U.S. patent application number 13/107461 was filed with the patent office on 2011-09-08 for catalyst for the hydrodesulfurization of residua and heavy crudes.
This patent application is currently assigned to INSTITUTO MEXICANO DEL PETROLEO. Invention is credited to Fernando Alonso Martinez, Jorge Ancheyta Juarez, Samir Kumar Maity, Jorge Fernando Ramirez Solis, Mohan Singh Rana, Patricia Rayo Mayoral.
Application Number | 20110218097 13/107461 |
Document ID | / |
Family ID | 38088281 |
Filed Date | 2011-09-08 |
United States Patent
Application |
20110218097 |
Kind Code |
A1 |
Rayo Mayoral; Patricia ; et
al. |
September 8, 2011 |
Catalyst for the hydrodesulfurization of residua and heavy
crudes
Abstract
A catalyst for hydrotreating, especially hydrodesulfurization,
of residua and heavy crudes is prepared by synthesizing the support
from titanium and boehmite, to form either a titanium/alumina
support (TiO.sub.2/Al.sub.2O.sub.3) or a titanium-alumina support
(TiO.sub.2--Al.sub.2O.sub.3) that is thereafter provided with at
least one hydrogenating metal from group VIB in oxide form and a
promoter from group VIII also in oxide form. The
(TiO.sub.2/Al.sub.2O.sub.3) support is prepared from boehmite,
which is peptized by using an inorganic acid, then extruded,
calcined and impregnated with a solution containing titanium, while
the (TiO.sub.2--Al.sub.2O.sub.3) support is prepared by admixing
boehmite with a titanium-containing solution, peptized using an
inorganic acid, extruded and calcined to obtain the
titanium-alumina support.
Inventors: |
Rayo Mayoral; Patricia;
(Mexico City, MX) ; Ancheyta Juarez; Jorge;
(Mexico City, MX) ; Ramirez Solis; Jorge Fernando;
(Mexico City, MX) ; Maity; Samir Kumar; (Mexico
City, MX) ; Rana; Mohan Singh; (Mexico City, MX)
; Alonso Martinez; Fernando; (Mexico City, MX) |
Assignee: |
INSTITUTO MEXICANO DEL
PETROLEO
Mexico City
MX
|
Family ID: |
38088281 |
Appl. No.: |
13/107461 |
Filed: |
May 13, 2011 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
11582552 |
Oct 18, 2006 |
7968069 |
|
|
13107461 |
|
|
|
|
Current U.S.
Class: |
502/150 ;
502/220; 502/309 |
Current CPC
Class: |
B01J 35/1038 20130101;
B01J 37/0009 20130101; B01J 37/0207 20130101; B01J 23/883 20130101;
B01J 35/1042 20130101; B01J 35/1019 20130101; B01J 23/85 20130101;
B01J 21/063 20130101; C10G 2300/202 20130101; C10G 65/04 20130101;
B01J 35/108 20130101; C10G 2300/206 20130101; C10G 2300/1033
20130101; C10G 2300/703 20130101; C10G 45/08 20130101; B01J 35/1061
20130101 |
Class at
Publication: |
502/150 ;
502/309; 502/220 |
International
Class: |
B01J 21/06 20060101
B01J021/06; B01J 35/10 20060101 B01J035/10; B01J 27/051 20060101
B01J027/051; B01J 31/02 20060101 B01J031/02 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 29, 2005 |
MX |
PA/A/2005/012893 |
Claims
1. A catalyst for the hydrodesulfurization of residua and heavy
crudes consisting essentially of a TiO.sub.2/Al.sub.2O.sub.3 or
TiO.sub.2--Al.sub.2O.sub.3 support having a concentration of 3-6 wt
% titanium, and active metal concentrations comprising 8-12 wt %
molybdenum and 2-6 wt. % nickel.
2. The catalyst of claim 1, wherein said catalyst support is
TiO.sub.2/Al.sub.2O.sub.3.
3. The catalyst of claim 1, wherein said catalyst has an acidity of
from 70 to 120 mg of pyridine per gram of catalyst, a specific
surface area of 90 to 300 m.sup.2/g, an average pore diameter of
from 5.0 to 15.0 nm and a total pore volume of from 0.2 to 0.7
cm.sup.3/g.
