Note: Descriptions are shown in the official language in which they were submitted.
209~66~
IMPROVED HYDROCONVERSION PROCESS AND CATALYST
(D#92,01~ -F)
CROSS-REFERENCES TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S.
Patent Application Serial Number 07/798,300, filed
November 22, 1991, which is a continuation-in-part of U.S.
Patent Application Serial Number 07/694,591, filed May 2,
1991, the texts of both of which are incorporated herein by
reference.
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates to the hydroconversion of
heavy hydrocarbon oils. More particularly, it relates to a
hydrotreating catalyst system with improved cumulative pore
volume properties and to processes for producing and using
such material.
Descri~tlon of Related Information
In petroleum refining there is frequently a need to
convert high boiling fractions of petroleum distillates, such
as vacuum resid, to lower boiling fractions which are of
higher value and more readily handleable and/or marketable.
1'he followlng patents illustrate va~ious ways or dealing w~th
this need.
U.S. Patent No. 4,579,646 discloses a bottoms
visbreaking hydroconversion process wherein hydrocarbon charge
is partially coked, and the coke is contacted within the
charge stock with an oil-soluble metal compound of a metal of
Group IV-B, V-B, VII-B, or VIII to yield a hydroconversion
catalyst.
U.S. Patent No. 4,226,742 discloses catalyst for the
hydroconversion of heavy hydrocarbon oils formed in situ from
oil-soluble metal compound by heating in the presence of
hh692018, ~pp
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209J66~
hydrogen. Oil soluble metal comp~und is added in amounts 10-
950 ppm, preferably 50-200, to feedstock. This mixture is
converted to a solid, noncolloidal form by heating the mixture
at 325-415C in the presence of hydrogen gas. Hydroconversion
is effected at 26-482OC and then the catalytic solids are
separated from the hydroconversion effluent.
U.S. Patent No. 4,178,227 discloses upgrading heavy
carbonaceous feeds by slurry hydroconversion and fluid coking
gasification, using as catalyst which is an in situ-formed
metal compound, and with recycled solid fines.
U.S. Patent No. 4,724,069 discloses hydrofining in
the presence of a supported catalyst bearing a VI-B, VII-B, or
VIII metal on alumina, silica, or silica-alumina. There is
introduced with the charge oil, as additive, a naphthenate of
Co or Fe.
U.S. Patent No~ 4,567,156 discloses hydroconversion
in the presence of a chromium catalyst prepared by adding a
water-soluble aliphatic polyhydroxy compound (such as
glycerol) to an aqueous solution of chromic acid, adding a
hydrocarbon thereto, and heating the mixture in the presence
of hydrogen sulfide to yield a slurry.
U.S. Patent No. 4,564,441 discloses hydrofining in
the presence of a decomposable compound of a metal (Cu, Zn,
III-B, IV-B, VI-B, VII-B, or VIII) mixed with a hydrocarbon-
containing feed stream, and the mixture is then contacted witha "suitable refractory inorganic material" such as alumina.
U.S. Patent No. 4,557,823 discloses hydrofining in
the presence of a decomposable compound of a IV-B metal and a
supported catalyst containing a metal of VI-B, VII-B, or VIII.
U.S. Patent No. 4,557,824 discloses demetallization
in the presence of a decomposable compound of a VI-B, VII-B,
or VIII metal admitted with the charge and a heterogeneous
catalyst containing a phosphate of Zr, Co, or Fe.
U.S. Patent No. 4,5~1,230 discloses demetallization
in the presence of a decomposable compound of a IV-B, V-B, VI-
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B, VII-B, or VIII metal admitted with the charge and a
heterogeneous catalyst containing NiAs~ on alumina.
U.S. Patent No. 4,430,207 discloses demetallization
in the presence of a decomposable compound of a V-B, VI-B,
VII-B, or VIII metal admitted with the charge and a
heterogeneous catalyst containing a phosphate of Zr or Cr.
U.S. Patent No. 4,389,301 discloses hydroprocessing
in the presence of added dispersed hydrogenation catalyst
(typically ammonium molybdate) and added porous contact
particles (typically FCC catalyst fines, alumina, or naturally
occurring clay).
U.S. Patent No. 4,352,729 discloses hydrotreating in
the presence of a molybdenum blue solution in polar organic
solvent introduced with the hydrocarbon charge.
U.S. Patent No. 4,338,183 discloses liquefaction of
coal in the presence of unsupported finely divided metal
catalyst.
