chloride, as determined by testing for chloride with silver nitrate
test solution. The particulate masses were then thoroughly dried in air for
15-25 hours and 190F. for periods ranging between 6 and 24 hours, and thereafter
calcined at 1000F. for periods of from 2 to 4 hours.
The materials formed in these syn-thesis reactions, which were
found admirably suitable as supports for use in the preparation of both R-l
and R-2 catalysts, are characterized in Table I as R-l Catalysts ~ and B and
- 29 -
' ' '~ , ' ''' ';'':-' " ' '
., ~ . , .
:' , , : ' .,''`,. , '', ,' ',: .
.... ,:, ,,: , ,, . . .. ~ . . :
R-2 Catalysts E and F, respectively.
Example 5 (Preparation of Cogel~Type Catalysts ~ and D'?
The foregoing procedure was repeated, except that in this
instance two cogels were separately prepared, each according to the following
specifics: 1160 grams of A1C13.6H20 was slurried in 500 cc deionized water and,
after addition of one-half of the required amount of ethylene oxide, solutions
were added which contained (a) 64.~ grams of CoC12.6H20 dissolved in 200 cc
H20 and (b) 95 grams of phosphomolybdic acid dissolved in 200 cc H20. The
balance of the ethylene oxide was then added. The final preparation of a
catalyst, which contained 6 wt. % CoO and 20.5 wt. % MoO3, was then completed,
these catalysts being identified as Catalysts~D and D' in Table I.
Examples 6-7 (Preparation of Improved Gel-Type Catalysts C and G) -~
Examples 1-4 were again repeated except that in this instance
1.0 wt. % rhodium or 3.5 wt. % lanthanum was slurried with the AlC13.6H20 in
preparation of the sol. The catalysts formed in this manner are identified in
Table I as Catalysts C and G, respectively.
The data presented by ~eference to Table I thus show that
catalysts, having only a marginal amount of pore sizes in diameters less than
50~, i.e., 50~-, and with a large amount, preferably a maximum of pore sizes in
diameters ranging 150-250~ can be prepared by maintaining molar ratios water:
aluminum chloride of about 15 to 30, preferably 18 to 27; molar ratios ethylene
oxide:HCl of about 1.5 to 2, preferably 1.5 to 1.7; and by aging the catalysts
for periods ranging from about 1 to 3 days, preferably from 1 to 2 days. In
preparing catalysts with smaller pores 9 these data show that such catalyst can
be also prepared with a minimum of pore sizes of diameter within the 500A- and
300~ ranges, and with a maximum of pore sizes of diameter ranging from about
100~ to 200~. This is accomplished by maintaining a molar ratio of water:
aluminum halide ranging about 22 to 30, preferably 2G to 28; a molar ratio of
- 30 -
-, ` ~ . ' ',' ': ' ' . ,, , " , ~ " ., ," ,".,. ~ , .. " " ~ ,.. ... .. . . .
~35~
ethylene oxide:HCl of about 0.3 to 1.5, ~efe~ably 1 to 1.2; and by aging the
catalyst for periods ranging about 1 to 3 days, preferably 1 to 2 days. This
limited aging improves the uniformity of pore size distributions with the
desired ranges, as relates to the preparation of gels and cogels. The use of
trace metals such as Group VIII noble metals or lanthanum and lanthanum series
metals is also found to increase the uni~ormity and maximization of the desirable
pore size distributions. Moreover, catalysts having very large pores can be
prepared having a minimum o pore sizes ranging 50~- and 350A~, and with a
large amount, preferably a m~ximum of pore sizes o diameter ranging 175-275~
suitably by preparation of a cogel as described, e.g., in Example 5, with sub-
sequent extrusion of a particulate mass of the cogel to provide an extrudate.
Extrusion of cogel of Example 5 can thus be employed to provide extrudates of
1/16 inch particle size diameter having the properties, e.g., of Catalyst XX
as described by reference to Table IV, Examples 10-17.
Once the gel is set by observing conditions which favor the
desired ranges of pore sixe distributions, it :is also important to wash the gel
sufficiently to remove essentially all traces of halides and syneresis liquid.
Failure to accomplish this removal will result in a loss of the developed pore
5ize distributions. An alcohol wash has been found particularly effective in
such capacity, the C2 to C6 alcohols, particularly the C3 or isopropyl alcohol,
having been found particularly effective in preserving the developed pore size
distribution throughout the subsequent steps required in completing the pre-
paration of the catalysts.
The actual water content of the alcohol used in the wash was
found to have a profound effect Oll the pore size distributions, the surface
areas and pore volumes of the catalysts, and on subsequent drying it was found
that these properties vary dependent on the amount of water, if any, contained
in the alcohol wash. As with the syneresis liquid, iE the wash alcohol contains
- 31 -
.
water, the pore volume shrinks with only minor ~ttendant reduction in surface
area. The result is a reduction in the average size of the pores. Thus,
because water decreases pore size distribution and pore volume, it is generally
preferred to use anhydrous alcohol for catalyst preparations. The following
examples demonstrate the effect oE water on these properties, especially on
pore volume and pore size distributions in the alcohol washing and drying
sequence.
.
'
.
32 -
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-- 33 -
.. : .: . : ., : . .. , . :...... : .. :
- .. : . :,, . , . :. : ` .. . . .. :
.' ' ;. . : . ' .. .. ' - ~.. ' - ::
xample 8
A series of gel type catalysts (-tl, I, J, K, L) was prepared,
the preparation steps employed and the composition of these catalysts being
similar to that previously described with regard to Catalyst B, except that
these catalysts were aged somewhat longer during the period of gellation. In
the preparation of these catalysts, except as regards Catalyst H, however, water
in varying concentrations was added to the isopropyl alcohol used as a wash.
The results of these runs are tabulated as follows:
T~BLE II
Catalyst H I J K L
H20 in Alcohol (Vol.%) o 2.5 5 10 25
Surface Area, m2/gm 382 393 398 373 354
Pore Volumej cc/gm 2.07 1.93 1.82 1.59 0.92
~vg. Diameter, ~
(4 PV/S~ x 104) 217 197 J :L83 112 104
These data thus show that, with isopropyl alcohol, pore volume
is decreased as the water content of the alcohol increases Erom 2.5 to 25 per-
cent (vol.) with only nominal change in the surface area. The result is to
decrease the average size of the pores.
The presence of water is also Eound to decrease the pore volume
and pore size distributions during the impregnation steps, wherein the hydro-
genation-dehydrogenation and other catalytic componen-ts are added to alumina
supports, For best results, it has been found desirable to add the metals by
impregnation of the supports with nonaqueous solutions of the metals salts,
preferably alcohol solutions. Water, however, should not be used. The presence
of wate~ has been found to decrease both pore volume and pore slze distribution
drastically. It is thus believed that water enters the pores, redissolves and,
,
- 34 -
" '
'
, : i , ,. , ; . : , .. ,: ,: ,
' :'' ' ' ' . ' ,` ' ., ' , .' ,'~ ~' ' ' ' ., " ' ' :;' .
during drying, some of the redistributed alumina ~orms deposits within the pores.
Thus, some shrinkage of the previously developed pore sizes results from the use
of water during the impregnation step and hence its use is preferably avoided.
The following example thus presents data showing preparation of a cobalt-moly-
bdenum on alumina catalyst by impregnation of a suitable alumina support with a
metals-containing methanol solution. Comparison is made between the surface
area, pore volume and pore size distribution of the catalyst and the unimpregna-
ted support from which the finished catalyst was made.