4. The catalyst of claim 1, wherein said catalyst has less than 30%
of its pore volume from pores of 0 to 5 nm, 55 to 80% of its pore
volume from pores of 5 to 10 nm, and less than 15% of its pore
volume from pores with diameters greater than 10 nm.
5. The catalyst of claim 3, wherein said catalyst has less than 30%
of its pore volume from pores of 0 to 5 nm, 55 to 80% of its pore
volume from pores of 5 to 10 nm, and less than 15% of its pore
volume from pores with diameters greater than 10 nm.
6. The catalyst of claim 1, wherein said residua and heavy crudes
have been previously treated in a first stage of a hydrotreating
process.
7. A catalyst for the hydrodesulfurization of residua and heavy
crudes produced by the process of: a. preparing a support from
boehmite in which 5-20 wt % of the total boehmite is peptized with
an inorganic acid to form a binder and the remainder of the
boehmite and deionized water are added to the binder to form a
homogenous paste, and forming said paste into extrudates; b. aging
said extrudates at a temperature of 20.degree.-25.degree. C. for
12-18 hours, drying said extrudates at a temperature of
100.degree.-120.degree. C. for 2-6 hours, and calcining said dried
extrudates at a temperature of 500.degree.-600.degree. C. for 3-5
hours using a heating ramp of 2.degree. C./min, to obtain gamma
alumina; c. impregnating the gamma alumina with a titanium
precursor by the incipient wetness impregnation method using an
organic solvent to provide content of 3-6 wt % of titanium; d.
aging the impregnated support at a temperature of
20.degree.-25.degree. C. for 12-18 hours, followed by drying at a
temperature of 100.degree.-120.degree. C. and calcining at a
temperature of 400.degree.-500.degree. C., to obtain the anatase
phase of titanium on the surface of the gamma alumina; and e.
impregnating the resulting titania/alumina support
(TiO.sub.2/Al.sub.2O.sub.3) with a precursor of a metal from group
VIB and group VIIIB of the periodic table by spraying or incipient
wetness methods, either in simultaneous or sequential form.
8. The catalyst of claim 7, wherein said catalyst consists
essentially of a TiO.sub.2/Al.sub.2O.sub.3 support having a
concentration of 3-6 wt % titanium, 8-12 wt % molybdenum and 2-6 wt
% nickel.
9. The catalyst of claim 8, wherein said catalyst has an acidity of
from 70 to 120 mg of pyridine per gram of catalyst, a specific
surface area of 90 to 300 m.sup.2/g, an average pore diameter of
from 5.0 to 15.0 nm and a total pore volume of from 0.2 to 0.7
cm.sup.3/g.
10. The catalyst of claim 7, wherein said catalyst has less than
30% of its pore volume from pores of 0 to 5 nm, 55 to 80% of its
pore volume from pores of 5 to 10 nm, and less than 15% of its pore
volume from pores with diameters greater than 10 nm.
11. The catalyst of claim 8, wherein said catalyst contains from a
small amount of metals up to 500 ppm of the total amount of nickel
plus vanadium, up to 10 wt % of asphaltenes and a sulfur content of
from 0.5 to 5 wt %.
12. The catalyst of claim 8, wherein said catalyst is capable of
providing an initial hydrodesulfurization conversion of up to 83%
of HDS and a stability of up to 60% of HDS, as well as
hydrodemetallization and hydrodenitrogenation conversions of at
least 20%, and a hydrodeasphaltenization conversion of at least
25%.
13. A catalyst for the hydrodesulfurization of residua and heavy
crudes produced by the process of: a. preparing a support by
incorporating a titanium precursor into boehmite, peptizing the
mixture of boehmite and titanium precursor using an inorganic acid
and deionized water to form a homogenous paste, and extruding said
paste to form extrudates; b. aging the extrudates at a temperature
of 20.degree.-25.degree. C. for 12-18 hours, and then said aged
extrudates are dried at 100.degree.-120.degree. C. for 2-6 hours,
and calcined at 500.degree.-600.degree. C. for 3-5 hours using a
heating ramp of 2.degree. C./min to obtain a titania-gamma alumina
support; and c. impregnating said titania-gamma alumina support by
spraying or incipient wetness methods, either in simultaneous or
sequential form, with a precursor of a metal from group VIB and
group VIIIB of the periodic table.