U.S. Patent No. 4,298,454 discloses hydroconversion
of a coal-oil mixture in the presence of a thermally
decomposable compound of a IV-B, V-B, VI-B VII-B, or VIII
metal, preferably Mo.
U.S. Patent No. 4,134,825 discloses hydroconversion
of heavy hydrocarbons in the presence of an oil-soluble
compound of IV-B, V-B, VI-B, VII-B, or VIII metal added to
charge, the compound being converted to solid, non-colloidal
form by heating in the presence of hydrogen.
U.S. Patent No. 4,125,455 discloses hydrotreating in
the presence of a fatty acid salt of a VI-B metal, typically
molybdenum octoate.
U.S. Patent No. 4,077,867 discloses hydroconversion
of coal in the presence of oil-soluble compound of V-B, VI-B,
VII-B, or VIII metal plus hydrogen donor solvent.
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U.S. Patent No. 4,067,799 discloses hydroconversion
in the presence of a metal phthalocyanine plus dispersed iron
particles.
U.S. Patent No. 4,066,530 discloses hydroconversion
in the presence of (i) an iron component and (ii) a
catalytically active other metal component prepared by
dissolving an oil-soluble metal compound in the oil and
converting the metal compound in the oil to the corresponding
catalytically active metal component.
The above-noted U.S. Patent Application Serial No.
07/694,591 teaches that under the conditions of operation
disclosed therein, such as in Examples II-IV* and related
Table II in particular, it is possible to attain improvements
in, for example, conversion and other factors, by adding 10-
200 wppm oil-soluble catalyst to the heterogeneous catalyst.
In particular, Example I shows that it is possible to attain
much higher conversion when using 160 wppm of molybdenum
additive.
SUMMARY OF THE INVENTION
This invention concerns a process for catalytically
hydroconverting hydrocarbon oil comprising three essential
steps. Step (a) involves contacting hydrocarbon oil
containing a substantial quantity of high boiling compounds,
boiling above about l,000F, in a conversion zone witn (1)
solid heterogenous catalyst containing hydrotreating metal on
a porous support and (2) oil-miscible compound comprising an
effective porosity modifying amount of metal compound. Step
(b) involves converting a substantial portion of high boiling
compounds in the hydrocarbon oil at conversion conditions in
the presence of hydrogen and mercaptan to low boiling
compounds, boiling below about 1,000F, to make hydrocarbon
oil containing a substantial portion of low boiling point
compounds. Step (c) involves producing solid heterogeneous
catalyst with: (1) hydrocarbonaceous deposits having a higher
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ratio of hydrogen to carbon; and (2) a greater cumulative pore
volume; than is correspondingly produced in the absence of the
oil-miscible compound.
A ~rocess is also provided for increasing the
effective porosity of a solid heterogeneous catalyst in situ
while catalytically hydroconverting hydrocarbon oil comprisi~g
such steps.
DETAILED DESCRIPTION OF THE INVENTION
The charge which may be treated by the process of
this invention may include high boiling hydrocarbons typically
those having an initial boiling point (ibp) above about 650-F.
This process is particularly useful to treat charge
hydrocarbons containing a substantial quantity of components
boiling above about 1000F to convert a substantial portion
thereof to components boiling below 1000F.
Typical hydrocarbon oils include, among others, one
or more of the following: heavy crude oil; topped crude;
atmospheric resid; vacuum resid; asphaltenes; tars; coal
liquids; visbreaker bottoms; and the like. Illustrative of
such charge streams may be a vacuum resid obtained by blending
vacuum resid fractions from Alaska North Slope Crude (59
vol%), Arabian Medium Crude (5 vol%), Arabian Heavy Crude
(27~), and Bonny Light Crude (9 vol%) having the following
characteristics:
25 API Gravity 5.8
1000~F +, wt% 93.1
Composition, wt%
C 84.8
H 10.09
N 0.52
S 3.64
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Alcor Microcarbon Residue (McR), wt% 19.86
n-C7 insolubles, wt% 11.97
Metals content, wppm
Ni 52
V 131
Fe g
Cr 0.7
Na 5
The hydrocarbon oil generally contains undesirable
10 components like: up to about 1 wt%, typically about 0.2-0.8
wt%, say 0.52 wt%, nitrogen; up to about 10 wt%, typically
about 2-6 wt%, say 3.64 wt%, sulfur, and metals, such as Ni,
V, Fe, Cr, Na, and others, in amounts up to about 900 wppm,
typically about 40-400 wppm, say 198 wppm. The undesirable
asphaltene content of the hydrocarbon oil may be as high as
about 22 wt%, typically about 8-16 wt%, say 11.97 wt%,
analyzed as components insoluble in normal heptane.