Example 9
Alumina prepared pursuant -to the procedure used in preparation
of Catalyst E was split into two portions, one, a precatalyst or support, termed
for convenience Catalyst 0, and a second 100-gram portion, termed Catalyst P,
which was impregnated with a solution containing 32.4 grams of CoC12.6H20 and
47.6 grams of phosphomolybdic acid dissol~ed in 162 cc of methanol. Catalyst
P was subsequently dried at room temperature and at 190F. and then calcined
for 2 hours at 1000F. The two catalysts are compared in Table II, as follows:
Catalyst 0 P
Wt. % CoO -- 6
Wt. % MoO3 -- 20.5
Wt. % P205 -- 1
Surface Area, m /gm 336 246
Pore ~olume, cc/gm 0.99 0.61
Pore Volume, Distribution
% in 50~ Pores -- 3.7
50-150~ Pores 95.3 59.4
150-250~ Pores 4.7 31.9
250-350~ Pores -- 4.7
350~ Pores -- 0 3
These data thus show that considerable pore volume shrinkage
occurred, particularly in the 50-150~ pore diameter ranges even as a result of
using alcohol. This shrinkage must be compensated for by forming in the gel or
cogel pores o~ larger pore size distribution than ultimately desired realizing
- 35 ~
.
.
.
~6~
that the shrinkage shall constitute a compensating factor. The shrinkage can be
further minimized by using C2 to C6 alcohols, preferably isopropyl alcohol,
as the solvent.
~ he following examples and demonstrations describe preparation
of a series of extrudates from cogels (and gels), and define certain critical
features required to obtain extrudates of good quality meeting the requirements
Df R-l and R-2 catalysts. The technique of making catalys-ts in the form of
extrudates is particularly applicable to the formation of catalysts in the 1/50-
1/25 and 1/25~1/8 inch particle size ranges, and sphere forming techniques,
particularly as described hereinafter9 are particularly applicable to the forma-
tion of catalysts in the 1/500-1/50 inch particle size ranges. In making
catalysts with the desired narrow pore size distributions, as shown, it is
necessary to limit the time of aging because aging produces shrinkage of pore
size but, on the other hand, aging is essential if extrudates of good strength
are to be made, particularly extrudates of high crush strength, especially crush
strength in excess of 7 pounds. High crush strength is desirable, or necessary,
in certain types of processes. Thus, teclmiques are described which have been
found to speed up the aging process and to counteract the effect of aging which
tends to decrease the pore sizes of the catalysts. The aging process can thus
be carried out by (1) contact of the gel or cogel with syneresis liquid at
ambient conditions for periods ranging to about 30 days, and longer; (~) contact
of the extrudate, or pelleti~ed form of the gel or cogel, for periods ranging
to about 30 days, or longer, in the syneresis liquid; (3) contact of the gel or
cogel in syneresis liquid in an initial step prior to contact of the extrudate,
or pelleti~ed form of the gel or cogel, in syneresis liquid, as described in
(1) and (2), which is preferred; (4) by high temperature contact of the gel or
extrudate (or pelletized form of the gel or cogel), or both, by (5) a combination
of these steps; and (6) Group YIII noble metals, or lanthanum and rare earth
: - 36 -
, ;'; ~ . , ', , 1, '. ' '
:; :~ ", ' ' .
metals of the lanthanum serles, are preferably included in the gellation step to
counteract the pore shrinkage effect of aging on pore size distribution. In
these data, it will also be observed that (7) critical solids contents are re-
quired prior to or su~sequent to certain steps to avoid deterioration or weaken-- -
ing of the gel or extrudate. These include: (a) drying to about 12 40 wt. %
solids prior to extrusion or pelletizing of the gel or cogel, (b) drying to
Z5~ wt. % solids prior to the aging of extrudates, or pelle-tized gel or cogel,
in syneresis liquid, and (c) again drying to 25~ wt. % solids prior to alcohol
washing.
Examples 10-17
Portions of gel, or ~ogel, comprising metals and alumina, were
each prepared by raising the temperature of sols prepared by reaction between
aqueous slurries of aluminum chloride and ethylene oxide as described for the
initial preparation of Catalysts D and D' (Example 5). The portions of cogel
were each used to prepare a series of catalysts defined in Table IV below,
referred to as Catalysts AA, BB, CC, DD, EE, FF (a gel), GG (A gel) 9 XX and YY.
The portions of cogel (or gel) were each aged at 75 F. (except
Catalyst EE which was aged at 160F.), prior to extrusion, in its own syneresis
li~uid for periods ranging from 24 hours (1 day) to 30t days. The portions of
cogel (or gel) were then dried in air for a time sufEicient to provide twenty
percent solids content, based on the total weight o~ the gel. In these cases,
to prepare Catalysts GG, XX and YY, the aged gel (or cogel) was crushed to ~10
mesh particle size before extrusion. After extrusion in a Model 0.810 Research
~xtruder manufactured by Welding Engineers of King of Prussia, Pa., using a
1/16 or 1/32-inch diè, some o~ the extrudates were then further dried in air for
a time sufficient to provide a twenty-five percent solids content, based on the
total weight o~ the cogel (or gel), Some of the extrudates were then returned,
without washing, to the syneresis liquid from which they were originally removed,
- 37 -
~'""' ' '. . . : ,' :' ' .: ,. ' -, . :
i:..... ., ,: . . . . , - :
. . . . ,. . : , , : . . ..
immersed therein and aged at 75F. for one day. The extrudates were again dried
in air to 25 wt. % solids content, then subsequently washed in isopropyl alcohol,
oven dried in air at 190F., and finally calcined at 1000~.
These several portions of gel or cogel, the manner in which
each was treated, and the properties of the series of catalysts, i.e., Catalysts
AA, BB, CC, DD, EE, FF, GG, XX and YYJ produced therefrom, respectively, are : -
referred to in Table I~ below. The table shows, in the first two rows of
figures, the number of days that each of the catalysts was aged in syneresis
liquid prior to extrusion, and the number of days, if any, that each of the
extrudates was aged in syneresis liquid subsequent to extrusion. The next two
rows of figures indicate, respectively, the solids content of the cogel (and
gel) before extrusion, and subsequent to extrusion. The next row of figures,
also given under "Extrusion Conditions" gives, respectively, the percent solids
of the cogel (and gel) prior to the alcohol wash. Isopropyl alcohol was used
as the wash liquid in each case. The last seven rows of figures give the
properties of the several extrudates. The pore diameter, for convenience, is
also listed in terms of average pore size as calculated by the conventional
formula 4 x 10 times pore volume divided by surface area. For the 1/16 inch
extrudate, 175-275~ pores are given where for 1/32 inch extrudates 150-250~
pores are given. As discussed later, these are the important ranges for the
particle sizes.
- 38 -
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- 39 -
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.' . ' . ' ' '~ '" " . ' , ', '. , ' '' ' '', ;',' .,, ' . ""':.;', . " ' ' , " ' '' '' ~'' "' "" ' ", ,'.; ' ''' " ' '
-
These data show that Catalyst ~A possesses a reasonably good
pore size distribution in that it has low pore volume in the 0-50~ pores and
350~+ pores and reasonably good pore volume in 175-275~ pores. It also has
good surface area and pore volume. Unfortunately, it has low strength~ i.e.,
1.3 lbs., but by allowing the cogel to age for 3 days prior to extrusion
(Catalyst BB), the strength can be markedly improved to 4.2 lbs. Catalyst CC
demonstrates the shrinkage oE pores when cogel is aged 30~ days prior to
extrusion. The strength is excellent at 10.7 lbs. but the low pore volume
(0.83 cc/g) and excessive pores in the 0-50~ confirm an excessive shrinkage
due to long term aging. Catalyst DD shows that by aging the extrudates in the
syneresis liquid, a catalyst with fair strength is formed (3.7 lbs.). In this
case, however, the 0-50R pores were excessive due to poor temperature control
during ~he sol forming step. It is important to control the sol forming
temperature at 40-50F. to minimize these pores. As shown by Catalyst XX, a
good extrudate is formed (4.4 lbs.) by good sol temperature control and aging
of the extrudates in syneresis liquid. This catalyst had low pore volume in
0 50~ and 350~ pores and high pore volume in 175-275~ pores.
