Note: Descriptions are shown in the official language in which they were submitted.
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
Hydroprocessing Catalysts and Methods for Making Thereof
CROSS-REFERENCE TO RELATED APPLICATIONS
[001] This application claims priority to US Patent Application Nos.
13/233455,
13/233477, and 13/233491, all with a filing date of September 15, 2011. This
application
claims priority to and benefits from the foregoing, the disclosures of which
are incorporated
herein by reference.
TECHNICAL FIELD
[002] The invention relates generally to catalysts for use in the conversion
of heavy
oils and residua and methods for making thereof.
BACKGROUND
[003] The petroleum industry is increasingly turning to heavy crudes, resids,
coals
and tar sands as sources for feedstocks. Feedstocks derived from these heavy
materials
contain more sulfur and nitrogen than feedstocks derived from more
conventional crude oils,
requiring a considerable amount of upgrading in order to obtain usable
products therefrom.
These heavier and high sulfur crudes and resides also present problems as they
invariably
also contain much higher metals contaminant metals such as nickel, vanadium,
and iron,
which represent operating problems in terms of metal deposit / build-up in the
equipment.
[004] The upgrading of heavy oil feedstock is accomplished by hydrotreating
processes, i.e., treating with hydrogen of various hydrocarbon fractions, or
whole heavy
feeds, or feedstocks, in the presence of hydrotreating catalysts to effect
conversion of at least
a portion of the feeds, or feedstocks to lower molecular weight hydrocarbons,
or to effect the
removal of unwanted components, or compounds, or their conversion to innocuous
or less
undesirable compounds.
[005] Catalysts commonly used for these hydrotreating reactions include
materials
such as cobalt molybdate on alumina, nickel on alumina, cobalt molybdate
promoted with
nickel, nickel tungstate, at least a group VIB metal compound with at least a
promoter metal
compound, etc. High catalyst dosage will improve the conversion rate and
reduce solid
accumulation in the process equipment. However, there is an economic
limitation as how
much catalyst can be used, as a high dosage will drive up capital and
operating costs.
1
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
[006] There is still a need for improved catalysts with balanced material
costs, while
still offering excellent morphology, structure and catalytic activity. There
is also a need for
improved processes to prepare catalysts for use in the conversion of heavy
oils and residua.
There is a further a need for improved heavy oil upgrade processes with
reduced build-up of
heavy metal contaminants.
SUMMARY OF THE INVENTION
[007] In one aspect, the invention relates to a catalyst feed system for use
in the
upgrade of heavy oil feedstock. The catalyst feed system comprises: a) a
deoiled spent
catalyst comprising a plurality of dispersed particles slurried in a
hydrocarbon medium as a
slurry, the deoiled catalyst retaining less than 80% but more than 10% of its
original catalytic
activity; and b) a fresh slurry catalyst comprising a plurality of dispersed
particles in a
hydrocarbon medium as a slurry. The deoiled spent catalyst is present in an
amount of at
least 10% the catalyst feed system to trap metal contaminants in the system
and reduce metal
deposits.
[008] In another aspect, the invention relates to a method to trap metal
contaminants
from a heavy oil feedstock in a system to upgrade the heavy oil feedstock. The
method
comprises providing to the heavy oil upgrade system a catalyst feed, which
contains: a) a
fresh slurry catalyst comprising a plurality of dispersed particles in a
hydrocarbon medium as
a slurry; and b) a deoiled spent catalyst comprising a plurality of dispersed
particles slurried a
hydrocarbon medium as a slurry. The deoiled spent catalyst has less than 80%
but more
than 10% of original catalytic activity, and the deoiled spent catalyst is
present in the catalyst
feed in a sufficient amount to trap the metal contaminants for the upgrade
system to have a
reduction of at least 5% in metal contaminant deposit.
[009] In yet another aspect, the invention relates to a method to prepare a
catalyst
feed for a heavy oil upgrade system. The method comprises the steps of:
providing spent
catalyst with a solid content ranging from 5 to 50 wt. % in soluble
hydrocarbons and having
less than 80% but more than 10% of original catalytic activity; removing at
least 50% of the
soluble hydrocarbons removed in a deoiling step, generating a deoiled spent
catalyst with at
least a metal contaminant; treating the deoiled spent catalyst with a treating
solution to
reduce the concentration of metal contaminants; slurring the treated deoiled
spent catalyst in
a hydrocarbon medium, generating a treated deoiled spent catalyst slurry; and
feeding the
treated deoiled spent catalyst slurry to a heavy oil upgrade system with a
fresh slurry catalyst.
2
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
BRIEF DESCRIPTION OF THE DRAWINGS
[010] FIG. 1 schematically illustrate embodiments of a hydroconversion process
to
upgrade heavy oil with a slurry catalyst feed system comprising a deoiled
spent catalyst.
[011] FIG. 2 shows a scheme with different embodiments of a hydroconversion
process to upgrade heavy oil, wherein the deoiled spent catalyst is first
treated to remove
contaminants.
DETAILED DESCRIPTION
[012] The following terms will be used throughout the specification and will
have
the following meanings unless otherwise indicated.
[013] "Bulk catalyst" may be used interchangeably with "slurry catalyst" or
"unsupported catalyst," meaning that the catalyst composition is NOT of the
conventional
catalyst form with a preformed, shaped catalyst support which is then loaded
with metals via
impregnation or deposition catalyst. In one embodiment, the bulk catalyst is
formed
through precipitation. In another embodiment, the bulk catalyst has a binder
incorporated
into the catalyst composition. In yet another embodiment, the bulk catalyst is
formed from
metal compounds and without any binder. The bulk catalyst is a dispersing-type
catalyst
("slurry catalyst") type with dispersed particles in a liquid mixture (e.g.,
hydrocarbon oil).
[014] "Fresh catalyst" refers to a catalyst that has not been used for
hydroprocessing.
[015] "Spent catalyst" refers to a catalyst that has been used in a
hydroprocessing
operation and whose activity has thereby been diminished. For example, if a
reaction rate
constant of a fresh catalyst at a specific temperature is assumed to be 100%,
the reaction rate
constant for a spent catalyst temperature is 80% or less in one embodiment
(retaining less
than 80% of the original catalytic activity), and 50% or less in another
embodiment.
[016] "Soluble hydrocarbons" refer to hydrocarbons that are soluble in
physical
solvents. An example is heavy oil / unconverted resid, and not coke which is
not soluble in
physical solvents.
[017] "Deoiled spent catalyst" refers to a spent catalyst after the removal of
at least
50 % of soluble hydrocarbons from the spent catalyst. The deoiled spent
catalyst contains
less than 25 wt. % soluble hydrocarbons in one embodiment; less than 10 wt. %
soluble
hydrocarbons in another embodiment; less than 5 wt. % soluble hydrocarbons in
a third
embodiment; and less than 2 wt. % soluble hydrocarbons in a fourth embodiment.
3
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
[018] "Heavy oil" feed or feedstock refers to heavy and ultra-heavy crudes,
including but not limited to resids, coals, bitumen, tar sands, oils obtained
from the thermo-
decomposition of waste products, polymers, biomasses, oils deriving from coke
and oil
shales, etc. Heavy oil feedstock may be liquid, semi-solid, and / or solid.
Examples of heavy
oil feedstock that might be upgraded as described herein include but are not
limited to
Canada Tar sands, vacuum resid from Brazilian Santos and Campos basins,
Egyptian Gulf of
Suez, Chad, Venezuelan Zulia, Malaysia, and Indonesia Sumatra. Other examples
of heavy
oil feedstock include residuum left over from refinery processes, including
"bottom of the
barrel" and "residuum" (or "resid") , atmospheric tower bottoms, which have a
boiling point
of at least 343 C. (650 F.), or vacuum tower bottoms, which have a boiling
point of at least
524 C. (975 F.), or "resid pitch" and "vacuum residue" which have a boiling
point of 524 C.