14. The catalyst of claim 13, wherein the inorganic acid used in
the support synthesis is nitric acid at a concentration of 5-15
volume %.
15. The catalyst of claim 13, wherein the titanium precursor used
in the support synthesis is titanium isopropoxide.
16. The catalyst of claim 13, wherein the simultaneous impregnation
is conducted using a basic aqueous solution at pH of 9-9.5, which
contains Mo and Ni.
17. The catalyst of claim 14, wherein the simultaneous impregnation
is conducted using a basic aqueous solution at a pH of 9-9.5, with
ammonium heptamolybdate and hexahydrate nickel nitrate.
18. The catalyst of claim 13, wherein sequential impregnation is
used with ammonium heptamolybdate at a basic pH of 9-9.5 followed
by aging, drying and calcination, and then impregnation using
hexahydrate nickel nitrate at a pH of 5.5.
19. The hydrodesulfurization catalyst produced by the process of
claim 13, wherein said catalyst consists essentially of a
TiO.sub.2--Al.sub.2O.sub.3 support having a concentration of 3-6 wt
% titanium, and active metal concentrations comprising 8-12 wt %
molybdenum and 2-6 wt % nickel.
20. The catalyst of claim 19, wherein said catalyst has a specific
surface area of 90 to 300 m.sup.2/g, an average pore diameter of
from 5.0 to 15.0 nm and a total pore volume of from 0.2 to 0.7
cm.sup.3/g.
21. The catalyst of claim 19, wherein said catalyst has less than
30% of its pore volume from pores of 0 to 5 nm, 55 to 80% of its
pore volume from pores of 5 to 10 nm, and less than 15% of its pore
volume from pores with diameters greater than 10 nm.
22. The catalyst of claim 19, wherein said catalyst contains from a
small amount of metals up to 500 ppm of the total amount of nickel
plus vanadium, up to 10 wt % of asphaltenes and a sulfur content of
from 0.5 to 5 wt %.
23. The catalyst of claim 19, wherein said catalyst is capable of
providing an initial hydrodesulfurization conversion of up to 83%
of HDS and a stability of up to 60% of HDS, as well as
hydrodemetallization and hydrodenitrogenation conversions of at
least 20%, and a hydrodeasphaltenization conversion of at least
25%.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional application of Ser. No.
11/582,552, filed Oct. 18, 2006, which claims the benefit under 35
U.S.C. .sctn.119 of Mexican Patent Application No.
PA/a/2005/012893, filed Nov. 29, 2005, which is hereby incorporated
by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to a catalyst for
hydrotreating heavy crude and residua. More particularly, the
present invention relates to hydrodesulfurization catalysts having
improved hydrodesulfurization activity and are not deactivated
quickly by contaminants, such as nickel and vanadium that are
present in heavy crude oil feedstock.
BACKGROUND OF THE INVENTION
[0003] In the last decades, the increase in the demand of fuels has
caused a decrease in the reserves of light crudes throughout the
world. As a consequence, there has been an increase in the
production and availability of heavy crudes, causing an increase in
the research to make better use of heavy crude oil.
[0004] The low yields of light distillates recovered from the heavy
crudes as well as the need to reduce the high levels of
contaminants such as sulfur, nitrogen asphaltenes carbon and metals
(Ni and V) have oriented the research efforts towards the
hydrotreatment processes with the aim of improving the properties
of heavy feeds.
[0005] At present, the environmental restrictions throughout the
world have made mandatory the search for more effective catalysts
in order to obtain better quality fuels with a minimum content of
polluting agents like sulfur and nitrogen.
[0006] The catalysts used for hydrotreating of residua and heavy
crudes are an interesting alternative to remove impurities such as
sulfur, metals, asphaltenes, etc., and to increase notably the
production of middle distillates. In this sense the formulation of
the catalyst involves the control of its properties, the
interaction of the active components with the support, and the
method of preparation. The methodology of incorporation of the
active phases or composition of the support can change the activity
and stability of the catalyst. At present there are few reports in
the literature that directly refer to the hydrotreatment of heavy
crudes and residua; the studies have rather focused on the
treatment of residua obtained from light or medium heavy
crudes.