The API gravity of the charge may be as low as about
-5, typically from about -5 to about 35, say 5.8. The content
20 of o~omponents boiling above about 1000F may be as high as 100
wt%, typically about 50-98+ wt%, say 93.1 wt%. The Alcor MCR
Carbon content may be as high as about 30 wt~, typically about
15-25 wt%, say 19.86 wt%.
The charge hydrocarbon oil may be passed to a
hydroconversion operation wherein conversion occurs in liquid
phase at any effective, including known, conversion
conditions. Typical operating conditions include about 700F-
850F, preferably about 750F-810F, say 800F; and hydrogen
partial pressure of about 500-5000 psig, preferably about
30 1500-2500 psig, say 2000 psig.
A catalytically effective amount of oil-miscible,
preferably oil-soluble, compound, typically of a metal of
Group IV-B, V-B, VI-B, VII-B or VIII of the Periodic Table, is
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209~66~
added to the charge hydrocarbon oil, preferably prior to
hydroconversion. When the metal is a Group IV-B metal, it may
be titanium (Ti), zirconium (Zr), or hafnium (Hf). When the
metal is a Group V-B metal, it may be vanadium (V), niobium
(Nb), or tantalum (Ta). When the metal is a Group VI-B metal,
it may be chromium (Cr), molybdenum (Mo), or tungsten (W).
When the metal is a Group VII-B metal, it may be manganese
(Mn) or rhenium (Re). When the metal is a Group VIII metal,
it may be a non~noble metal such as iron (Fe), cobalt (Co), or
nicXel (Ni) or a noble metal such as ruthenium (Ru), rhodium
(Rh), palladium (Pd), osmil1m (Os), iridium (Ir), or platinum
(Pt). Preferably the metal. is a Group VI~B metal, and most
prererably molybdenum (Mo).
Typical oil-miscible or oil-soluble compounds
include, among others, one or mixtures of the following:
metal salts of aliphatic carboxylic acids like molybdenum
stearate, molybdenum palmitate, molybdenum myristate and
molybdenum octoate; metal salts of naphthenic carboxylic acids
like cobalt naphthenate, iron naphthenate and molybdenum
~0 naphthenate; metal salts of alicyclic carboxylic acids like
molybdenum cyclohexane carboxylate; metal salts of aromatic
carboxylic acids like cobalt benzoate, cobalt o-methyl
benzoate, cobalt m-methyl benzoate, cobalt phthalate and
molybdenum p-methyl benzoate; metal salts of sulfonic acids
like molybdenum benzene sulfonate, cobalt p-toluene sulfcnate
and iron xylene sulfonate; metal salts of sulfinic acids like
molybdenum benzene sulfinate and iron benzene sulfinate; metal
salts of phosphoric acids like molybdenum phenyl phosphate;
metal salts of mercaptans like iron octyl mercaptide and
cobalt hexyl mercaptide; metal salts of phenols like cobalt
phenolate and iron phenolate; metal salts of polyhydroxy
aromatic compounds like iron catecholate and molybdenum
resorcinate; organo metallic compounds like molybdenum
hexacarbonyl, iron hexacarbonyl and cyclopentadienyl
molybdenum tricarbonyl; metal chelates like ethylene diamine
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tetra carboxylic acid-di-~errous salt; and metal salts of
organic amines like cobalt salt of pyrrole; and the like.
Preferred compounds include cobalt naphthenate, molybdenum
hexacarbonyl, molybdenum naphthenate, molybdenum octoate, and
molybdenum hexanoate.
The metal compounds to be employed are oil-miscible
and preferably oil-soluble, in that they are readily
dispersible, and preferably soluble, in the charge hydrocarbon
oil in amount of at least 0.01 g/lOOg typically 0.025-0.25
g/lOOg, say about 0.1 g/lOOg. The metal compounds, when
activated as hereinafter set forth, are also oil-miscible in
the hydrocarbon oils during the hydroconversion process.
The oil-miscible compound is generally present in
small amounts, typically about 60 wppm or less, of metal, say
10-60 wppm based on hydrocarbon oil to be hydroconverted,
unexpected results may be achieved. It is unexpectedly found,
if the noted amount is 15-60, preferably 15-45, most
preferably 15 wppm, that the cumulative pore volume of the
catalyst is improved. Specifically, the cumulative pore
volume increases generally at least about 1%, preferably from
about 5% to about 50% or more, say 31 %, when compared to the
baseline pore volume in the absence of oil-miscible compound.