(975 F.) or greater.
[019] Properties of heavy oil feedstock may include, but are not limited to:
TAN of
at least 0.1, at least 0.3, or at least 1; viscosity of at least 10 cSt; API
gravity at most 15 in one
embodiment, and at most 10 in another embodiment. A gram of heavy oil
feedstock
typically contains at least 0.0001 grams of NiN/Fe; at least 0.005 grams of
heteroatoms; at
least 0.01 grams of residue; at least 0.04 grams C5 asphaltenes; at least
0.002 grams of micro
residue (MCR); per gram of crude; at least 0.00001 grams of alkali metal salts
of one or more
organic acids; and at least 0.005 grams of sulfur. In one embodiment, the
heavy oil feedstock
has a sulfur content of at least 5 wt. % and an API gravity ranging from -5 to
+5. A heavy oil
feed such as Athabasca bitumen (Canada) typically has at least 50% by volume
vacuum
reside. A Boscan (Venezuela) heavy oil feed may contain at least 64 % by
volume vacuum
residue. A Borealis Canadian bitumen may contain about 5% sulfur, 19% of
asphaltenes and
insoluble THF1 (tetrahydrofuran) of less than 1 kg/ton.
[020] "Treatment," "treated," "upgrade", "upgrading" and "upgraded", when used
in
conjunction with a heavy oil feedstock, describes a heavy oil feedstock that
is being or has
been subjected to hydroprocessing, or a resulting material or crude product,
having a
reduction in the molecular weight of the heavy oil feedstock, a reduction in
the boiling point
range of the heavy oil feedstock, a reduction in the concentration of
asphaltenes, a reduction
in the concentration of hydrocarbon free radicals, and/or a reduction in the
quantity of
impurities, such as sulfur, nitrogen, oxygen, halides, and metals.
[021] The upgrade or treatment of heavy oil feeds is generally referred herein
as
"hydroprocessing" (hydrocracking, or hydroconversion). Hydroprocessing is
meant as any
4
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
process that is carried out in the presence of hydrogen, including, but not
limited to,
hydroconversion, hydrocracking, hydrogenation, hydrotreating,
hydrodesulfurization,
hydrodenitrogenation, hydrodemetallation, hydrodearomatization,
hydroisomerization,
hydrodewaxing and hydrocracking including selective hydrocracking. The
products of
hydroprocessing may show improved viscosities, viscosity indices, saturates
content, low
temperature properties, volatilities and depolarization, etc.
[022] Hydrogen refers to hydrogen, and / or a compound or compounds that when
in
the presence of a heavy oil feed and a catalyst react to provide hydrogen.
[023] "Catalyst precursor" refers to a compound containing one or more
catalytically active metals, from which compound the slurry catalyst is
eventually formed,
and which compound may be catalytically active as a hydroprocessing catalyst.
[024] "One or more of' or "at least one of' when used to preface several
elements
or classes of elements such as X, Y and Z or X1-X, Y1-Yõ and Z1-Z, is intended
to refer to a
single element selected from X or Y or Z, a combination of elements selected
from the same
common class (such as Xi and X2), as well as a combination of elements
selected from
different classes (such as Xi, Y2 and 4).
[025] SCF / BBL (or scf / bbl) refers to a unit of standard cubic foot of gas
(N2, H2,
etc.) per barrel of hydrocarbon feed, or slurry catalyst, depending on where
the unit is used.
[026] The Periodic Table referred to herein is the Table approved by IUPAC and
the
U. S . National Bureau of Standards, an example is the Periodic Table of the
Elements by Los
Alamos National Laboratory's Chemistry Division of October 2001.
[027] "Metal" refers to reagents in their elemental, compound, or ionic form.
"Metal precursor" refers to the metal compound feed to the process. The term
"metal" or
"metal precursor" in the singular form is not limited to a single metal or
metal precursor, i.e.,
Group VIB or promoter metals, but also includes the plural references for
mixtures of metals.
"In the solute state" means that the metal component is in a protic liquid
form.
[028] "Group VIB metal" refers to chromium, molybdenum, tungsten, and
combinations thereof in their elemental, compound, or ionic form.
[029] "Promoter metal" refers to a metal in its elemental, compound, or ionic
form
selected from any of Group IVB, Group VIII, Group IIB, Group HA, Group IVA and
combinations thereof The Promoter metal increases the catalytic activity of
the Primary
metal, and is present in a smaller amount than the Primary metal.
5
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
[030] "Group VIII metals" refers to iron, cobalt, nickel, ruthenium, rhenium,
palladium, osmium, iridium, platinum, and combinations thereof
[031] 1000 F+ conversion rate refers to the conversion of a heavy oil
feedstock
having a boiling point of greater than 1000 F+ to less than 1000 F (538. C)
boiling point
materials in a hydroconversion process, computed as: (100% * (wt. % boiling
above 1000 F
materials in feed - wt. % boiling above 1000 F materials in products) / wt. %
boiling above
1000 F materials in feed)).
[032] "Dispersion" also known as "emulsion" in the context of slurry catalyst
refers
to two immiscible fluids in which one fluid (e.g., catalyst) is suspended or
dispersed in the
form of droplets in the second fluid phase (e.g., heavy oil feedstock or
hydrocarbon diluent)
as the continuous phase. In one embodiment, the droplets are in the range of
0.1 to 20
microns in size. In another embodiment, from 1 to 10 microns. The droplets can
subsequently coalesce to be larger in size. Droplet size can be measured by
methods known
in the art, including particle video microscope and focused beam reflectance
method, as
disclosed in Ind. Eng. Chem. Res. 2010, 49, 1412-1418, the disclosure of which
is herein
incorporated in its entirety by reference.
[033] Pore porosity and pore size distribution in one embodiment are measured
using mercury intrusion porosimetry, designed as ASTM standard method D 4284.
In
another embodiment, pore porosity and size distribution are measured via the
nitrogen
adsorption method. Unless indicated otherwise, pore porosity is measured via
the nitrogen
adsorption method.
[034] In one embodiment, the invention relates to a novel slurry catalyst
system for
use in heavy oil upgrade with improved properties including but not limited to
high surface
area / large pore volume, wherein the slurry catalyst system comprises in part
a deoiled spent
catalyst. The invention also relates to a method for the hydroconversion or
upgrade of heavy
oils, by sending the heavy oil feed to the upgrade process in the presence of
the a slurry
catalyst containing a deoiled spent catalyst.
[035] Deoiled Spent Catalyst: In one embodiment, the spent catalyst originates
from a bulk (unsupported) Group VIB metal sulfide catalyst optionally promoted
with at least
a Promoter Metal selected from a Group VB metal such as V, Nb; a Group VIII
metal such as
Ni, Co; a Group VIIIB metal such as Fe; a Group IVB metal such as Ti; a Group
IIB metal
such as Zn, and combinations thereof Promoter Metals are typically added to a
catalyst
formulation to improve selected properties, or to modify the catalyst activity
and/or
6
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
selectivity. In yet another embodiment, the spent catalyst originates from a
dispersed (bulk
or unsupported) Group VIB metal sulfide catalyst promoted with a Group VIII
metal for
hydrocarbon oil hydroprocessing. In another embodiment, the spent catalyst
originates from
a Group VIII metal sulfide catalyst. In yet another embodiment, the spent
catalyst originates
from a catalyst consisting essentially of a Group VIB metal sulfide. In one
embodiment, the
spent catalyst originates from a bulk catalyst in the form of dispersed or
slurry catalyst. In
another embodiment, the bulk catalyst is a colloidal or molecular catalyst.
[036] Further details regarding the catalyst wherefrom the spent catalyst
originates
are described in a number of publications, including US Patent Publication
Nos.