Fllrther improvements in strength can be obtained by aging the
gel (or cogel) at high temperature for short times as with Catalyst EE. By
aging at 160F., a catalyst with 14 lbs. crush strength was formed. However,
excessive pore volume shrinkage occurred resulting in excessive pore volume in
the 0-50~ pores and a low total pore volume (0.92 cc/gm).
Catalysts can also be prepared by first extruding a gel followed
by impregnation of that extrudate with catalyst metals. This is demonstrated
by Catalysts FF and GG. These data are for the gels prior to impregnation.
Good strength was obtained (4-8 lbs.) but pore volume shrinkage occurred. Pore
volume in 0-50~ range is not unduly excessive, however,
- 40 -
.. .. . : .
.. . , .. : .. :
One example of a 1/32-inch catalys~ is given (Catalyst YY).
Strength is below that desired (3.7 lbs.) but for 1/32-inch extrudates it has
a good pore size distribution with minimum 0-50~ pores and 350~ pores and a
large amount of pore volume is 150-250~ pores which are best for 1/32-inch
particles.
Spheres are the preferred forms of catalysts for use in ebullat-
ing beds and slurry reaotors (reaction zones), the size thereof ranging about
1/50 inch particle size diameter, and smaller. Spheres, of course, can be
utilized in a fixed bed (e.g., in particle size diameter ranging about 1/32-
1/8 inch), but most often are utili~ed in ebullating bed and slurry reactors
where particle size diameters most often range 1/32-1/250 inch, and smaller.
A very effective range for spheres in ebullating and slurry reactors is from
about 100 to about 500 micron diameters. There are several known techniques
for forming spheres, to wit: (1) prilling, (2) gelling in a column, (3) centri-
fugal force, (4~ gelling in a sti~red vessel~ or tank, and the like. In the
preferred stirred tank me~hod, a sol (gel or cogel) is heated and aged, while
agitated, in a mineral oil bath generally at temperatures ranging ~rom about
75 F. to about 150 F., preferably Erom about 100 F. to about 125 ~. The amount
of t~ineral oil:sol, on a volume basis, ranges generally from about 5:1 to about20:1, prefer~bly from about 8:1 to about 12:1. The amol1nt of agitation of the
bath, and the height and diameter of the tank, is selected to provide part~cles
of desi~ed size. Such technique is described in greater detail in Examples
18-20, below.
Examples 18-20
Portions of cogel, which contain metals and alumina, or portions -
of gel which contain alumina, were each prepared first by ~orming a sol as
disclosed ln the preparation of Catalysts D and D' (Example 5), and the sols
~ere then added to a stirred vessel containing tnineral oil.
- 41 -
. ' ' .
: : :
.
Ihe preparatlon o~ tiie sols was as described by reEerence to
Examples 1-5, the slurried material formed by reaction between the aluminum
salt and ethylene oxide having been removed from the beakers at temperatures
of about 35F., and the temperature adJusted to about 55-65~. over a period
of one-quarter hour prior to lntroduction of the portion o~ sol into the vessel
containing the mineral oil. The sol was added slowly, i.e., at a rate of about
5-75 cc/min., over a period o~ one-quarter hour to avoid gelling prior to the
introduction.
The amount of mineral oil:sol, on a volume basis, ~as maintained
at 10:1, and the temperature was maintained at 100-150F. Turbine type agitators
using various blade designs were employed, the size of the particles produced
being controlled by blade design, vessel design, and the speed of revolu-tion
(revolutions per minute, RP~) of the blade.
For the formation of relatively small particles (e.g., 100-200
microns) a single blade turbine operated at 250 RP~ proved best. For larger
particles (e.g., 300-400 microns), a six blade turbine at 75 RP~ proved best.
The design of the vessel is critical. It was found that the ratio of the
height of the vessel (H) to its diameter (D), i.e., H/D, should range between
about 1:5-1:2, preferably 1:4 to 1:3. The design of the turbine should be such
; 20 that the impeller abuts the walls and bottom of the vessel. The ratio o~ the
height of the impeller (HI) to the height of the vessel, HI/H, should range
from about 1:2 to about 4:5, preferably fro~l about 2~3 to about 3:4.
It is found that as the sol is added to the mineral oil, small
spheres form in the oil. After completion of sol addition, the agitator is
allowed to continue agitating for at least 30 minutes, preferably for a period
ranging up to 2 hours. During this time, the spheres are gelled. The spheres
are next separated ~rom the oil, and the solids particles either spread out
over a solid sur~ace to age, or surface washed to remove the mineral oil to
- 42 -
., . : . . . . .
.. , , , , . , : ,, .: , . :, , ~, :
, ,,, ,. ~ . ., : . :, . : , ,, , "
avoid agglomeration of the solids particles. Suitably, the spheres can be
surface washed with varsol or isopropyl alcohol, or both, to avoid agglomeration,
but care must be taken to avoid removal of syneresis liquid from the pores as
opposed to mere removal of the surface oil. The spheres are aged for about
1 day. After this, the spheres are washed in isopropyl alcohol, with or without
added an~onia, oven dried at 190F., and then calcined at 1000F. for 4 hours.
Catalysts W , W and WW, so produced, are characterized as
having the following properties:
T~BLE V
Catalyst uu(a) W (b) ww(c)
~ol. of Mineral Oil, cc lO00 10,000 10,000
Vol. of sol, cc 100 1000 1000
Mixing
Turbine 1 Blade 6 Blades 6 Blades
RPM 250 100 100
Gellation Temp., F. 150 100 120
Catalyst Properties
Surface Area, m~~g 278 244 330
Pore Volume, cc/g 0.54 0.49 1.15
Avg. Pore Dia., A 85 80 139
Pore Size Dist., % PV in
0-50~ 1.9
100-200~ 33.8
-- 21.0
Particle Size, microns 100-200 100-500 100-300
, . .. . .
(a) No rinse/No NH3 in wash
(b) Rinse, no NH3 ln wash
(c) No rinse, NH3 in wash
Catalyst W was formed in quantity with a l-blade turbine at
high RPM (250) and high temperature (150F.). The particles were small due to
high RPM and impeller design. The low surface area and pore volume are due to
high gellation temperature (150F.) and the fact that NH3 was excluded from the
isopropyl wash. Catalyst W was made in a larger vessel with a 6-blade impeller
operated at 100 RPM and 100 F. The catalyst spheres were rinsed with varsol
- 43 -
. .
.
and isopropanol in this case to avo~d ~gglomer~tion, and no ammonia was included
in the wash. Due to the lower P~M and impeller design, particle size was in-
creased to 100-500 microns. Due to the improper rinse (i.e., varsol and iso-
propanol pretreated spheres prior to aging) and the lack of NH3 in the wash,
the surface area and pore volume are lower than desired. Catalyst WW represents
an excellent spherical catalyst prepared by this technique. By forming the
spheres in the larger vessel using the 6-blade turbine at 100 RP~ and 120F.,
spheres ranging in size from 100-300 ~icrons were made. Further, by carefully
handling the spheres before aging to avoid agglomeration without the use of
varsol and isopropanol rinse, the resulting spheres possessed good surface
area and pore volume. In addition, 50~ pores and 300~ pores were minimized
while maximizing 100-200~ pores which are highly desirable for particles in
this size range. By decreasing the RPM to 75, particle size is further in-
creased to 300-400 microns.