Conversion is calculated from the ratio of the
percentage of 1,000F+ material in the feed minus the
percentage of 1,000F+ material in the product diviaed by ~he
percentage of l,000F+ material in the feed.
The level of miscible metal, in the 15-60 wppm
range, which will be employed will depend upon the particular
charge to the ebullated bed and the desired cumulative pore
volume for the catalyst. In any instance, an economic study
will permit a ready determination of the desired level of
metal to be employed.
The oil-miscible compound may be added by any
effective means, such as a solution or mixture thereof with a
highly aromatic heavy oil. The highly aromatic heavy oil
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which may be employed, typically those oils which contain
sul~ur such as a heavy cycle gas oil (HCG0), may be
characterized as follows:
Broad NarrowTypical
API Gravity -5 to 20 0-10 2
Temperature, F
ibp 500-1,000 650-850 650
50% 800-900 825-875 850
ep - 1,000-1,2001,000-1,1001,050
10 Aromatics Content, wt% 25-90 30-85 85
Sulfur Content, wt% 0.5-5 2-4 3.5
Illustrative highly aromatic heavy oils which may be
employed may include:
A - Heavy Cycle Gas Oil
API Gravity -3.0
Temperature F
ibp 435
10% 632
50% 762
90% 902
ep 1,056
Aromatics Content, wt% 85
Sulfur Content, wt% 2.5-3.5
B - MP Extract
API Gravity 8
?emperature oF
ibp 600
ep 1,000
Aromatics Content, wt% so-go
Sulfur Content, wt% 3
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209~rj66~
C - Decant Oil
API Gravity -2.7
Tem~erature F
ibp 525
10~ 708
50% 935
90% 975
ep 1,100
Aromatics Content, wt% 80
Sulfur Content, wt% 1.75
The oil-miscible compound may be added in an amount
to form a solution or mixture with the heavy oil typically of
about 0.01-0.04 wt%, preferably about 0.01-0.03 wt%, say 0.02
wt%. The compound may be added to the heavy oil and stored
and used in such form. When this is added to the charge
hydrocarbon oil to hydrotreating, the amount added may be
about 5-20 wt%, preferably about 15 wt%, say 13 wt% of
solution or mixture which will provide the 10-60 wppm of metal
desired to effect the results noted previously. Typically,
the oil-miscible compound is added continuously, such as with
the charge hydrocarbon. The oil-miscible compound may be
added at any stage of the hydroconversion reaction, preferably
during the first stage of multi-stage, such as two-stage
reactions.
Activation of the oil-miscible compound may be
effected either by pre-treatment (prior to hydroconversion) or
situ (during hydroconversion). It is preferred to effect
activation in situ in the presence of the hydrogenation
catalyst to achieve a highly dispersed catalytic species.
Activation according to the preferred method may be
carried out by adding metal compound, in amount to provide
desired metal content, to charge hydrocarbon at about 60~F-
300~F, say 200F. The mixture is activated by heating to
about 400F-~35F, typically about 500F-700F, say 600F at
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209~66~
partial pressure of hydrogen of about 500-5,000 psig,
typically about 1,000-3,000 psig, say 2,000 psig and at
partial pressure of a gaseous mercaptan of about 5-500 psig,
typically about 10-300 psig, say 50 psig. Total pressure may
be about 500~5,500 psig, typically about 1,000-3,300 psig, say
2,650 psig. Commonly the gas may contain about 40-99 vol%,
typically about 90-99 vol%, say 98 vol~ hydrogen and about 1-
10 vol%, say 2 vol% mercaptan, such as hydrogen sulfide. The
time for conducting activation may be about 1-12, typically
about 2-6, say 3 hours. Activation may occur at a temperature
which is lower than the temperature of conversion.
The mercaptans which may be employed may include,
among others, one or more: hydrogen sulfide: aliphatic
mercaptans, typified by methyl mercaptan, lauryl mercaptan,
lS and the like; aromatic mercaptans; dimethyl disulfide: carbon
disulfide; and the like. These mercaptans apparently
decompose during the activation process. It is not clear why
this treatment activates the metal compound. It may be
possible that the activity is generated as a result of metal
sulfides formed during the treatment.
When the sulfur content of the charge hydrocarbon is
above about 2 wt%, it may not be necessary to add a mercaptan
during activation since hydrodesulfurization of the charge may
provide enough mercaptan to properly activate, meaning
sulfide, the oil-miscible decomposable compound.
It is possible to activate the oil-miscible metal
compound in the solution or mixture with the heavy aromatic
oil. Activation may be effected under the same conditions as
are used when activation is carried out in the charge stream.