US20110005976A1, US20100294701A1, US20100234212A1, US20090107891A1,
US20090023965A1, US20090200204A1, US20070161505A1, US20060060502A1, and
US20050241993A1, the relevant disclosures with respect to the catalyst are
included herein
by reference.
[037] The bulk catalyst in one embodiment is used for the upgrade of heavy oil
products as described in a number of publications, including US Patent Nos.
US7901569,
US7897036, U57897035, U57708877, US7517446, US7431824, US7431823,
US7431822, U57214309, U57390398, U57238273 and U57578928; US Publication Nos.
U520100294701A1, U520080193345A1, U520060201854A1, and U520060054534A1, the
relevant disclosures are included herein by reference. In one embodiment,
after being used
in a hydroprocessing or heavy oil upgrade process, the spent catalyst has
diminished catalytic
activity compared to a fresh catalyst that has not been used in
hydroprocessing. In one
embodiment, the deoiled spent catalyst has less than 75% but more than 10% of
its original
catalytic activity. In another embodiment, the spent catalyst has more than
25% but less
than 50% of the original catalytic activity.
[038] After being used in hydroprocessing, the spent catalyst in one
embodiment
first undergoes "deoiling" treatment for the removal of hydrocarbons such as
oil, precipitated
asphaltenes, other oil residues and the like. The spent catalyst prior to
deoiling contains
carbon fines, metal fines, and (spent) unsupported slurry catalyst in
unconverted resid
hydrocarbon oil, with a solid content ranging from 5 to 50 wt. % in soluble
hydrocarbons as
unconverted heavy oil feedstock (resid). In another embodiment, the solid
content is 10-15
wt. % catalyst in soluble hydrocarbons. In one embodiment, the treatment is a
deoiling
process for oil removal. In another embodiment, the deoiling process further
comprises a
subsequent liquid / solid separation step for the recovery of deoiled spent
catalyst. The
7
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
deoiling process in one embodiment employs a filtration process such as cross-
flow filtration,
dynamic filtration, microfiltration, and combinations thereof, which may or
may not include
the use of a solvent for the removal of heavy oil from the spent catalyst. In
one embodiment,
the filtration process employs at least a membrane, e.g., filtration equipment
from VSEP
Technology. In yet another embodiment, sedimentation is used in combination
with a
filtration process.
[039] In one embodiment, the deoiling process comprises a number of separate
sub-
units including solvent wash (solvent extraction), filtration, sedimentation,
drying, and
solvent recovery sub-units. In one embodiment, the spent slurry catalyst is
first combined
with solvent to form a combined slurry-solvent stream prior to being filtered
via membrane
filtration. In another embodiment, the feedstock stream and the solvent are
fed to the filter as
separate feed streams wherein they are combined in the filtration process. The
ratio of spent
catalyst to solvent (as volume ratio) ranges from 0.10/1 to 100/1 (based on
the spent catalyst
slurry volume). In one embodiment, solvent is added in a volume ratio of
0.50/1 to 50/1. In
another embodiment, solvent is added in a volume ratio ranging from 1:1 to 1:6
(solvent to
heavy oil in the spent slurry catalyst).
[040] In one embodiment in addition to the oil removal step, the spent
catalyst
treatment further includes a thermal treatment step, e.g., drying,
calcination, and / or
pyrolizing, for removal of hydrocarbons from the spent catalyst. In one
embodiment, the
thermal treatment is under inert conditions, i.e., under nitrogen. In another
embodiment, the
drying temperature is at a sufficiently high temperature to decompose at least
90% of solvents
and other compounds that may be bound to the spent catalyst particles. In yet
another
embodiment, the deoiling is with the use of a sub-critical dense phase gas,
and optionally
with surfactants and additives, to clean / remove oil from the spent catalyst.
[041] The deoiling or removal of hydrocarbons from spent catalyst is disclosed
in a
number of publications, including US7790646, US7737068, W020060117101,
W02010142397, US20090159505A1, US20100167912A1, US20100167910A1,
US20100163499A1, US20100163459A1, US20090163347A1, US20090163348A1,
US20090163348A1, US20090159505A1, US20060135631A1, and US20090163348A1, the
relevant disclosures are included herein by reference.
[042] In one embodiment after deoiling, at least 50% of the soluble
hydrocarbons
(e.g., heavy oil) in the spent catalyst is removed. In another embodiment, the
removal rate is
at least 75%. In a third embodiment, at least 90% of the soluble hydrocarbons
in the spent
8
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
catalyst is removed. The spent catalyst after deoiling in one embodiment
contains less than
25 wt. % soluble hydrocarbons as unconverted resid. In a second embodiment,
less than 10
wt. % hydrocarbons (on a solvent free basis). In a third embodiment, the
deoiled spent
catalyst has less than 1 wt. % soluble hydrocarbons (on a solvent free basis).
In one
embodiment after deoiling, the spent catalyst has less than 500 ppm soluble
hydrocarbons in
the form of residual solvents.
[043] In one embodiment, after the oil removal process and after thermal
treatment,
the deoiled spent catalyst is in the form of a coke-like material. In yet
another embodiment,
the deoiled spent catalyst is the form of aggregate of particles, or clumps,
than can be ground
or crushed to the desired particle size, e.g., less than 20 microns, for
subsequent incorporation
into the slurry catalyst. The grinding or crushing can be done using
techniques known in the
art, e.g., via wet grinding or dry grinding, and using equipment known in the
art including but
not limited to hammer mill, roller mill, attrition mill, grinding mill, media
agitation mill, etc.
[044] The deoiled spent catalyst is characterized as having relatively high
surface
and pore volume, with the surface and pore volume characteristics varying
depending on the
residual catalytic activity and the amount of catalytic metal to heavy oil in
the upgrade
process where it was previously used. For example, a deoiled spent catalyst
with 30% of
original catalytic activity has lower surface area and pore volume compared to
a deoiled spent
catalyst with 75% of original catalytic activitiy. In another example, a
deoiled spent
catalyst with twice the amount of Mo (as wt. %) as a second deoiled spent
catalyst is
expected to have better surface area and pore volume.
[045] In one embodiment, the deoiled spent catalyst has a surface area ranging
from
0.5 to 100 m2/g. In a second embodiment, from 5 to 40 m2/g. In a third
embodiment, from
20 to 80 m2/g. The total pore volume (TPV) ranges from 0.02 to 0.5 cc/g in one
embodiment; from 0.05 to 0.3 cc/g in another embodiment; and from 0.10 to 0.2
cc/g in a
third embodiment. The mean particle size ranges from 1 to 100 gm (volume
basis, sonic) in
one embodiment; from 5 to 50 gm in a second embodiment. On a number basis, the
mean
particle size varies from 0.1 to 2 gm in one embodiment and 0.2 to 1 gm in a
second
embodiment.
[046] Optional Contaminant Metal Removal: After the oil removal process, the
amount metals left in the deoiled spent catalyst depends on the compositional
make-up of the
catalyst for use in hydroprocessing, e.g., a sulfided Group VIB metal
catalyst, a bimetallic
catalyst with a Group VIB metal and a promoter Group VIII metal, or a multi-
metallic
9
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
catalyst with at least a Group VIB and at least a Promoter metal. In some
embodiments, the
deoiled spent catalyst may comprise contaminants previously present in the
heavy oil
feedstock being upgraded with the catalyst. Examples of contaminants include
but are not
limited to Ni, Fe, V, Mg, Ca, etc. Depending on the catalyst concentration in
the heavy oil
upgrade process, its composition, the upgrade operations, as well as the
properties of the
heavy oil feedstock being used, in one embodiment, the deoiled spent catalyst
contains at
least 1 wt. % of metal contaminants in the form of vanadium primarily in
either oxide or
sulfide form. In another embodiment, the deoiled spent catalyst contains at
least 1 wt. %
nickel. In another embodiment, the amount of contaminants such as vanadium
ranges from 2
to 10 wt. %. In yet another embodiment, the amount of vanadium for removal /
pre-
treatment of the deoiled spent catalyst is at least 3 wt. %.