Exam~
Runs were conducted with each of Catalyst D, Q and R, of l/3~
inch average particle size, by contact with Cold Lake and Jobo Crudes, respec-
tively, in a reactor which contalned the catalysts as fixed beds. The runs
were each conducted at two different temperature levels, at approxima~ely the
same pressure level of 2250 psig, at two different flow velocities and at
hydrogen rates varying between 5500-8500 SC~/B. The following Table ~III shows
the product inspections at the end of two different time periods, the conditions
of reaction being given at the time the products were withdrawn for analysis.
Shown immediately below in Table VI are the analyses for Cold
Lake and Jobo cru~es. In addition, the catalyst inspections for Catalysts Q and
R are given in Table VII. Catalyst 0~ is a commercially available hydrodesulfur-
ization catalyst having most of its pore volume in the 0-lO0~ region. Catalyst
R was made in a manner similar to Catalyst D but with longer aging of the gel.
- 44 -
.~ '. .
:: , ,, . . . ; . . . , . . .:
:: ~ ~: - ... . . .
. : . , ~:. . .
.:: ' .
TABLE VI
FEED ~N~LYSES
Cold Lake Crude Jobo Crude Kuwai-t Resid.
Gravity, API 11.1 8.5 16.5
Sulfur, Wt. % 4.5 3.8 3.6
Carbon, Wt. % 83.99 83.92 84.64
Hydrogen, Wt. %10.51 10.49 11.41
Con.Carbon, Wt. % 12.0 13.8 9.0
Asphaltenes, Wt. % 17.9 17.7 --
Nitrogen, Wt. %0.46 0.68 0.22
Metals, ppm
Ni 74 97 12
V 180 459 58
Distillation, l mm
IBP, F. 463 518 451
5% (Vol.) 565 627 577
622 682 648
712 '798 737
817 895 805
916 978 865
1019 1037 937 -
% Recovered 56.4 50.8 64.0
% Residue 42.4 48.2 36.0
FBP, F. 1047 1047 1047
TABLE VII
.~
CATALYST INSPECTIONS
Catalyst R Q
Surface Area, m /g 362 260
Pore Volume, cc/g 1.79 0.50
Pore Volume Distribution,
% Pore Volume in
0-50R Pores 1.4 11.1
50-150R 10.9 79.5
150-250~ 17.6 6.1
250-350~ 23.4 1.8
350~ 46.7 1.5 ; -
% CoO 6 3.5
% ~oO3 20 12.0
- 45 -
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~ ~ o ~ ~ C~ o ~ ~ C~ ~ l
`D ~ ~D ~ ~ ~ ~
~ O . ~0 ~ 1--~ . . ~ .
L~ ~ I--00 ....... 0~ ~ I . I~
O O ~D ~ ~ ~ I
o~ ~
Ln ~ Ln ~ Ln a~ ~ -
o a~ oo ~D CO
~D O ~ ~ ~i O ~ ~ I` ~ I
rl r~ I~ `D O ~ CO ~
o ~ .
Lr~ . ~~ . . . ~ , ~ ,~
~ I~ o a~ ~~ ~ _I
H u~
H ~ ~ Ln
.u .~ ~ ;r ~
r ~i o ~Ln ~1 1
~-1 00 a~ L~n Ln Ln ~ O
o ~ o a~
n ~ oo ~r ~o a~
r~ I o o ~ ~ ~ ~ c~J
JJ
P ~ o c~ ~;r ~- ~ ~ ir
~ cr ~ r -
..,~ Ln ~ ~ ~ . . o ~ O ~ I
~ ~ O ~ ~ C~ O ~r o~
:
?,~
.
~, ?,~
?,~ ?,~ ~ .
rl P 5
P:l L~ rl ?i~
P ri 1--1 ?,~r-l JJ do
14 ~ h ~ ~ 5 d U~ E~ d ~ ~ ~
O P ~ ) ~ aP 1~ A ~d
~ ~ ~ (IJ +
P~ . O
~ o ~ri a ~ ~ ~ ~ -
:~ r~ O 1--1 r ~ rl O O ~ O
~ ~ V a ~ ~ æ P Ln Ln ~
)-I O ~ ~ ~r O ¢ ~ O O
rq ~
E~
:
'- 46 ~- :
. ~
, .,
:, ,.. , . :, , . . ., . . : .
~5~
These data thus show that Catalyst Q, the commercial hydro-
desulfurization catalyst, is completely unsuitable for the treatment of these
heavy crudes at hydroconversion conditions, although Catalysts D and, to a
lesser extent, Catalyst R are well suited for such purpose. Whereas Catalyst
Q does efFectively hydrodesulfurize the cured in some cases, the data clearly
show that it is entirely unsuitable for removal of heavy metals, for the
reduction of Con. car~on, and for the conversion of asphaltenes.
In other comparative runs, for purposes of demonstra-tion,
Kuwait residua, a more conventional crude characteriæed as a light ~rabian
eedstock, the inspections on which are given in Column 4 of Table V, above,
Catalyst Q and Catalyst D were compared at similar but varying conditions in
hydrodesulfurization reactions with the results described in Table IX, below.
T~BLE I~
Temperature, ~. 650-750 F.
Pressure, psig 2000
Hydrogen Pate, SCF/Bbl. 4000
Catalyst Q Catalyst D
Days on Oil 26 26
~verage Temperature, F. 710 710
Space ~elocity, V/Hr./V 0.4 0.6 0.4 0.2
Product Ins~ections
Gravity, ~API 24.8 22.7 23.6 24~1
Sulfur, Wt. % 0.25 0.64 0.45 0.28
Nickel, ppm 5.3 2.7 1.1 0.2
Vanadium, ppm 12.5 5.4 2.3 1.7
Nitrogen, Wt. % 0.09 0.17 0.16 0.14
.
These data sho~ that Catalyst Q is better for desulfurization
(and denitrogenation) of a light feedstock than Catalyst D which is less satis-
factory. However, the catalyst of the invention (Catalyst D) is superior in
metals removal even for this light feed.
- 47 -
Example 22
Diffusion plays a very l~portant role in the conversion of
asphaltenes and removal of nickel and vanadium from heavy crudes. This is due
to the larger size of the diffusing molecules. Since sulfur is found in smaller
molecules, the sulfur removal reaction is much less restricted ~y diffusion.
This is demonstrated in the following example. A catalyst was prepared in a
manner similar to that used in the preparation of Catalys-t D. This catalyst
is designated Catalyst AAA. Properties of this catalyst are given in the
table below:
CAT~LYST AAA
Surface Area, m /g 366
Pore Volume, cc/g 1.33
Pore Volume Distribution, %
0-50~ Pores 4-3
50-100~ 10.0
100-150~ 13.3
150-175~ 5.2
175-200~ 6.5
200-250~ 13.4
250-275~ 6.3
275-300X 6.9
300-350~ 9.7
350~ 24.7
CoO 6
~ ~1003 20
~ This catalyst was divided into three parts, each crushed, and si~ed to provide
particles having average diameters equal to 1/85, 1/43 and 1/29 inch, respec-
tively. Each of these catalysts was loaded into reactors and used to hydro-
convert Cold Lake Crude~ the properties of which are given in Table VI.
Conditions for the tests were 775 F., 2250 psig, 2.6 V/Hr./V and 6000 SCF/B
hydrogen gas rate. ~roduct inspections were obtained after 20 hours on oil
and are shown below:
.
- 48 -
'. - . ' ~ .,~, ' ' . ~. .
~, : : . :
Catalyst Size, Inch 1~85 1/43
Sulfur, Wt. % 0.37 0.37 0.40
~sphaltenes, ~t. % 1.1 2.3 3.5
Nickel, ppm 3.1 5.9 11.2
Vanadium, ppm 1.0 9.0 19.1
These data show that the asphaltene, nickel and vanadium removal reactions are
strongly dependent upon catalyst particle size indicating strong diffusion
limitations. On the other hand, sulfur appears to be much less dependent upon
particle size. It is found from these data that as particle size increases it
is desirable to increase the size of the pores to decrease the diffusion
limita-tions with larger particles. On the other hand, as particle size is
decreased it is desirable to decrease the pore size, since less diffusion
resistance will be encountered. ~hus, larger particles (e.g., 1/16 inch) will
require larger pores (e.g., 175-275~) and smaller particles (e.g. 1/64 inch)
will require smaller pores (e.g., 100-200~) while intermediate particles (e.g.,
1/32 inch) will require intermediate po~es (e.g., 150-250~).