The compatible oil containing the now activated metal may be
admitted to the charge stream in amount sufficient to provide
therein activated oil-miscible metal compound in desired
amount.
In still another embodiment, activation may be
carried out by subjecting the charge hydrocarbon oil
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209~ 66~
containing the oil-miscible compound to ~ydroconversion
conditions including temperature of about 700F-850-F,
preferably about 750~F-810~F, say 800F at hydrogen partial
pressure of about 500-5,000 psig, preferably about 1,500-2,000
psig, say 2,000 psig, in the presence of a mercaptan but in
the absence of heterogeneous hydroconversion catalyst.
In the preferred embodiment, activation may be
carried out during hydroconversion in the presence of the
heterogeneous, hydroconversion catalyst, hydrogen, and
mercaptan.
Hydroconversion is carried out in the presence of
solid heterogeneous catalyst generally containing, as a
hydrogenating component, a metal of Group IV-B, V-B, VI-B,
VII-B, or VIII on a porous support which may typically contain
carbon or metal oxide, such as of aluminum, silicon, titanium,
magnesium, zirconium or the like. Preferably, the catalyst
may contain a metal of Group VI-B and VIII, typically nickel
and molybdenum. When the metal is a Group IV-B metal, it may
be titanium (Ti) or zirconium (Zr). When the metal is a Group
V-B metal, it may be vanadium (V), niobium (Nb), or tantalum
(Ta). When the metal is a Group VI-B metal, it maybe chromium
(Cr), molybdenum (Mo), or tungsten (W). When the metal is a
Group VII-B metal, it maybe manganese (Mn) or rhenium (Re).
When the metal is a Group VIII metal, it may be a non-noble
metal such as iron (Fe), cobalt (Co), or nickel (Ni) or a
noble metal such as ruthenium (Ru), rhodium (Rh), palladium
tPd), osmium (Os), iridium (Ir), or platinum (Pt).
The solid heterogeneous catalyst may also contain,
as a promoter, a metal of Groups I-A, I-B, II-A, II-B, or V-A.
When the promoter is a metal of Group I-A, it may preferably
be sodium (Na) or potassium (K). When the promoter is a metal
of Group IB, it may preferably be copper (Cu). When the
promoter is a metal of Group II-A, it may be beryllium (Be),
magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), or
radium (Ra). When the promoter is a metal of Group II-B, it
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may be zinc (Zn), cadmium (Cd), or mercury (Hg). When the
promoter is a metal of Group IV-B, it may be titanium ~Ti),
zirconium (Zr), or hafnium (Hf). When the promoter is a metal
of Group V-A, it may preferably be arsenic (As), antimony
(Sb), or bismuth (Bi).
The hydrogenating metal may be loaded onto the solid
heterogeneous catalyst by any effective, including known,
technique, such as by immersing the catalyst support in
solution, say ammonium heptamolybdate, for about 2-24 hours,
say 24 hours, followed by drying at about 60F-300F, say
200F, for about 1-24 hours, say 8 hours, and calcining for
about 1-24 hours, say 3 hours, at about 750F-1,100F, say
930F.
The promoter metal may be loaded onto the solid
heterogeneous catalyst by any effective, including known,
technique, such as by immersing the catalyst support,
preferably bearing the calcined hydrogenating metal - although
they may be added simultaneously or in any order, in solution,
of for example bismuth nitrate, for about 2-24 hours, say 24
hours, followed by drying at about 60F-300F, say 200F for
about 1-24 hours, say 3 hours, and calcining at about 570F-
1,100F, say 750F for about 1-12 hours, say 3 hours.
Fresh, solid heterogenous catalyst employed in the
method of this inventlon may be characterized by a total pore
2S volume of about 0.2-1.2 cc/g, say 0.77 cc~g; a surface area of
about 50-500 m2/g, say 280 m2/g; and a pore size distribution
as follows:
Pore Diameter A Volume cc/g
30-100 0.15-0.8, say 0.42
30100-1000 0.10-0.50, say 0.19
1,000-10,000 0.01-0.40, say 0.16
In another embodiment, it may have a pore size
distribution as follows:
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Pore Diameter. A Pore ~lolume cc~g Typical
>250 0.12-0.35 0.28
~00 0.11-0.29 0.21
>1,500 0.08-0.26 0.19
5~4,000 0.04-0.18 0.11
The solid heterogeneous catalyst typically may
contain about 4-30 wt%, say 9.5 wt% Mo, about 0-6 wt%, say 3.1
wt% Ni and about 0-6 wt%, say 3.1 wt% of promoter metal, say
bismuth. Liquid hourly space velocity (LHSV) in the
10 hydroconversion reactors may be about 0.1-2, say 0.7.