[0007] The majority of patents relating to the present invention
claim the use of metals of groups VIB and VIII of the periodic
table, supported on alumina. Likewise, other patents claim the use
of Mo with Ni and/or Co. Several others include the use of
compounds based in the elements of groups IA, IIA, VA, VIIA, IIB,
IVB, VB and VIIB of the periodic table using different types of
supports such as alumina, zeolites, silica, silica-alumina,
magnesium, silica-magnesium, titanium, activated carbon, clays,
alumina-boron, zirconium and combinations of them. Some of these
patents are described below.
[0008] U.S. Pat. No. 4,687,757 discloses an alumina support which
can contain compounds of transition metals from the groups IB, VB,
VIIB, VIIB and the VIII of periodic table, the support contains at
least one compound of titanium and one of molybdenum, having a
surface area in the 100-250 m.sup.2/g interval. In the detailed
description of the patent, a pore volume of 0.2-2.0 cm.sup.3/g is
mentioned, which was determined in a mercury penetration equipment,
used to determine macro-porosity, as demonstrated in example 1, in
the preparation of the catalyst D having pore volume 1.03
cm.sup.3/g. From these data, it is evident that the catalyst of the
referred patent is used mainly in the hydrodemetallization stage
and not in the hydrodesulfurization stage.
[0009] U.S. Pat. No. 5,545,602 discloses a catalyst with a
composition containing 13-24 weight % of metals of group VIII, 0-2
weight % of metals of group VIB and one phosphorus oxide, with a
surface area of 150-240 m.sup.2/g, total pore volume of 0.7-0.98
cm.sup.3/g, and a pore volume distribution where less than 20%
corresponds to the micro-pore zone with diameter of 100 .ANG. (10
nm), around 34-74% corresponds to pores within the 100-200 .ANG.
interval (10-20 nm), from 26-46% corresponds to the region of
meso-pores with pore diameter of 200 .ANG. (20 nm), 22-32% with
pore diameters of 250 .ANG. (25 nm), and the macro-pore region with
diameters of 1,000 .ANG. (100 nm) contributes with 14-22%. This
catalyst is used mainly for residua feedstock having 4-6.degree.
API gravity.
[0010] Chinese Patent No. 1,552,520 claims a catalyst for the
hydrodesulfurization of hydrocarbons which consists of a support of
gamma alumina with titania and active metals of groups VIB and
VIII. A mixture of dry aluminum hydroxide and titanium dioxide
(TiO.sub.2) powder. To this mixture an alkaline solution containing
molybdenum and/or tungsten is added.
[0011] U.S. Pat. No. 6,218,333 discloses a detailed method for the
preparation of a catalyst by means of a porous support (alumina,
silica-alumina, silica, titanium, boron, zeolites, zirconium,
magnesium and their combinations) with one or more active metals
(Mo, W, Co, Ni and their oxides, sulfides and mixtures of them).
This results in an initial catalytic prototype which contains
volatile compounds. Later, the concentration of these volatile
compounds is diminished by means of an ex-situ or in situ reduction
stage. The catalyst is used for the hydrotreating of hydrocarbon
feedstocks.
[0012] The patent WO 0,253,286 claims a hydroprocessing catalyst
for the conversion of the heavy oil hydrocarbons, which contains a
transition metal of group VI in a concentration of 7 to 20 weight %
and a metal of group VIII in a concentration of 0.5-6 weight %,
calcined to obtain the corresponding oxide over a support of
alumina. The resultant catalyst has 100 to 180 m.sup.2/g specific
surface area and total pore volume of 0.55 cm.sup.3/g or higher.
The catalyst lowers the metals contained in heavy hydrocarbons and
enhances the elimination of asphaltenes, sulfur, nitrogen and
Conradson carbon, besides, the catalyst shows a decrease in the
formation of sediments and better conversion in ebullated bed
operations. In fixed bed operation a product with improved
stability for its storage is obtained. A hydroprocessing of heavy
hydrocarbon feedstock with the catalyst in fixed or ebullated bed
is disclosed.
SUMMARY OF THE INVENTION
[0013] A hydrotreating catalyst has now been found that has
significant use, for example, in the second stage of a
hydrotreating process for residua and heavy crudes, mainly for the
hydrodesulfurization reaction.