[047] Removal or passivation of contaminant metals such as vanadium is helpful
in
maintaining catalyst performance in heavy oil upgrade. Without being bound by
theory, it is
believed that metal contaminants from petroleum feed cover pores or sites in a
catalyst,
which may reduce the catalytic activity of or eventually deactivate a catalyst
feed.
[048] In one embodiment after deoiling (with or without thermal treatment),
the
deoiled spent catalyst is treated for the removal of contaminants. After
treatment, the
concentration of vanadium, a contaminant, is reduced by at least 20% in one
embodiment; at
least 40% in a second embodiment; and at least 50% in a third embodiment. In a
third
embodiment after treatment, the concentration of vanadium is reduced to less
than 500 ppm.
In a fourth embodiment, the reduced concentration of vanadium is less than 200
ppm.
[049] In one embodiment, the treatment is with a treating solution, with the
volume
ratio of treating solution to deoiled spent catalyst ranging from 2:1 to
100:1, with the deoiled
spent catalyst being "washed" upon contact with the treating solution to
remove the
contaminants. The treatment can be a single wash, or a multi-cycled wash, with
the deoiled
spent catalyst being treated with the same treating solution multiple times
(recycled), a fresh
treating solution for every wash cycle, or a different fresh treating solution
for each wash
cycle.
[050] The washing is carried out by soaking in the treatment solution or
mixing with
the treatment solution in a mixing tank for at least 5 minutes in one
embodiment, at least 30
minutes in a second embodiment, at least 1 hour in a third embodiment, and
from a period of
2 to 5 hours in a fourth embodiment. In yet another embodiment, the treating
or washing can
be carried out in a continuously operated, counter-current washing unit. The
washing is
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
ambient temperature in one embodiment, 50 F in a second embodiment, and at
least 100 F in
a third embodiment.
[051] In one embodiment with a deoiled spent catalyst containing vanadium
oxide as
a metal contaminant, the treating (washing) solution is plain water. In
another embodiment,
the treating solution comprises at least an inorganic mineral acid with a
relatively high
ionization constant such as sulfuric acid, hydrochloric acid, phosphoric acid,
nitric acid, etc.
In one embodiment, the acid has a strength ranging from 0.2 to 12.0 normal.
[052] In one embodiment for a deoiled spent catalyst with vanadium sulfide as
a
metal contaminant, the washing solution comprises at least an oxidizing agent
or oxidant in
an aqueous form. Examples of oxidizing agents include halogens, oxides,
peroxides and
mixed oxides, including oxyhalites, their acids and salts thereof Suitable
oxidizing agents
also include active oxygen-containing compounds, for example ozone. In one
embodiment,
the treating solution comprises hydrogen peroxide in the form of an aqueous
solution
containing 1% to 60% hydrogen peroxide (which can be subsequently diluted as
needed).
In yet another embodiment, the treating solution comprises hypochlorite ions
(0C1- such as
Na0C1, Na0C12, Na0C13, Na0C14, Ca(0C1)2, NaC103,NaC102, etc.), and mixtures
thereof.
In one embodiment, the amount of oxidizing agents / oxidants used is at least
equal to the
amount of metal contaminants to be removed on a molar basis, if not in an
excess amount.
[053] In one embodiment, the treating solution is selected depending on the
source
of the spent catalyst. In some embodiments with a spent catalyst containing
vanadium oxide
which is slightly soluble in water, water can be selected as the treating
solution to dissolve
and remove vanadium oxide. Aqueous acid solution can also be used for removing
vanadium contaminants with minimal removal of other metals in the sulfide
form. In other
embodiments with metal contaminants existing as vanadium sulfide, an oxidizing
agent can
be used as the treating solution to first oxidize the vanadium sulfide for
subsequent removal
with water or non-oxidizing acid water.
[054] In one embodiment, the washing is via a multi-step treatment, e.g., the
deoiled
spent catalyst is first treated with in a reductive wash with an aqueous
solution of a reducing
agent such as sulfur dioxide, oxalic acid, carbon monoxide or the like. The
reductive wash is
followed by an oxidative wash with an aqueous solution of the likes of an
organic peroxide,
hydrogen peroxide, ozone or a perchlorate. In another embodiment, the deoiled
spent
catalyst is first treated with an oxygen-containing gas, then followed by a
water wash to
remove any oxidized metal contaminants. After treatment, the deoiled catalyst
fines cluster
11
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
or settle by gravity to the bottom portion of the treatment tank, wherein the
treating solution
can be withdrawn / removed and subsequently separated from the deoiled spent
catalyst.
[055] Fresh Catalyst Portion: In one embodiment, a fresh catalyst is employed
in
addition to the deoiled spent catalyst, constituting the slurry catalyst feed
to the heavy oil
upgrade system. The fresh catalyst in one embodiment is an active (sulfided)
catalyst in a
hydrocarbon oil diluent, in the form of a slurry with dispersed particles or
clumps of particles.
In another embodiment, the fresh catalyst portion comprises a sulfided water-
based catalyst
precursor, which can be subsequently mixed with a hydrocarbon diluent and the
deoiled spent
catalyst, forming an oil based slurry catalyst. Examples of hydrocarbon oil
diluents include
VG0 (vacuum gas oil), naphtha, MCO (medium cycle oil), light cycle oil (LCO),
heavy cycle
oil (HCO), solvent donor, or other aromatic solvents, etc., in a weight ratio
ranging from 1:1
to 1:20 of catalyst to diluent.
[056] In one embodiment, the fresh slurry catalyst comprises a sulfided
catalyst
having at least a Group VIB metal, or at least a Group VIII metal, or at least
a group IIB
metal, e.g., a ferric sulfide catalyst, zinc sulfide, nickel sulfide,
molybdenum sulfide, or an
iron zinc sulfide catalyst, with a concentration of 200ppm to 2 wt. % metal as
a wt. % of
heavy oil feedstock. In another embodiment, the concentration of metal ranges
from 500
ppm to 3 wt. %. In another embodiment, the fresh catalyst portion comprises a
multi-metallic
catalyst comprising at least a Group VIB metal and at least a Group VIII metal
(as a
promoter), wherein the metals may be in elemental form or in the form of a
compound of the
metal. In one example, the fresh catalyst portion comprises a MoS2 catalyst
promoted with
at least a group VIII metal compound.
[057] In one embodiment, the fresh slurry catalyst has an average particle
size of at
least 1 micron. In another embodiment, the fresh slurry catalyst has an
average particle size
in the range of 1 ¨ 20 microns. In a third embodiment, the fresh slurry
catalyst has an
average particle size in the range of 2 ¨ 10 microns. In one embodiment, the
fresh slurry
catalyst particle comprises aggregates of catalyst molecules and/or extremely
small particles
that are colloidal in size (e.g., less than 100 nm, less than about 10 nm,
less than about 5 nm,
and less than about 1 nm). In yet another embodiment, the fresh slurry
catalyst comprises
aggregates of single layer MoS2 clusters of nanometer sizes, e.g., 5-10 nm on
edge. In
operations, the colloidal / nanometer sized particles aggregate in a
hydrocarbon diluent,
forming a slurry catalyst with an average particle size in the range of 1-20
microns.
12
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
[058] In one embodiment, at least 30% of the fresh slurry catalyst has pore
sizes
>100 Angstroms in diameter. In another embodiment, at least 40%. In yet
another
embodiment, at least 50% are in the range of 50 to 5000 Angstrom in diameter.
In one
embodiment, the fresh slurry catalyst has a total pore volume (TPV) of at
least 0.1 cc/g. In a
second embodiment, a TPV of at least 0.2 cc/g. In one embodiment, the fresh
slurry catalyst
as a surface area of at least 100 m2/g. In one embodiment, the surface area is
at least 200
m2/g. In another embodiment, the surface area is in the range of 200 to 900
m2/g.