Preferably, the heterogeneous catalyst may be employed in the
form of extrudates of diameter of o.7-6.5 mm, say 1 mm and of
length of 0.2-25 mm, say 5 mm.
Although it is possible to carry out hydroconversion
lS in a fixed bed, a moving bed, a fluidized bed, or a well-
stirred reactor, it is found that the advantages of this
invention may be most apparent when hydroconversion is carried
out in an ebullated bed. Hydroconversion may be carried out
in one or more beds. It is found that the active form of the
catalyst is formed in or accumulates in the first of several
reactors and accordingly increases in conversion and
heteroatom removal activities appear principally to occur in
the first of several reactors.
E~fluent from hydroconversion is typically
characterized by an increase in the content of liquids boiling
below l,000F. Commonly the wt% conversion of the l,000F
+ boiling material is about 30%-90%, say 67% which is
typically about 5%-25%, say 12% better than is attained by
prior art techniques.
It is a feature of this invention that it permits
attainment of improved removal of sulfur (HDS Conversion), of
nitrogen (HDN Conversion), and of metals (HDNi and HDV
Conversion). Typically, HDS Conversion may be about 30-90%,
say 65% which is about 1%-10%, say 4% higher than the control
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runs. Typically, HDN Conversion may be about 20%-60%, say 45%
which is about 1%-10%, say 4% higher than control runs.
Typically, HDNi plus HDV conversion may be about 70~-99~, say
90% which is about 5%-20%, say 13% higher than control runs.
This invention provides improved solid heterogeneous
catalyst having (1) hydrocarbonaceous deposits having a higher
ratio of hydrogen to carbon than is produced when operating
outside the conditions of this invention; as well as (2) a
correspondingly greater cumulative pore volume. The addition
of oil-miscible compound with hydrocarbon oil permits the
attainment of hydrocarbonaceous deposits characterized by a
hydrogen to carbon ratio typically up to about 30% greater
than those obtained in the absence of oil-miscible compound.
Typically, the hydrogen to carbon ratio may increase from a
base ratio of about 0.062 to an experimental ratio as high as
about 0.0885.
Increased total pore volume will increase the
activity of the aged catalyst in situ since the number of
micropores are increased when compared to the baseline
catalyst. This increase in micropores will increase the
ability of the catalyst to perform hydrogenation reactions,
such as sulfur removal.
The following examples illustrate some embodiments
of this invention and are not intended to limit its scope.
All percentages and amounts given in the disclosure and claims
are based on weight, unless otherwise stated.
EXAMPLES
Exam~les lC-5
In these Examples the oil miscible compound is
molybdenum naphthenate added in an amount to provide from 15
to 60 wppm molybdenum in the feed to the unit. The feedstock
is a blend of (i) vacuum resid, (ii) visbreaker bottoms, (iii)
vacuum bottoms recycle (iv) and heavy cycle gas oil having the
following properties:
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VR + VB Bottoms HCGO
Gravity, API (ASTM D-287) 4.7 -3.5
X-Ray Sulfur, wt% (ASTM D-4294) 5.52 3.41
Carbon Residue, wt% (ASTM D-189) 21.98 10.9
Total Nitrogen, wppm (Chemiluminesence) 4,348 1,582
CHN Analysis, wt% (Leco Combustion Analysis)
Carbon 85.65 88.23
Hydrogen 10.47 7.67
Nitrogen 0.6 0.18
Metals, wppm
V 170
Ni 40.8
Fe 15.5
Cr 0.2
lS Na 5.5
Kinematic Viscosity, Cst (ASTM D-445)
@ 212 Deg F 2,368.1
@ 250 Deg F 664.8
@ 300 Deg F 117.1
The mixture of feedstock and heavy cycle gas oil
containing the oil-soluble molybdenum naphthenate is admitted
at 780-790~F and 2,500 psig and 0.39 LHSV. Hydrogen feed is
4,300 SCFB of 92% hydrogen.
The supported catalyst in the ebullated bed is
cylinders (0.8 mm diameter and 5 mm length) of commercially
available catalyst containing 2.83 wt% nickel and 8.75 w~%
molybdenum on alumina, having a surface area of 285.2 m2/g, a
total pore volume of 0.78 cc/g, and a pore slze distribution
of 0.28 cc/g at >250A, 0.21 cc/g at >500A, 0.19 cc/g at
30 >1, ssoA and 0.11 cc/g at >4, oooA . The catalyst is activated
in situ during hydroconversion.