[0014] The catalyst is produced by a process which comprises
forming a support for the catalyst from titanium and boehmite by
either [0015] a) peptizing a first portion of boehmite by admixture
with an inorganic acid to form a binder, contacting the binder with
a second portion of boehmite and deionized water to form a
homogeneous paste, forming the homogeneous paste into extrudates,
aging, drying and calcining to obtain gamma alumina, impregnating a
titanium precursor in the gamma alumina extrudate, aging, drying
and calcining the impregnated gamma alumina support to obtain a
TiO.sub.2/Al.sub.2O.sub.3 catalyst support in which the titanium is
deposited on the surface of the gamma alumina; or [0016] b)
admixing a titanium precursor with boehmite, peptizing the
admixture by further admixture with an inorganic acid and deionized
water to obtain a homogeneous paste, extruding the paste to form
extrudates which are aged, dried and calcined to form gamma alumina
and a TiO.sub.2--Al.sub.2O.sub.3 catalyst support in which the
titanium is incorporated into the gamma alumina structure; [0017]
and impregnating the support with at least one precursor of a metal
of group VIB and at least one precursor of a metal of group VIII of
the periodic table.
[0018] The catalyst of the present invention includes at least one
hydrogenating metal from group VIB in oxide form, a promoter from
group VIII also in oxide form deposited on a catalytically active
inorganic mixed oxide support, constituted mainly of gamma-phase
alumina and titanium. Thus, the present invention provides two
processes of support synthesis: one of them from, for example, a
commercial boehmite, which is peptized by using an inorganic acid,
extruded, calcined and then impregnated with a solution containing
titanium to obtain a titanium/alumina support
(TiO.sub.2/Al.sub.2O.sub.3); and other one in which the commercial
boehmite is mechanically mixed with a titanium containing solution,
it is peptized by using an inorganic acid, it is extruded and
calcined to form gamma alumina and a TiO.sub.2/Al.sub.2O.sub.3
catalyst support in which the titanium is incorporated into the
gamma alumina structure on which the active phases and the promoter
will be deposited.
[0019] The catalyst is activated by converting the metallic oxides
into sulfides, which are responsible for the catalytic activity.
The activation is carried out by means of a sulfidation process of
the oxides that constitute the catalyst.
[0020] The catalysts synthesized with the processes of the present
invention considerably improve the hydrodesulfurization activity.
In addition, they are not quickly deactivated by poisoning from the
contaminants that are contained in the heavy crudes, mainly metals
such as nickel and vanadium. Thus, the catalysts produced in the
present invention have a particular use in the hydrodesulfurization
stage of hydrotreating processes for heavy crude and residua.
[0021] Accordingly, previous technologies are surpassed by the use
of the catalyst of the present invention, particularly when it is
used in the second reaction stage of hydrotreating process of
residues and heavy crude oils, where the compounds of sulfur and
metals (Ni and the V) are more refractory. Also, the catalyst of
the present invention has physical, chemical and textural
properties advantageously used in the hydrodesulfurization of
residua and heavy crude with good activity, stability and minimum
deactivation in long operating times.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] For better understanding the catalyst of the present
invention, used principally for hydrodesulfurization of residua and
heavy crude oil, in what follows we will refer to the figures that
go with this document.
[0023] FIG. 1 is a diagram of the methodology used for the
micro-reaction and pilot plant scale evaluation of the catalysts
obtained with the processes of the present invention;
[0024] FIG. 2 is a graph showing the results of the effect of type
of boehmite used as catalyst support on the activity and stability
of the catalysts of the present invention;
[0025] FIG. 3 is a graph the effect of the catalyst metal
concentration on the activity and stability of the catalysts
obtained by the process of the present invention;
[0026] FIG. 4 shows the results on the effect of the titanium
content on the activity and stability of the catalysts obtained by
means of the process of the present invention;
[0027] FIG. 5 is a graph of the results on the effect of the method
of titanium incorporation onto the alumina
[TiO.sub.2/Al.sub.2O.sub.3] and within the structure of boehmite
[TiO.sub.2--Al.sub.2O.sub.3] on the activity and stability of the
catalysts of the present invention;
[0028] FIG. 6 is a graph showing the results on the effect of the
method of impregnation of molybdenum and nickel, simultaneous and
successive, on the activity and stability of the catalysts of the
present invention; and
[0029] FIG. 7 is a graph showing the results of the activity and
stability of the catalyst of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0030] The present invention relates to a catalyst to be used
principally in the second stage of a hydrotreating process for
residua and crude oil particularly for the hydrodesulfurization
reaction. More specifically, the present invention relates to the
synthesis of catalysts for the hydrotreatment of streams containing
hydrocarbons produced in the first stage of a catalytic
hydrotreatment process. The stream to be processed in the second
stage contains compounds of sulfur, nitrogen and metals (nickel and
vanadium), as well as asphaltenic hydrocarbons.