[059] Details regarding the fresh catalyst and methods for preparation thereof
can be
found in US Patent Nos. 7947623, 7678730, 7678731, 7737072, 7737073, 7754645,
7214309, 7238273, 7396799, and 7410928; US Patent Publication Nos.
U520100294701A1,
U520090310435A1, U520060201854A1, U520110190557A1; and U520050241993A1; and
PCT Patent Publication No. W02011091219, the relevant disclosures are included
herein by
reference.
[060] Forming Slurry Catalyst Feed: In one embodiment, the deoiled spent
catalyst
is first slurried or reconstituted in a hydrocarbon diluent, forming a slurry
with dispersed
particles or clumps of particles, then fed to a heavy oil upgrade system as a
separate feed
stream from the fresh slurry catalyst. The separate feed system allows for the
tailoring or
proportioning of fresh slurry catalyst to deoiled spent catalyst. In yet
another embodiment,
the deoiled spent catalyst (in hydrocarbon diluent) is added directly to a
fresh slurry catalyst
(in hydrocarbon diluent), forming a single slurry catalyst feed stream for use
in heavy oil
upgrade. In yet a third embodiment, the deoiled spent catalyst can be mixed
with the
sulfided water-based catalyst precursor prior to the transformation step,
forming a slurry
catalyst. In another embodiment, the mixing of the deoiled spent catalyst and
the sulfided
water-based catalyst precursor is after the transformation step. In a fifth
embodiment, the
feed system can be flexible with fresh catalyst being provided as the sole
feed source at first,
then the deoiled spent catalyst is subsequently introduced as part of the
total slurry catalyst
feed to the system after the system is in operation for a period of time. In
yet another
embodiment with a flexible feed, the deoiled spent catalyst is provided to
some but not all
reactors in the system, on a continuous or intermittent basis, at the same or
different rates to
the different reactors in the system, all depending on the operating
conditions of the system
and the desired results.
[061] In one embodiment, the deoiled spent catalyst is first "reconstituted"
(or
"slurried") with the addition of a diluent such as a hydrocarbon oil feed,
e.g., VG0 (vacuum
13
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
gas oil), naphtha, MCO (medium cycle oil), light cycle oil (LCO), heavy cycle
oil (HCO),
solvent donor, or other aromatic solvents, etc., in a weight ratio ranging
from 1:1 to 1:25 of
deoiled spent catalyst to diluent, forming a slurry with the mixing of the
deoiled spent
catalyst with the hydrocarbon diluent. In another embodiment, the ratio of
deoiled spent
catalyst to hydrocarbon diluent ranges from 1:3 to 1:20. In a third
embodiment, the ratio of
deoiled spent catalyst to hydrocarbon diluent ranges from 1:5 to 1:10. The
reconstituted
stream can be added as part of the slurry catalyst feed to a heavy oil upgrade
system as a
separate feed stream, or combined with a fresh catalyst as a single feed
stream.
[062] The amount of deoiled spent catalyst to fresh slurry catalyst varies
depending
on a number of factors, including but not limited to the properties of the
heavy oil feedstock
amongst other process variables. In one embodiment, a sufficient amount of
deoiled spent
catalyst is employed for a ratio of fresh slurry catalyst to deoiled spent
catalyst from 1:5 to
5:1 (on a dry basis based on total solid catalyst weight to the system). In
another
embodiment, the amount of deoiled spent catalyst ranges from 20 to 75 % of
total slurry
catalyst to the heavy oil upgrade system (on a dry basis). In a third
embodiment, the amount
ranges from 30 to 66 %. In a fourth embodiment, the amount of deoiled spent
catalyst is at
least 10% of the total slurry catalyst feed to the system.
[063] The total amount of slurry catalyst feed to the heavy oil upgrade system
varies
from a slurry catalyst concentration of at least 500 wppm to 3 wt.% (based on
amount of the
Primary catalyst metal in the slurry catalyst, fresh and deoiled, to heavy oil
feedstock ratio).
In one embodiment, the total amount of slurry catalyst is added to the
feedstock for a primary
catalyst metal to oil rate of 0.01 to 3 wt. %. In a second embodiment, at a
rate of 0.15 to 2
wt. %. In a third embodiment, at a rate of 1000 to 4000 ppm Primary metal,
e.g., a Group
VIB metals such as molybdenum. In a fourth embodiment, the catalyst feed is
added to the
heavy oil feedstock at a sufficient rate for the total amount of Primary metal
in the reaction
zone reaches 0.05 to 0.5 wt. % (catalyst metal in the slurry catalyst as a
percent of the total
weight of the feedstock).
[064] The slurry catalyst (whether the fresh catalyst itself, the
reconstituted spent
catalyst, or a mixture of both) comprises a dispersed suspension of particles
in a hydrocarbon
diluent or medium. The hydrocarbon medium can be a heavy oil feedstock itself;
a
hydrocarbon transforming agent (diluent) such as VG0, naphtha, MCO, LCO, HCO,
solvent
donor, or other aromatic solvents, etc., and mixtures thereof; or a mixture of
heavy oil
14
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
feedstock and a hydrocarbon diluent. The mixing with the hydrocarbon medium in
one
embodiment is under high shear mixing to generate an emulsion catalyst.
[065] In one embodiment, the slurry catalyst with deoiled spent catalyst and
fresh
catalyst comprises a plurality of suspended or dispersed droplets in solution
("emulsion
catalyst") with the droplets having a mean size of 0.005 to 500 microns. In a
second
embodiment, the dispersed particles or droplets have an average droplet size
of 0.01 to 100
microns. In a third embodiment, an average droplet size of 0.5 to 50 microns.
In a fourth
embodiment, an average droplet size of 1 to 30 microns. In a fifth embodiment,
a size of 5 to
20 microns. In a sixth embodiment, an average droplet size in the range of 0.3
to 20 ,um. In
a seventh embodiment, an average droplet size ranging from 0.10 to 50 microns.
[066] In one embodiment, the slurry catalyst comprises a plurality of
dispersed
particles in a hydrocarbon medium, wherein the dispersed particles have a mean
particle size
ranging from 0.05 to 300 microns. In another embodiment, the particles have a
mean particle
size ranging from 2 to 200 microns. In yet another embodiment, a mean particle
size of less
than 40 microns. In a fourth embodiment, the slurry catalyst has an average
particle size of
2 to 200 microns. In a fifth embodiment, the slurry catalyst has an average
particle size of 5
to 100 microns. In one embodiment, the slurry catalyst has a mean particle
size ranging from
colloidal (nanometer size) to about 1-2 microns. In another embodiment, the
catalyst
comprises catalyst molecules and/or extremely small particles, forming a
slurry catalyst with
"clusters" of colloidal particles having an average particle size in the range
of 1 ¨ 20 microns.
[067] In one embodiment, the slurry catalyst with deoiled spent catalyst and
fresh
catalyst is characterized as having a polymodal pore distribution with at
least a first mode
having at least about 80% pore sizes in the range of 5 to 2,000 Angstroms in
diameter, a
second mode having at least about 70% of pore sizes greater in the range of 5
to 1,000
Angstroms in diameter, and a third mode having at least 20% of pore sizes of
at least 100
Angstroms in diameter. As used herein, polymodal includes bimodal and higher
modal. In
one embodiment, at least 20% of pore sizes are >100 Angstroms in diameter. In
another
embodiment, at least 30%.
[068] In one embodiment, the slurry catalyst with a total concentration of at
least
4000 ppm (as catalyst metals in heavy oil feed) having at least 25% deoiled
spent catalyst is
characterized as having an increase in pore volume (over 100 Angstroms) of at
least 20%
over a catalyst without any deoiled spent catalyst and the same concentration
of catalyst
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
metals. For a slurry catalyst with at least 50% deoiled spent catalyst, the
increase in PV (>
100 Angstrom) is at least 40% over a comparable catalyst feed without any
spent catalyst.