A base line, prior to oil-miscible compound
addition, analysis of the weight ratio of hydrogen to carbon
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in the hydrocarbonaceous deposits and catalyst porosity, in
total pore volume, is taken in Example lC; and similar
determinations are made at the end of each addition, with the
results given in Tables I through V.
Example lC:
A baseline was run to determine the product
qualities as well as the solid catalyst properties prior to
adding the liquid molybdenum compounds. The baseline
conditions were LHSV of 0.39 based on total feed, reactor
10 temperatures of 780F and 790F, first and second stage
respectively, and at a system pressure of 2,500 psig. Daily
catalyst withdrawals were conducted to maintain the catalyst
inventory at the re~uired age. After 5 test periods, each one
24 hours apart, a portion of the withdrawn catalyst was
submitted for analyses to determine pore volume, carbon,
hydrogen, sulfur as well as other qualities to develop a
reference point for comparison purposes. Baseline data
indicated the equilibrated, solid heterogenous catalyst had
a H/C ratio of 0.062 in the first stage reactor and 0.0574 in
the second stage reactor. Surface area for the baseline case
was approximately 95 m2/g.
Example 2:
Molybdenum naphthenate is mixed with heavy cycle gas
oil in amounts to result in 15 ppm molybdenum in the fresh
feed to the reactor. The feedstock consists of a blend of
vacuum resid, visbroken bottoms, and vacuum bottoms recycle.
The molybdenum naphthenate is fed to the process for 9
successive days. Catalyst withdrawals are conducted daily.
The catalyst withdrawn from day 9 is submitted for analysis.
Comparisons between the analyses from day 9 and the baseline
indicate increasing amounts of carbon, molybdenum, vanadium
and sulfur depositing on the surface of the catalyst when the
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molybdenum is injected. Comparisons between the hydrogen to
carbon weight ratio for the baseline catalyst and the catalyst
that is withdrawn for the first staqe, show an increase over
the baseline ratio by 29.~go~ The hydrogen to carbon weight
ratio in the second stage increases by 7.7%. This indicates
that the coke formed on the catalyst contains a higher amount
of hydrogen than that of the baseline. HDS MAT activity test
shows increased sulfur removal for the catalyst withdrawn
during the 15 ppm injection for both stages.
Example 3:
Molybdenum naphthenate is mixed with heavy cycle gas
oil in amounts to result in 30 ppm molybdenum in the fresh
feed to the reactor. The feedstock consists of a blend of
vacuum resid, visbroken bottoms, and vacuum bottoms recycle.
The molybdenum naphthenate is fed to the process for 8
successive days. Catalyst withdrawals are conducted daily.
The catalyst withdrawn from day 8 is submitted for analysis.
Comparisons between the analyses from day 8 and the baseline
indicate increasing amounts of carbon, molybdenum and sulfur
depositing on the surface of the catalyst when the molybdenum
is injected. The hydrogen to carbon weight ratio in the first
and second stages was higher than the baseline ratio by 18.8
and 2.9% respectively. This indicates increased hydrogen
loading in the coKe formed on the catalyst. HDS MAT activity
tests shows a drop in sulfur removal when compared to the MAT
activity for Example 2.
Example 4:
Molybdenum naphthenate is mixed with heavy cycle gas
oil in amounts to result in 45 ppm molybdenum in the fresh
feed to the reactor. The feedstock consists of a blend of
vacuum resid, visbroken bottoms, and vacuum bottoms recycle.
The molybdenum naphthenate is fed to the process for 4
successive days. Catalyst withdrawals are conducted daily.
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The catalyst withdrawn from day 8 is submitted for analysis.
Comparisons between the analyses ~rom day ~ and th~ baseline
indicated increasing amounts of carbon, molybdenum, vanadium
and sulfur depositing on the surface during the period the
molybdenum is injected. The hydrogen to carbon weight ratio
in the first and second stages increases over the baseline by
20.7 and 2.9~ respectively. This would indicate higher levels
of hydrogen in the coke formed on the catalyst.
Example 5:
Molybdenum naphthenate is mixed with heavy cycle gas
oil in amounts to result in 60 ppm molybdenum in the fresh
feed to the reactor. The feedstock consists of a blend of
vacuum resid, visbroken bottoms, and vacuum bottoms recycle.
The molybdenum naphthenate is fed to the process for 11
successive days. Catalyst withdrawals are conducted daily.