The following examples show that R-l catalyst can be used to
treat 1050F.~ in heavy crudes or residua at a variety of conditions ranging
~rom hydrotreating, with minor canversion of the 1050 F.~ materia1s~ through
hydroconversion conditions wherein a major amount o~ the 1050 F.~ material is
converted to lower boiling products.
Examples 23-29
Catalyst D, the R-l catalyst o~ Example 5, having an average
particle size of 1/32 inch, was used for treating Jobo Crude (Table VI) in a
series of runs wherein the severity of the reaction was gradually increased
principally by a combination of decreased space veloclty and increased tempera-
ture to obtain increasing rates of conversion. In Examples 23-26 the start-of-
run (SOR) temperature was set at 650F., and gradually increased during the
operation to maintain a given reaction Xate. In Exa1nples 27-29 the start-of-run
- 49 -
.
:.: . .
,: ;: ~ , : .
. . , , . :
:. ," ,. , "
~Si6~
temperatu~e Was 700F. These ~nd other conditions o~ operation of the several
runs, and t~e inspections obtained on the products of the series of reactions
are given in Table X, below. Data a~e shown for Examples 23-26 at 662F. after
517 hours on oil. Data for Examples 27~29 are at 736F. after 805 hours on
oil. In this series o~ runs, Examples 23 through 26 can be considered as
essentially hydrotreatin~ runs, and Examples 27 through 29 as hydroconversion
runs.
T~BLE X
Pressure, psig 2250
Hydrogen Rates, SCF/Bbl. 6000
Temperature, F. ~SOR)
Examples 17-20 650
Examples 21-23 700
~xample No. 23 24 25 26 27 28 29
Space Vel.,
VlH/V 0.79 0.59 0.39 0.19 0.98 0.49 0.24
Product
Inspections
Gravity, API 12.4 13.4 14.1 16.0 15.4 18.1 21.4
Sulfur, Wt. %2.56 2.23 1.87 1.11 1.45 0.78 0.15
Nitrogen, Wt. % 0.65 0.62 0.60 0.55 0.56 0.49 0.26
Con. Carbon,
Wt. % 10.4 11.0 10.3 7.9 8.3 6.3 3.8
Asphaltenes,
Wt. % 10.6 10.0 9.3 5.4 7.8 4.2 --
Metals 9 ppm
~i 52.2 48.2 38.9 29.5 28.3 16.1 5.1
V O 242.6 207.2 183.0 107.5 1~l3.4 72.0 0.8
1050 F.~, Conv.,
Wt.% 1~.8 12.2 7.5 13.4 21.9 33.4 46.6
1050F.
Quality
S~lfur,Wt. %3.47 3.09 2.83 1.89 2.51 1.49 0.30
Con.Carbon,
Wt. % 23.3 22.7 20.4 17.5 21.3 18.4 10.4 ~-
Metals, ppm
Ni 108.6 112.5 97.9 65.4 86.2 59,0 8.7
504.4 476.0 391.5 248.3 341.5 196.8 9.5
~e~al on Cat.
Wt.%* 115 60 75 -- 168 100 --
*Wt. % on ~esh catalyst at end o~ ope~ation.
- 50 ~
.,
.. , , ~ . . , . : .~ . ........... . .
., . . , . , ~ , ..
These data thus show that relatively high temperature i9 required
to obtain high rates of hydroconversion of the 1050 F.~ materials, and con-
versely that low temperatures cannot provide adequate conversion rates, even
with relatively low space veloclties. The product of Examples 23 through 26
is unsuitable for coker feed because the metals content is too high, and un-
suitable even as fuel because of the high sulfur content. The product of
Example 26 is of marginal utility as a coker feed, but coke produced from such
product would necessarily be of poor quality. The sulfur content is too high
for use as fuel, and further treatment is required to render the product
suitable as a fuel oil. As to the series of hydroconversion reactions, the
data show that the product of Example 29 is of good quality, and even suitable
as a feed for a resid catalytic cracker using amorphous silica~alumina catalysts.
The product of Examples 28 and 29 can be split into 1050~.~ and 1050F.-
fractions, and the 1050F.~ fraction coked as presented in Example 30 below.
Best use of the Example 28 product requires that it be treated in R-2 service
to obtain a material having from 2 to 3 wt. % Con. carbon and <5 ppm metals,
preferably C2 ppm metals, which material can then serve`as a prime feed for a
conventional hydrocracker or catalytic cracker. The product of Example 29 is
a marginal feed ~or a conventional hydrocracker or catalytic cracker. The
product o~ Example 29 is a prime feed for a resid catalytic cracker as pre~
sented in Example 38.
The product of Example 27 is marginally suitable for R-2 service
or as a marginal feed for use in a coker. None of the products of Examples 27 ;~
through 29 is suitable for direct use in a conventional hydrocracker or catalytic
cracker.
The following example illustrates certain advantages in use of
the product of Example 29 as coker ~eed.
51
~,
, . ; ::
Exam~le 30
Case A: ~obo crude was split into two fractions, 1050F.+ and
1050F.- fractions. Yields for coking the 1050F.+ ~raction were predicted
using correlations. The total yields were then calculated by mathematical
blending.
Case B: The Example 29 product was separated into 1050 F.+
and 1050 F.- ~ractions. Yields for coking the 1050 ~.+ ~raction were predicted
using correlations. The total liquld yields were calculated by mathematical
blending.
The results o~ these calculations are given in Table XI below:
TABLE XI
Basis: 50 MB/~ o~ Jobo Crude
Case ~ Case B
-
C3, M Lb./D 0.87 0.4
C4, B/D 893 777
C5/430 F., B/D ~,434 3,446
430/650F., B/D 8,323 11,950
650/1050F., B/D 28,108 31,703 -
Coke, T/D 1,223 (5.9% S) 373 (2.5% S)
C3 Yield, Vol. % 86 97
These comparative data show that the C3 volume percent yield
of product is 97 ~hen coking the 1050 F.~ product of Example 29 vis-a-vis the
86 C3 volume percent yield obtained when coking the 1050F.+ material o~ the
Jobo crude per se, an 11 volume percent improvement in C3+ liquid yield.
Moreover, both the coke and the liquid product resulting from coking the
Example 29 1050 F.+ material vis-a~vis the 1050 F.+ material from the original
Jobo crude is superior.
` - 52
,-. '.
... . . . . . . . . .
The following presents a series of runs which show -that products
can be produced Erom 1050F.~ heavy crudes and residua by reaction with an R-l
catalyst which are admirably suitable as feeds for R-2 ser~ice. In the follow- -
ing series of data, the initial temperature of the several runs is further
increased as contrasted with the runs of preceding Examples 27 through 29. The
space ~elocity is then gradually decreased, and as space velocity is lowered,
it will be observed that product quality improves.
Example 31
A series of runs, vi~., Example 31, Runs 1-4, was conducted
using an R 1 type catalyst, identical to Catalyst D previously described
(Example 5), except that the catalyst contained 0.35 wt. % Sn (by impregna~ion)
in addition to cobalt and molybdenum. Again particles averaging 1/32 inch
diameter were used. Jobo crude (Table V) was contacted in each instance with
the catalyst at a start-of-run temperature of 760F., the temperature being
increased during the operations at an average rate of from about 1.8 to 2.2 F.
per day to maintain a substantially constant rate of reaction for a given run.