[069] Heavy Oil Upgrade System. The slurry catalyst feed with deoiled spent
catalyst can be used in hydroprocessing processes to treat a plurality of
heavy oil feedstock
under wide-ranging reaction conditions such as temperatures from 200 to 450
C., hydrogen
pressures from 5 to 300 bar (72 to 4351 psi or 0.5 to 30 MPa), liquid hourly
space velocities
from 0.05 to 10 h-1 and hydrogen treat gas rates from 35 to 2670 m3/ m3(200 to
15000
SCF/B), with the fresh slurry catalyst and the deoiled spent catalyst being
fed to the process
as separate feed streams, or as a single feed stream.
[070] The hydroprocessing (or hydrocracking) can be practiced in one or more
reaction zones and can be practiced in either countercurrent flow or co-
current flow mode,
where the feed stream flows counter-current to the flow of hydrogen-containing
treat gas. In
one embodiment, the hydroprocessing also includes slurry and ebullated bed
hydrotreating
processes for the removal of sulfur and nitrogen compounds. In one embodiment,
the
upgrade system includes a plurality of reaction zones (reactors) and at least
a separation zone
(separator). The deoiled spent catalyst can be supplied to only one reactor
such as the first
reactor, or it can be fed to different reactors in the system, as a continuous
feed, or
intermittently depending on the operation.
[071] In the reactors under hydrocracking conditions, at least a portion of
the heavy
oil feedstock is converted to lower boiling hydrocarbons, forming upgraded
products. The
mixture of upgraded products, the spent slurry catalyst, the hydrogen
containing gas, and
unconverted heavy oil feedstock is sent to the next reactor in series, which
is also maintained
under hydrocracking conditions. In the next reactor with additional hydrogen
containing gas
feed and optionally with additional heavy oil feedstock, at least a portion of
the heavy oil
feedstock is converted to lower boiling hydrocarbons, forming additional
upgraded products.
[072] In some embodiments before going to the next reactor in series (or after
the
last reactor in series), the mixture exiting the reactor is sent to a
separator (separation zone),
whereby the upgraded products are removed with the hydrogen containing gas as
an overhead
stream, and the spent slurry catalyst and the unconverted heavy oil feedstock
are removed as
a non-volatile stream.
[073] In one embodiment, water (and / steam) is added to at least one of the
reactors
(or all the reactors) in the system in ratio of 1 to 25 wt. % of the heavy oil
feedstock. The
water can be added separately or to the catalyst feed system, in combination
with the deoiled
16
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
spent catalyst slurry and / or the fresh catalyst slurry. It is believed that
the presence of the
water in the process favorably reduces heavy metal deposit.
[074] It should be noted that the use of deoiled spent slurry catalyst does
not
preclude incorporating spent catalyst (but not deoiled) in a recycled stream
as a feed to the
heavy oil upgrade system. The recycled stream herein comprises at least a
portion of the
non-volatile stream from at least one of the separation zones in the heavy oil
upgrade system,
e.g., from an ISF (interstage flash unit) or from a separation zone after the
last reactor in the
system, and / or an interstage deasphalting unit. In one embodiment, the
recycled stream is
sent one of the reactors in the system as part of the feed to control the
heavy metal deposits.
The recycled stream ranges between 3 to 50 wt.% of total heavy oil feedstock
to the process;
5 to 35 wt. % in a second embodiment; at least 10 wt. % in a third embodiment;
at least 35
wt. % in a fourth embodiment; and 35 to 50 wt. % in a fifth embodiment. The
recycled
stream comprises non-volatile materials from the last separation zone in the
system,
containing unconverted materials, heavier hydrocracked liquid products, slurry
catalyst, small
amounts of coke, asphaltenes, etc. The recycled stream contains between 3 to
30 wt. %
spent slurry catalyst in one embodiment; 5 to 20 wt. % in a second embodiment;
and 1 to 15
wt. % in a third embodiment.
[075] Details regarding operations of the hydroprocessing reactors in heavy
oil
upgrade can be found in US Patent Application Nos. 13/103790, 12/506840,
12/233393,
12/233439, 12/212737; US Patent Nos. 7,943,036; 7,931,797; 7,897,036;
7,938,954;
7,935,243; 7,943,036; 7,578,928; and US Patent Publication Nos. 2011-0017637
and 2009-
0008290, the relevant disclosures are included herein by reference.
[076] The deoiled spent catalyst can be added to the upgrade system as an
additional
or supplemental feed stock, i.e., added to an upgrade system with the regular
dosage of fresh
catalyst feed at a rate of 0.10X to 3X the fresh catalyst feed to help reduce
the build-up of
metal contaminants. In another embodiment, the deoiled spent catalyst can be
added as a
replacement feed, allowing the amount of fresh catalyst feed in the regular
dosage to be
reduced, with the deoiled spent catalyst being supplied at a rate ranging from
1X to 5X of the
fresh catalyst feed that it replaces, depending on the retained catalytic
level of the deoiled
spent catalyst. The replacement or supplemental feed can be on a long-term
continuous
basis, or on a short-term basis to temporarily reduce or relieve deposit build-
up in the system.
[077] In one embodiment, the slurry catalyst feed system with deoiled spent
catalyst
is characterized as giving excellent conversion rates in heavy oil upgrade,
i.e., giving a
17
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
1000 F+ conversion of at least 50% in the upgrade of a heavy oil having an API
of at most
15, when applied at less than 1 wt. % Primary metal such as a Group VIB (wt. %
relative to
heavy oil feedstock), a 1000 F+ conversion of at least 75% in a second
embodiment, a
1000 F+ conversion of at least 80% in a third embodiment, and at least 90% in
a fourth
embodiment.
[078] In one embodiment, a heavy oil upgrade system with additional deoiled
spent
catalyst as part of the feed system is characterized as having less
contaminants / metal deposit
in the reactor system, e.g., build-up of metal contaminants such as vanadium.
It is believed
that the deoiled spent catalyst provides additional surface area to trap
contaminants while still
offering left-over catalytic activity. The additional surface area in the
deoiled spent catalyst
traps at least a contaminant such as vanadium, the trapped vanadium is then
removed from
the reactor system as spent catalyst, thus reducing the amount of vanadium
deposit left in the
upgrade system. In addition to the reduction in deposit build-up, the deoiled
spent catalyst
helps reduce cost with the fresh catalyst being replaced with the less
expensive spent catalyst.
[079] In one embodiment of a heavy oil upgrade system with deoiled spent
catalyst
as a supplemental feedstock, e.g., having an additional 25% of the catalyst
feed in the form of
deoiled spent catalyst, is expected to have at least 5% reduction in vanadium
build-up and
with the same or better conversion rates, as compared to an upgrade system
with no
additional deoiled spent catalyst in the feed (and the same amount of fresh
catalyst in the
heavy oil feedstock). In another embodiment with a feed system comprising
deoiled spent
catalyst to fresh catalyst at a weight ratio of at least 2:1, with the Primary
metal concentration
of the fresh slurry catalyst is at least 1000 ppm (wt. % of metal to heavy oil
feedstock), the
reduction in vanadium build up is at least 10% for a comparable conversion
rate, compared to
an upgrade system with the same amount of fresh catalyst only.
[080] In one embodiment of a heavy oil upgrade system with deoiled spent
catalyst
as a replacement feedstock and with a Primary metal concentration in the
catalyst feed system
of at least 1000 ppm, the deoiled spent catalyst is provided at a rate of at
least 2X the amount
of the fresh catalyst it replaces for a reduction of metal build up of at
least 5% at comparable
conversion rates. In another embodiment with a replacement feed rate of 3X
(deoiled spent
catalyst to fresh catalyst being replaced), the reduction in metal build up is
at least 10%.