The catalyst withdrawn from day 11 is submitted for analysis.
Comparisons between the analyses from day ll and the baseline
indicate increasing amounts of carbon, molybdenum, vanadium
and sulfur depositing on the catalyst surface during the
period of molybdenum injection. The hydrogen to carbon weight
ratio in the first stage decreases by 4.4% when compared to
the baseline. The hydrogen to carbon weight ratio on the
second stage catalyst actually increases by 10~ over the
baseline. It would appear that the coke ~ormed in the first
stage during the 60 ppm injection period was of the same type
as would normally be formed during resid hydrotreating
operations. The second stage catalyst might not have been
affected as much since the molybdenum was injected into the
first stage only.
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Table I
FIRST SI'AGE CATALYST WITHDRAWALS
H/C % Increase
Mo,ppm C* ~H* N* S* Mo H/C over Baseline
0 22.2 1.38 0.28 10.3 6.36 0.062
14.8 1.31 0.30 11.4 5.70 0.0885 29.9
19.4 1.48 0.22 10.7 6.76 0.0764 18.8
15.9 1.24 0.33 11.5 S.96 0.0782 20.7
28.6 1.70 0.24 9.67 8.08 0.0594 -4.4
* - Wt%, using LECO Carbon-Hydrogen-Nitrogen-Sulfur Analyzer
Table II
FIRST STAGE
ELEMENTAL RATIOS ON EXTERIOR SURFACE OF WIT~DRAWN CATALYST*
Mo.wppm Ni/Al Mo/Al V~Al CtAl S~Al
150 0.0 0.121 0.14525.423 1.693
0.125 0.650 0.33451.264 5.169
0.0 1.911 0.0117.724 10.26
0.0 0.841 0.21744.854 5.614
0.0 0.996 0.0100.231 4.968
* - Using x-ray photoelectron spectroscopy (XPS analysis)
Table III
SECOND STAGE CATALYST WITHDRAWALS
H/C % Increa~e
Mo,w~Pm C* H* N* S* Mo H/C over Baseline
0 26.0 1.49 0.37 7.13 6.73 0.0574 --
21.7 1.35 0.36 8.56 6.69 0.0622 7.7
26.4 1.56 0.30 8.16 6.37 0.0591 2.9
23.4 1.38 0.45 ----6.98 0.0590 2.9
3060 24.8 1.58 0.31 8.33 6.62 0.0638 10.0
* - Wt%, using LECO Carbon-Hydrogen-Nitrogen-Sulfur Analyzer
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Table IV
SECOND STAGE
ELEMENTAL RATIOS ON EXTERIOR SURFACE OF WITHDRAWN CATALYST
Mo.w~pm Ni/Al Mo/Al V/Al C/Al S/Al
0 0.0 0.086 0.194 41.272 2.338
0.0 0.238 0.376 32.286 3.074
0.037 0.196 0.226 42.814 2.893
0.0 0.184 0.248 27.187 2.263
0.0 0.209 0.163 24.606 1.853
* - Using x-ray photoelectron spectroscopy (XPS analysis)
Table V
Percentage Area (m2/g) Increase Over Baseline
Pore Average
Diameter Pore Di-
Interval ameter Oil-Miscible Compound Metal Concentration
(A~ (A) 15 ppm 30 ppm 45 p~m 60 ppm
Sta~e: First Second First Second First Second First Second
30-45 38 37.82 24.24 22.83 29.31 40.00 16.67 4.00 8.33
45 67 56 35.50 28.7g 25.34 33.80 39.44 23.95 8.7914.55
2067-83 75 33.66 21.23 24.07 28.12 36.14 20.69 6.82 6.12
83-100 91.5 30.80 24.56 23.08 28.33 33.33 19.78 4.76 6.52
100-200 150 28.85 21.57 22.92 26.74 32.73 17.36 5.13 6.98
200-300 250 27.08 22.59 23.91 27.45 32.43 19.57 2.78 5.13
30~-400 35U 2~.44 22.87 22.37 28.33 30.61 20.00 0.00 8.59
25400-500 450 27.27 23.70 22.33 30.00 31.91 19.10 3.0310.56
500-600 550 26.67 22.44 22.61 27.73 30.32 18.46 3.75 6.47
600-700 650 29.50 23.59 25.79 29.05 34.42 21.58 6.00 6.88
700-1000 850 26.46 25.93 22.78 29.29 30.50 22.22 4.14 6.67
1000-10000 5500 41.03 50.00 42.50 50.00 54.00 48.72 48.8928.57
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