The following data, given ln Table XII, below, were obtained at a temperature
of 765F. after 166 hours on oil.
- 53 -
.~ . .
., . ' . ' ,, , ,, ' ' .
~-~t
TABL~
Pressure, psig 2250
Hydrogen Rate, ~C~/Bbl 6000
Run No. 1 2 3 4
Space Velocity
V/Hr./V 1.90 1.45 0.91 0.46
Product InsPection
Gravity, API 17.3 17.3 18.5 20.7
Sulfur, Wt. % 1.29 1.08 0.80 0.20
Con Carbon, Wt. % 7.6 7.0 7.1 4.0
Asphaltenes, Wt. % 6.1 6.2 4.8 1.9
Metals, ppm
Ni 29.2 24.8 17.~ 2.7
V 26.1 93.9 46.9 0.9
1050+F., Con~.,
Wt.% 44.3 38.2 43.5 56.6
1050+F., Quality
Sulfur, Wt. % 1.98 1.81 1.48 0.43
Con Carbon, Wt. %26.0 21.7 24.3 17.2
Metals, ppm
Ni 96.8 73.5 64.5 20.6
V * 3630~ 308.0 189.0 1.5
Metal on Cat~, Wt.%69 88 91 46
*Wt.% on fresh cat at end o~ operation~ ~uns terminated at different times
on oil.
It is thus apparent by reference to Runs 3 and 4, as contrasted
with Runs 1 and 2, ~hat temperatures above about 750 F., at space velocities
about 1, can provide an R-2 feed of desirable quality. Suitably, the R-2 feed
~ is about 90 Wt. % demetalli~ed, and hence the product of R-l service is usually
one containing metals below about 60 ppm, which metals content can be further
reduced in R-2 service to 5 ppm or less. Also, Con. carbon at levels o~ about
7 Wt. % can be reduced to levels ranging about 2-3 Wt. ~ as required for use in
R-2 service. In operating at these condltions, the ~-1 catalyst was found
suitable for about 3-4 weeks of continuous R-l ser~ice.
The product of ~xample 31, Run 4, on the other hand, can ba fed
directly to a catalyticcracker employing zeolite catalyst as shown by reference
to Example 38, if desired. The product produced in Example 29, described by
.. .. .
~5~
reference to Table X, is a ~ri~e feed ~o~ resld caLalytic cracking as shown
in Example 38.
Example 32
Several catalysts of varying pore si~e distribution were
obtained for demonstrative purposes. Catalysts S and T are commercially
available alumina which was impregnated with cobalt and molybdenum salts and
then dried and calcined at conditions similar to that used in Example 9.
Catalyst V, the catalyst of the invention, was pre~ared in a manner similar
to that used for Catalyst D described by reference Example 5. A portion of
each having an average particle size of 1/32 inch was then employed in a fixed
bed reactor for hydroconversion o~ whole ~obo crude to measure the effective-
ness of each in R-1 service. The pore size distributions of each of these
several catalysts, termed Catalysts S, T, U, and V for convenience, the conditions
under which the hydroconversion runs were conducted, and product data are tabu-
lated in Table XIII, as follows:
TABLE XIII
(a) ~escription of Catalysts:
Catalyst S T U V
Surface ~rea, m2/g 250 217 259(()) 362
Pore Volume, cc/g 0.55 0.53 0.58 1.51
Pore Volume Distribution, %
.
0-50~ Pores 4.3 10.7 5.0 2.8
50-150~ 73.8 33.0 40.5 15.7
150-250~ 12.2 22.6 33.1 25.2
250-350~ 5.4 16.8 15.~ 27.3
35 ~ 4.3 16.9 6.1 29.1
% CoO 3 3 r 6 6
% MoO3 13 21~- 20 20
(b) Process Conditions:
Temperature, F. 789 (after 665 hours on oil,
750 F. SOR)
Space Velocity, V/Hr./V 1.0
Gas Rate, SCF/BBl 6600
- . . . .
- . : , , :, . :, ..
:: . ''. .' . ~ . ' ' , '
,; , , : . .. . .
-
~5~
(c) Product Inspections:
Catalyst S T U V
Product Inspection
Sulfur, ~t. % l.l63 1.254 l.588 1.074
Metals, ppm
Ni 27.9 28.1 23.8 21.1
V 72.1 83.1 49.9 38.0
Metal on Cat., Wt. %* 43 41 62 99
(1) Data obtained from pore size distribution measurement due to problem
with single point nitrogen measurements for surface area and pore volume.
* Wt. % on fresh cat at 665 hours on oil.
- These data thus show that Catalyst V, an R-l catalyst, which
inter alia, contains greater than 20% of its total pore volume in the 150~ to
250~ range, less than 5% of its pore volume in 0-50~ pores and less than 30%
of its pore volume in the 350~ range, is far superior to the other catalysts
none of which are R-1 catalysts, in terms of both sulfur and metals removal,
but particularly as relates to metals removal, in terms of metals removal an
average of about 35% less of Catalyst V is required to remove the same amounts
of metals as would be removed by the other catalysts.
The following example shows that as total pore volume in the
150-250~ range is increased, the catalyst becomes even more effective in terms
of removing metals.
Example 33
The following data are illustrative of that obtained from two
different R-l catalysts, one (Catalyst W) of which contains 56.7% of the pores
in the 150-250~ range and the other (Catalyst D), also described by reference
to Table I except that it contains 0.3 wt. % Sn, by impregnation) of which
contains 44.1% of its total pore volume in pore sizes ranging 150-250~. Each
is used at similar conditions for the hydroconversion of Cold hake Crude
(Table VI). Catalyst W was prepared similarly to Catalyst C except that La was
~ - .
- 56 -
: : , - :
'. ' . ' '. ., , . :.. , - , ~ : ,, .
- - \
not included. The gel was impregnated by the methods of Example 9. Both
catalysts were constituted of particles averaging 1/32 inch diameter. The
description of these catalysts in terms of their pore size distributions, the
conditions of the run and the inspections on the products from the runs are
given in Table XIV below:
TABLE XIV
(a) Description of catalyst:
Catalyst 2 _ W ~1~ D
Surface Area, m /g 271'(1) 330
Pore Volume, cc/g 1.22 1.23
Pore Volume Distribution, %
0~50~ __ 1.5
50-150~ 3.0 15.5
150-250~ 56.7 44.1
250-350~ 25.3 33.0
3502f 15.0 5.9
% CoO 6 6
% MoO3 20 20.5
(b) Process Conditions:
Temperature, F. 750 F. (210-240 hours on oil)
Pressure, psig 2250
Hydrogen Rate, SCF/Bbl. 6000
Space Velocit~, V/Hr./V 0.5
(c) Product Inspections:
Catalyst O W D
Gravity, ~PI 23.4 24.0
Sulfur, Wt. % 0.16 0 09
Con Carbon, Wt. % 2.5 2.1
Asphaltenes, Wt~ % 0.9 1.2
Metals, ppm (Ni and V) 2.0 5.8
1050F.f
Sulfur, Wt. % 0.29 0.26
Con Carbon, Wt. % 8.0 9.7
_etals, ppm
Ni 1.7 6.6
V 4.7 ~ 9.3
(1) Data obtained from pore size distribution measurements due to problems
with nitrogen measurements for surface area and pore volume.
- 57 -
. .:,::, . ., . : . .,
. . ` .
; , ~ : , . , :. ; - ,
, : ' . ': . , . : ,
: -`
3S~
The advantages of maximizing pores within t~e 150-250X pore
diameter range for demetallization is thus clearly illustrated. Catalys-ts
similar to Catalyst W, but with higher pore volume in the 150-250~ pore dia-
meter range, and greater surface area, provide even greater improvements.
The following additionally shows that a Group IV~ metal is
effective in increasing the rate of demetallization of the catalysts of this
invention.