[081] Reference will be made to the figures with block diagrams schematically
illustrating different embodiments of a process for making a slurry catalyst
with a deoiled
spent catalyst for heavy oil upgrade.
18
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
[082] FIG. 1 schematically illustrates various embodiments of a
hydroconversion
process with a slurry catalyst feed including a deoiled spent catalyst. In the
process to
upgrade a heavy oil feedstock, fresh catalyst feed is made in a synthesis unit
10 and supplied
directly to the reactor 20 as a separate feed stream 12. In another
embodiment, the fresh
catalyst feed can also be made off-site or commercially purchased and supplied
as feed
stream 21. In the embodiment as shown, heavy oil feedstock is fed as a
separate feed stream
25. In other embodiments (not shown), the heavy oil feed can be combined with
the fresh
slurry catalyst feed, and / or the deoiled spent catalyst feed, and / or a
recycled stream
containing spent catalyst and unconverted heavy oil as a single feed stream to
the reactor 20.
[083] From the heavy oil upgrade system 20, spent catalyst 22 undergoes a
deoiling
step 30, wherein at least 50% of the soluble hydrocarbons are removed. The
deoiled spent
catalyst can be incorporated into the slurry catalyst feed system as feed
stream 24. In one
embodiment, the deoiled spent catalyst is first thermally treated in dryer 40
before being sent
to the reactor as feed stream 41. In another embodiment, after drying, the
deoiled spent
catalyst 42 is calcined in calcination unit 50. In yet another embodiment,
deoiled spent
catalyst 33 is fed directly to calciner 50, then sent to upgrade reactor as
feed stream 51.
Although not shown, the deoiled spent catalyst is first slurried in a
hydrocarbon diluent prior
to being fed to the reactor 20. The slurried deoiled catalyst can be fed to
the reactor system
as a separate feed stream 24, combined with the fresh slurry catalyst 11 as a
single feed
stream 23, or combined with the heavy oil feedstock as a single feed stream
(not shown).
[084] FIG. 2 shows a scheme wherein the deoiled spent catalyst is first
treated to
remove contaminants. In this embodiment, at least some or all of the deoiled
spent catalyst
is sent to treatment unit 60, wherein undesirable contaminants such as
vanadium can be
removed with a treating agent, a water wash, a treatment solution containing
at least a
mineral acid, an oxidizing agent or an oxidant, or combinations of the above
treatment
methods. The treatment step 60 further comprises a separation step (not
shown), wherein
the deoiled spent catalyst is separated from the treatment agent. Although not
shown, after
treatment, the deoiled spent catalyst can be dried in a dryer or thermally
treated in a calciner,
before it is slurried in a hydrocarbon diluent. The slurried treated / deoiled
spent catalyst can
be fed to the upgrade reactor system as a separate feed stream, or combined
with the fresh
slurry catalyst and / or the heavy oil feedstock as a single feed stream.
[085] EXAMPLES: The following illustrative examples are intended to be non-
limiting. VR refers to "vacuum resid" or a heavy oil feedstock. In the
examples, the heavy
19
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
oil feedstock VR1 contains 20.8 wt% microcarbon residue (MCR), 10.7 wt% hot
heptane
asphaltenes (HHA), 1.86 wt% sulfur, 1.2 wt% nitrogen, 150 ppm vanadium, 146
ppm nickel,
and 4.8 degrees of API at 60 F. The heavy oil feedstock VR2 contains 29.9 wt.%
microcarbon residue (MCR), 25.7 wt.% hot heptane asphaltenes (HHA), 5.12 wt. %
sulfur,
0.79 wt% nitrogen, 672 ppm vanadium, 142 ppm nickel and 2.7 degrees of API at
60 F.
[086] Example 1: A Ni-Mo slurry catalyst as described in US Patent Nos.
7737072
and 7737073 was used in a heavy oil upgrade process as described in US Patent
No.
7390398. The catalyst was used at a high concentration of Mo relatively to VR
feed (4 wt. %
Mo to VR), so it is "lightly-deactivated" with ¨ 50% of the original catalytic
activity (relative
to a fresh catalyst). The spent catalyst underwent a deoiling step similar to
the procedures
described in US Patent Publication No. 20100163499, employing a combination of
sedimentation and a cross-filtration system wherein a solvent is added to the
filtration feed
stream, generating a deoiled solids coke product containing metal sulfides.
The deoiled spent
catalyst was slurried in VG0 or VGO-based fresh slurry catalyst, at a VG0 to
deoiled spent
catalyst weight ratio of 2:1 to 20:1, forming a slurried catalyst ("SCS" or
spent catalyst
slurry).
[087] Example 2: A second Ni-Mo deoiled spent catalyst was generated as in
Example 1, except that the catalyst was employed at a low concentration of Mo
relative to
heavy oil feed (0.5 wt. % Mo to VR), retaining less than ¨ 1/3 of the original
catalytic
activity. Table 1 summarizes the properties and characteristics of the deoiled
spent catalyst
samples. The deoiled spent catalyst was slurried in VG0 or VGO-based fresh
slurry catalyst,
at a VG0 to deoiled spent catalyst weight ratio of 2:1 to 20:1, forming a
slurried catalyst
("SCS" or spent catalyst slurry).
[088] Table 1
Composition Example 1 Example 2
Mo, wt% 39.27 30.37
Ni, wt% 4.05 3.56
V, wt% 0.66 2.91
C, wt% 23.35 34.28
Porosimetry
SA, m2/g 33.11 9.14
TPV, cc/g 0.137 0.065
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
PV (> 100 A), cc/g 0.109 0.062
Particle Size Distribution
Mean Dp (volume-basis, sonic), gm 8.2 29.0
Mean Dp (number-basis, sonic), gm 0.27 0.72
[089] Example 3: A third Ni-Mo deoiled spent catalyst was generated as in
Example 1, an analysis of the spent catalyst solid shows 24.91 wt. % Mo, 4.42
wt. % Ni, and
6.22 wt. % V (primarily oxide form).
[090] Example 4: Another Ni-Mo deoiled spent catalyst was generated as in
Example 1, an analysis of the spent catalyst solid shows 20.55 wt. % Mo, 3.52
wt. % Ni, and
9.98 wt.% V (primarily sulfide form).
[091] Example 5: The deoiled spent catalyst of Examples 3 and 4 were washed
with water at a ratio of 1:30 spent catalyst to water (by weight). After
filtration, analysis
showed that 21% vanadium was removed from Example 3 sample and 1% of vanadium
was
removed from Example 4 sample.
[092] Example 6: The deoiled spent catalyst of Example 3 was washed with H2SO4
solution at 1:30 weight ratio at a molar ratio H2SO4 to V of 2Ø With the use
of acid as the
treating solution to increase the solubility of vanadium oxide, 47% of
vanadium was
removed. The deoiled spent catalyst of Example 4 was also treated H2SO4
solution under
the same condition, only 1% was removed.
[093] Example 7: The deoiled spent catalyst of Example 4 was treated with
1.2wt%
hydrogen peroxide solution at 1:30 wt ratio. After filtration, the analysis
showed that 44% of
vanadium was removed from the deoiled spent catalyst by hydrogen peroxide
(instead of only
1 wt% of removal by water or sulfuric acid solution).
[094] Example 8: The spent catalyst of Example 3 was washed with water at a
ratio
of 1:30 spent catalyst to 0.9 % H2SO4 aqueous solution (by weight). After
filtration, an
analysis of the filtrate showed 10.5 ppm Mo, 121 ppm Ni, and 131 ppm V,
indicating that
contaminant metals in the spent catalyst can be removed by washing with water
with 17% V
removal.
[095] Example 9: In this example, 9000 grams of ammonium dimolybdate (ADM)
solution (12% Mo) was heated to 750 RPM, 150 F and 400 PSIG. To this heated
ADM
21
CA 02848508 2014-03-12
WO 2013/039950 PCT/US2012/054723
solution, a gas stream comprising 20% H2S, 20% CH4, 60% H2 was bubbled through
the
solution until the S/Mo atomic = 3.4. After the H2S addition, then an
appropriate amount of
nickel sulfate solution (8% Ni) was added to the mixture for a Ni/Mo wt% of ¨
10%. The
product can be transformed to an oil base catalyst as in Comparative Example 1
on a batch
basis, or a continuous basis. The resulting water-based catalyst was
transformed to a fresh
slurry catalyst, e.g., an oil-based catalyst with vacuum gas oil (VGO) and
hydrogen in a
pressure test autoclave in situ, at a VG0 to catalyst weight ratio of 2:1.
[096] Example 10: In this example, another fresh slurry catalyst is provided.
9000
grams of ADM solution (12% Mo) was heated to 750 RPM, 150 F and 400 PSIG. To
this
heated solution, a gas stream comprising 20% H25, 20% CH4, 60% H2 was bubbled
through
the solution until the S/Mo atomic = 3.4. After the H25 addition, then an
appropriate amount
of nickel sulfate solution (8% Ni) was added to the mixture for a Ni/Mo wt% of
¨ 23%. The
rest of the procedures and tests were similar to Example 9 to transform the
catalyst to an oil-
based catalyst.
[097] Example 11: Different slurry catalyst samples were made by adding the
deoiled spent catalyst from Example 1 ("SCS 1" or spent catalyst slurry) with
the fresh slurry
catalyst from Example 9 ("FCT" or fresh catalyst"). Table 2 lists the catalyst
dosage for
fresh catalyst and deoiled catalyst of the slurry catalyst feed mixtures:
[098] Table 2
Mo from Mo from
FCT, SCS,
ppm PPm
100% Ex. 9 FCT 4000 0
25% SCS 1 - 75% FCT
3000 1000
Ex. 9
50% SCS 1 - 50% FCT
2000 2000
Ex. 9
79% SCS 1 - 21% FCT
2000 7500
Ex. 9
[099] Example 12: Different slurry catalyst samples were made by adding the
deoiled spent catalyst from Example 2 ("SCS 2" or spent catalyst slurry) with
the high Ni
fresh slurry catalyst from Example 10 ("FCT High Ni"). Table 3 lists the
catalyst dosage for
fresh catalyst and deoiled catalyst of the slurry catalyst feed mixtures:
22
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
[0100] Table 3
Mo from Mo from
FCT, SCS,
ppm ppm
FCT Hi-Ni (Base Case 1) 6000 0
FCT Hi-Ni (Base case 2) 3000 0
25% SCS 2 ¨ 75% FCT
4500 1500
Hi-Ni
50% SCS 2 ¨ 50% FCT
3000 3000
Hi-Ni
[0101] Examples 13 - 16: Catalyst samples from Example 11 were tested in a
continuous flow unit with three 1-gallon continuous stirring tank reactors
(CSTRs) in series.
VR Liquid Hourly Space Velocity (LHSV) and reaction temperature are listed in
Table 4.
The VR feed was VR1.
[0102] Table 4 compares the heavy oil upgrade performance using a fresh slurry
catalyst (standard Mo-only of Example 9) vs. slurry catalyst feed systems
containing deoiled
spent catalyst prepared in Example 11. The slurry catalyst feed examples with
deoiled spent
catalyst showed excellent metal removal characteristics, as indicated by low V
trapping. V
trapping is measured as total vanadium not recovered from (coming out of) the
system vs. total
vanadium fed into the system. A low percentage is more desirable, meaning less
contaminant
is trapped in the reactor. It should be noted that in Example 16, keeping the
fresh Mo dosage
at 2000 ppm and increasing the spent catalyst dosage to 7500 ppm Mo, the
catalytic conversion
(HDS, and HDN) increased by 4-6% as compared to Example 15 with a 50 / 50
fresh catalyst
to deoiled spent catalyst ratio.
[0103] Table 4
Example 13
Comparativ Example 15 Example 16
Example 14
e
25% SCS 1 - 50% SCS 1 - 79% SCS 1 -
100% Ex. 9
Catalyst 75% FCT Ex. 50% FCT Ex. 21% FCT Ex.
FCT
9 9 9
VR1 LHSV 0.125 0.125 0.125 0.125
Avg. Rx Temp., F 819.5 819.5 819.3 820.0
Mo from FCT, ppm 4000 3000 2000 2000
23
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
Mo from SCS, ppm 0 1000 2000 7500
Conversion
Sulfur, % 85.94 85.80 85.75 89.80
Nitrogen, % 35.81 33.60 34.07 41.39
MCR, % 76.98 76.61 76.58 77.58
VR (1000 F+), % 91.88 91.26 91.55 91.37
Metal trapping
V trapping 14% 5% 11% 0%
[0104] Examples 17 - 20: Catalyst samples from Example 12 were tested in a
continuous flow unit with three 1-gallon continuous stirring tank reactors
(CSTRs) in series.
VR Liquid Hourly Space Velocity (LHSV) and reaction temperature are listed in
Table 5.
The VR feed was VR2.
[0105] Table 5 compares the heavy oil upgrade performance using a fresh slurry
catalyst (high Ni Mo-Ni of Example 10) vs. slurry catalyst feed systems of
Example 12,
containing deoiled spent catalyst. The slurry catalyst feed examples with
deoiled spent
catalyst showed excellent metal removal characteristics as indicated by very
low V trapping,
even for deoiled spent catalyst with little catalytic activity (< 1/3 original
catalytic activity for
SCS 2). Additionally, it is noted that the use of deoiled spent catalyst still
allows for excellent
HDS and HDN activity with less fresh catalyst feed requirements.
[0106] Table 5
Example 17 Example 18
Comparative Comparative Example 19
Example 20
Std. Hi-Ni25% SCS 2 - 50% SCS 2 -
Hi-Ni
Catalyst (Base Case Std.
(Base Case 2) 75%. FCT Hi- 50% FCT Hi-
1) Ni
VR2 LHSV 0.10 0.10 0.10 0.10
Avg. Rx Temp., F 818.7 818.5 818.7 818.6
Mo from FCT,
6000 3000 4500 3000
PPm
Mo from SCS, 0 0 1500 3000
PPm
Conversion
Sulfur, % 91.42 88.81 91.13 90.69
24
CA 02848508 2014-03-12
WO 2013/039950
PCT/US2012/054723
Nitrogen, % 53.35 48.13 52.11 51.39
MCR, % 83.53 83.32 83.19 83.47
VR (1000 F+), % 94.03 93.75 93.80 93.53
Metal trapping
V trapping 1.4% 23.7% 2.4% 1.9%
[0107] For the purposes of this specification and appended claims, unless
otherwise
indicated, all numbers expressing quantities, percentages or proportions, and
other numerical
values used in the specification and claims, are to be understood as being
modified in all
instances by the term "about." Accordingly, unless indicated to the contrary,
the numerical
parameters set forth in the following specification and attached claims are
approximations
that may vary depending upon the desired properties sought to be obtained by
the present
invention. It is noted that, as used in this specification and the appended
claims, the singular
forms "a," "an," and "the," include plural references unless expressly and
unequivocally
limited to one referent. As used herein, the term "include" and its
grammatical variants are
intended to be non-limiting, such that recitation of items in a list is not to
the exclusion of
other like items that can be substituted or added to the listed items.
[0108] This written description uses examples to disclose the invention,
including the
best mode, and also to enable any person skilled in the art to make and use
the invention.
The patentable scope is defined by the claims, and may include other examples
that occur to
those skilled in the art. Such other examples are intended to be within the
scope of the claims
if they have structural elements that do not differ from the literal language
of the claims, or if
they include equivalent structural elements with insubstantial differences
from the literal
languages of the claims. All citations referred herein are expressly
incorporated herein by
reference.