Example 34
Two catalysts were prepared, each at the same conditions and
identical in composition one to the other~ except that one contained 3 wt. %
germanium by impregnation and the other did not. These catalysts, identified
as Catalyst V and V', are similar in their composition (except as to the
presence of germanium in Catalyst V~) and in their physical characteristics
as relates to pore ~olume and pore size distribution, and method of preparation
which is the same as that of Catalyst D identified by reference to Table I.
A~erage particle size for both catalysts was 1/32 inch. Each catalyst was
employed for the hydrocon~ersion of Jobo crude, at conditions very similar to
those used in Example 32 to provide products as identi~ied in Table X~, below:
TABLE ~V
.
Process Conditions:
Temperature, F. 778 F. (496 hours on oil)
Pressure, psig 225
Space Velocity, V/H/V 1.0
Hydrogen Rate, SCF/B 6000
Catalyst V V~
Promoter ~ None 3% Ge
Product Inspection
Sulfur, Wt. % 1.098 1 308
Metals, ppm
Ni 19.4 14,6
V 34,1 23.
- 58 -
- , . . .. . ~, . - - . . : .... . ... . . .
. ~
The rate of demetaIlization o~ Catalyst V' used for hydro-
conversion of the crude is thus appreciably increased as contrasted with
Catalyst V which does not contain the germanium promoter.
The following examples are exemplary of an ~-2 catalyst of pre-
ferred composition, the catalyst being described as used in a typical R-2
service situation for hydroconversion of an R-l product resultant from the
treatment of a whole Jobo crude by contact with R-l catalyst as typical R-l
service conditions. The performance of the R-2 catalys~ is compared with an
R-l catalyst for similar use, and with a commercially available catalyst in
similar service.
Example 35
Runs were made wherein whole Jobo crude (Table VI) was intro-
duced into an R-l reactor containing a fixed bed of R-l catalyst (Catalyst V)
and treated at hydrocon~ersion conditions, the R-l product produced being
defined in Column 2 of Table ~VI, below:
T~BLE X~I
(a) Conditions o~ Operation:
R-l Reactor:
Temperature, ~. 750 ~SO~)
Pressure, psig 2250
2 Hydrogen Rate, SCF/Bbl. 600V
Space Velocity, V/H/V l.O
(b) R-l Product:
Gravity, API 16.8
Sulfur, Wt. % 1.40
Carbon, Wt. % 86.44
Hydrogen, Wt. % 11.25
Con.Carbon, Wt. % --
~sphaltenes, Wt. % 5.49
Metals, ppm
Ni 24.6
V 39.7
Nitrogen, Wt. % 0.577
- 59 -
TABLE XVI (Cont'd)
Distillation~ Wt. %
IBP 300
5% 4S5
515
600
675
747
825
g44
% Recovered 65
% Residue 35
FBP 1047
The R-1 product, characteri~ed in Table XVI (b), was then
successively passed over Catalyst V ~Example 34), having particles averaging
1/32 inch diameter, at a start-of~run temperature of 750F., 6000 SCF/Bbl H2,
2250 psig and with space velocities varying from 0.49 to 1.93 V/Hr./V. Data
shown in Table XVII are for products withdrawll from the reactor at 755F. after
161 hours on oil.
TABLE XVII
V/Hr./V 0 49 0.83 0 95 1.93
Product Ins~ections
Gravity, API 23.5 19.8 18.3 17.5
Sulfur, Wt. % 0.10 0.38 0.71 1.05
Asphaltenes, Wt. % 0.86 2.48 3.88 4.32
Metals~ ~pm
~i 1.7 9.5 1406 18.0
V 0.1 0.3 5.7 37.3
These results show that the R-l type of catalyst is not ideally
-~ suited for ~2 service. High temperatures and low space velocities are required
to reach the R-2 catalyst target of < 5 ppm metals and 2-3 wt. % Con. carbon
~< 1 wt. % asphaltenes).
A catalyst with-maximum pores in the 100-200~ range is preferred
for ~-2 service as shown in the next example. In addition, it is preferred to
operate at lower temperature where equilibriam ~avors aromatics saturation
enhancing Con. Carbon removal.
- 60
' :'' ', ':" ' "' ''' ' ' "' ' ' ' ,,',' ~' ', "'''"'.."' '. ' ' ,'.".' ' .'' ' ' "' '. '' ' ' "~' .'' ' '','`'' . ''
: , ' : .. .i . ' ' '; . " " '. ~ ' ' ' ~ " : ' ' ' '
, :. : . ., . , . :. .: , . , . ,: : :.
. . . . ..
Example 36
The R~l product characteri~ed in Table XVI ~b) was successively
passed over Catalyst V and a commercially available hydrotreating Catalyst V
and a commercially available hydrotreating Catalyst X which is characterized
in Table XVIII (a). The catalysts, averaging l/32 inch in particle diameter,
were evaluated at a start-of-run tempe~ature of 700 ~., 6000 SCF/B H2, 2250 psig
and 0.5 V/Hr~/V. Data shown in Table XVIII (b) are for products withdrawn
from ~he reactor at 700F. after 93 hours on oil.
T~BLE X~III
(a) Description of Catalyst X
Surface Area, m /g 222
Pore Volume, cc/g 0.58
Pore Volume Distribution, %
0-50~ Pores 1.6
50-l00~ 32.9
100-200~ 51.8
200-300~ 9.0
300~+ 4.7
% NiO 3.0
3 18.0
~b) Characterization of R-2 Product
Catalyst X V
Product Inspection
Gravity, API 20.7 19.8
Sulfur, Wt. % 0.207 0.282
: Asphaltenes, Wt. %0.83 1.29
Metals, ppm
Ni 7.7 8.4
V 0.1 0.1
The data sho~ that the commercial Ni/Mo catalyst with 52~ of its pores in the
100-200~ region is more active for sul~ur, asphaltene and metals removal at the
conditions than the R~l catalyst which has less o~ its pores in 100-200
_ 61 -
1 region.
2 The ca~alyst of th~ inventlon for R 2 sen~ire
3 whereln pores in the 100~200A region are further maximized
4 is shown ~o be super~or to the commercially ~va~lable cata-
lyst (Catalyst X) ln Ex~mple 37O
6 ~
.
7 The R~l product (Table XVI [b~) was successively
8 pa~sed over Catalyst X (Commercial catalyst of Example 36)
9 and Cat~lyst P (Exampl~ 9) 9 having average partlcle size
diameters of 1/32 inch9 ~t 650F. start~of-run temperature,
lL 6000 SCFjB H2, 2550 psig ~nd 0O5 V/Hr./VO Cat~lyst Y is
12 ch~racterized in T~ble XIX (a) and the product inspection
13 for produet withdrawn at 650Fo after 48 hours .on oil is
14 shown in Table XIX.
... .... .. .
TABLE XIX
16 (a) Description of Catalyst Y
17 Surfaee Area, m2~g 212
18 Pore Volume, cc/g 0O43
19 Pore Volume Dis~ributlon %
__ .
0~50~ ~ores 8O1
21 $0~100A 1904
~2 ~00~00~ 58O3
23 200~300~ 13O1 .
24 30~A~ l o l
% Niû 6
26 /0 MoO3 20
27 (b) Char~cteriz~t~on of R~2 Product
~8 ~at~lyst ~ X Y P
29 ~3559b5 ~E~:~l~ .
~ravity, API 1805 1806 1808
31 ~ulur~ Wtr % 00436 00533 00287
3~ Asphaltenes, Wt~% 2~1 2~5 107
33 Met~ls ~m
34 ~ 904 9OO 600 ~ .
V ~8 0O9 0O7
36 These d~t~ thus show the advant~ge for h~ving less th~n 10%~ -
37 of the pore volume ln O~SOA pores ~nd greater th~n 55% of
38 the pore vvlume in 100~200A pores and less than 25% of it~
. .1
~2
.. . . . , . . , ., ,.. , , ~ . . ..
.,
1 pores in 300A+ poresO Catalyst Y wi~h 58% of its pores in
2 the 100~200A reglon sh~ws some advantage for demetallization
3 over Cakalyst X whleh had 52% of its pore volume in 100-200A.
4 poresO Both were NiiMo catalysts~ Cat~lyst P9 a Co/Mo c~t~
- 5 lyst with 58% of its pore volume ;n 100~200~ pores and 3O7%
~ of its pore vol~me in 0~50A pores and 1.6% of its pores in
7 300A-~ pore~ was the most outstanding catalyst for R~2 ser~
8 vice.
The conditions for the R~l reactor c~n be varied
11 ~o yield product whieh is ~uitable for coking~ for resid --
12 catalytic cracking by contac~ with amorphous ~ilic2 alumina
13 (3A)9 for use in z~olite catalytic cracking or for further
14 treatment in the R~2 reactor to produce a product contain~
ing C5 ppm metal~9 preferably ~2 ppm met~ls, with a Con.
16 carbon of less than 3 wt- %. ~he material from R~2 ~ervice
17 i~ suitable for conversion ~n a conventional catalytic
18 cr~cking or hydro~r~cking unit. Results of such runs are
19 summarized in Table ~X~ below.
TABL~ XX
21 Jobo Feed ~ 2250 pSig9 6000 SCFIB H2
22 R~l R-l/R~2
23 R-l R~l Plus Plu~
24 Plu~ Plu~ Zeolytic Zeolytic :~
Proce~s ~ ~ ~ ~L~ clc
.
26 R~l Condition~ ~:
27 SOR TempO,FO ~ 700 700 760 760
28 Space Velocity,
29 V/Hr-/Y G ~ D 0O4 0.25 0O5 1.0
~ uc~
. .
31 Sul~ur3Wt~% 0.6~ 0O32 0O22~ ) 0 D 76( )
32 Metal~ 9 ppm ~ 62 10 5 60
33 Con.Carbon
34 Wto% ~ 5.3 308 4.~ 605
:,
~3
., ~
1 TAB (Continued)
2 R~l R~l/R~2
3 R~l R~l Plus Plus
4 Plus Plus Zeolyt~c Zeolytic
~ 3A C/C C/C C/C
,
7 430Fo~ ~nv.~
8 % ~ 25 80 ~0
9 Catalyst
Addition
11 Rate9
12 Lb/Bo ~ 0 0O4
13 ~ ~ ~i N ee~
V31 % 86 97 97 107 110
1~ Wt.70 1308 404 705(3) 7.5(3) 6.7(3)
18 Su~ in
19 Cdke,
7.0 Wt.% 5 .9 2 o5
21 (1) Analyses averaged fo.r total run3 life expected to be
22 greater than 2 mvnths.
~3 (2) Analyse~ averaged for total run, life expected to be
24 3~4,wee~.
(3) Cok~ m~ke on cat Cracking (C/'C) catalyst.
26 These d~ta show that coking of raw Jobo crude
~7 result~ in 86 vol. % yi~ld of C3+ and a,l3.8 WtJ ~/0 y~el~
28 of sour coke (509% S~0 When the crude is treated in R~l st
29 700Fo and at 0~4 V/HrO/V09 the product is a prime coker
feed~ Coking the feed increases the C3~ yield to 97 volO%
31 and reduces the coke to 404% ~2.5% S)u ~ublished dat~ and ~ ~-
32 correlati~ns show that if the sever~ty of R~l is lncre~sed
33 by reducing the space veloclty to 0~25 V/HrO~V~ the product
34 is then suit~ble for re$id c~ta1ytic cr~cking us~-ng ~m~r~
phous S102/A1203 catalyst~ The yields produced are 97 vol.%
36 C3~ and 7.5 wto% cokeO If the severity of R~l i9 furth~r
37 increased to 76~F~ and 005 V~HrO~V/ khe product is suit~
38 able for c3taly~ic cracking using zeoli~e cracking cata~yst.
39 In this i~stance9 the yields produced are 107 vo10 % C3+
and 7.5 wt~ v~O coke. Moreover9 using the preferring re~c~n
, . . . . . . . . .
.. ..
1 sequenees of R~ltR~2 ca~alysts3 this product can be cata
2 ly~ically craeked using zeolite catalysts to produce yields
3 of llO volO % C3 and 6~7 wt. % coke D These results show
4 the wide versa~ility and capabllities of these catalysts and
- 5 processes.
6 It is ~pparent that various modifications and
7 changes can be made wlthout departing the spirit and scope
8 of the present invention.
9 Pore size distributions9 as percent of total pore
volume, for purpose of the present invent~on are measured by
11 nitrogen adsorption wherein nitrogen is adsorbed at ~arious
12 pre~sures us~ng the Aminco Adsorptomat Cat. No. 4~4680, and
13 mNltiple sample acces~ory Cat. No~ 4~4685. The detailed
14 pro~edure is described in the ~minco Instruction Manual No.
~: ;1S 861~A furnished with the instrumeni:. A descr~p~ion of thè
16 Adsorptomat prototype instrument alld procedure is given in
17 Analytic~l C4emistry9 Volume 32J p~lge 5329 April l960.
18 An outline of the procedure i~ given here~ includ-
19 ing sample preparationO
From 0.2 ~o loO g~ of sample is used and ~he iso~
21 therm is run in the ad30rption mode only. All sampleg are
22 placed on the preconditioner beore ana~ysis where they are
23 out~ga~sed and dried at 190Co under vacuum (lO 5 torr) for
24 5 hours. Ater pretreatment the weighed sample is charged
to the Ad~orpt~mate and pumped down to 10~5 torr~ At thls
26 point~ th~ instrum0nt.i~ set in the autom~tic adsorption mode
27 to charge ~ s~andard volume of gas to the catalyst. This i5
28 done by charging a predetermined num~er of volumes as doses
29 and ~hen allowing time or adsorption of the nitrogen to
re~ch equilibrium pressure. rrhe pressure ls measured in ~ -
31 ~enm3 of its ratiQ to ~he saturation pressure o:E boiling
32 liquld nitrogen. Three do~es are injected ~nd 8 minutes
,: . . .. . . . . .
6~ 0 ~
1 allowed for equilibration of each measured relative pressure.
2 The dosing and equilibration are continued until a pressure
3 ratio of 0.97 ;s exceeded and maintained for 15 minutes.
4 The run îs then automatically terminated.
The data obtained with the dead space factor for
6 the sample, the vapor pressure of the liquid nitrogen bath,
7 and the sample weight are sent to a digital computer which
8 c~lculates the volume points of the isotherm, the BET area,
9 and the pore size distribution of the Barrett, Joyner, and
Halend~ m~thodO [Barrett, Joyner, ~nd Halenda9 J~ Am, Chem.
ll Soc. 73, p. 373.] It is believed th~t the B~rrettg Joyner,
2 8nd Halenda method is as complete a treatment as can be ob~
tained~ based on the assumptions of cylindrical pore~ and
14 the validity of the Kelvin equation.
Hydrocarbon or hydrocarbonaceous feedstocks wkich
l6 c~n be treated pursuant to the practice of this invention
.~- . ... . . .
17 include he~vy p~troleum crudes, synthetic crudes derived
l8 from coal, shale~ tar sands, heavy oils and tars which con-
19 tain relatively high concentrations-of asphaltenes9 high
carbon:hydrogen ratios9 high metals con~ents~ considerable
21 amounts of sand and s~ale9 considerable amounts of 1050F.+
22 materials 9 and generally high sulfur and nitrogan~ -
:
,'~.
... :
: ~ .