[0031] Similar to the hydroprocessing of residua, the heavy crude
oil hydroprocessing requires of a first hydrodemetallization (HDM)
stage followed by a hydrodesulfurization (HDS) stage, with the
objective of maximizing the useful life of the catalysts used in
the second stage of reaction. The properties of the catalysts used
in the two reaction stages must be different.
[0032] The catalyst used in the first hydrodemetallization stage
must possess a high metal retention capacity. Therefore the
greatest percentage of the pore distribution must be in the range
of meso pores and macro pores (>25 nm), whereas for the catalyst
used in the second reaction stage, which is to be used mainly for
the hydrodesulfurization reaction, the greatest percentage of the
pore size distribution must be in the range of meso pores (5-25
nm).
[0033] The pore size distribution in the catalyst support plays a
key role in the catalyst performance. By adequately tailoring the
catalyst pore volume it is possible to avoid problems of plugging
by carbon or other contaminants which cause poor diffusion of the
reactants to the interior of the catalyst and consequently its
deactivation. The optimization of the pore size in the catalysts
depends on the nature of the feedstock to be hydrotreated.
[0034] When heavy feedstocks are processed an ideal combination
must exist between the specific surface area and catalyst pore
diameters, to obtain high catalytic activity in the elimination of
sulfur compounds. In this respect when the catalyst has large pore
diameters, above 50 nm, catalyst deactivation is minor because the
pores can not be blocked by deposits of contaminants such as metals
(Ni and V) and carbon.
[0035] The chemical factors that control the good functioning of a
catalyst are: the variety, the content and the proportion of active
species (metals), the chemical state of the active species and
their dispersion on the catalyst support. Other factors also
important are the catalyst physical properties such as the specific
surface area, average pore diameter and total pore volume, which
are part of a good design of the support. Thus, the combination of
the physical and chemical properties of the catalyst, as well as
proper knowledge of the feedstock composition, and the optimization
of the process variables result in a highly active, stable and
selective catalyst.
[0036] Particularly, the present invention provides two processes
for obtaining a catalyst to be used mainly in the
hydrodesulfurization reaction, particularly of residua and heavy
petroleum crude oil, produced in a first hydrotreatment reaction
stage. The objective of the present invention is to use the
catalyst described in the present invention to mainly diminish the
sulfur content, although other parallel reactions such as
hydrodemetallization (HDM), hydrodenitrogenation (HDN), and
hydrodeasphaltenization (HDAs) can also take place, in order to
produce a light crude oil and to improve the quality of the
distillates. This catalyst has moderate initial activity but a
great stability taking into account that the sulfur present in this
reaction stage is contained in aromatic compounds of greater
size.
[0037] In the second stage or second reaction zone, the catalyst
can be used in a fixed bed reactor mode with an effective particle
diameter of, for example, at least 1/16'' (1.5875 mm). With some
minor changes in the physical properties such as form and size, the
catalyst can also be used in an ebulated bed reactor.
[0038] The catalyst of the present invention can process
effectively feedstocks having, for example, small amounts of metals
or up to 500 ppm of nickel plus vanadium, up to 10 weight % of
asphaltenes, and sulfur content within the interval of 0.5-5 weight
%.
[0039] To obtain the catalyst with the adequate properties to be
used mainly in the second hydrotreating stage of residua and heavy
crude oils either of the two following preferred processes can be
used: [0040] 1. To prepare the binder, a fraction (5-20 wt %) of
the total commercial boehmite is peptized with an inorganic acid,
preferable using a ratio of binder/acid of 0.1-0.5. Then the
remaining part of the boehmite (95-80 wt %) is added together with
the amount of deionized water necessary to obtain a homogeneous
paste adequate to be extruded. The extrudates obtained with the
paste are maintained at 20-25.degree. C. during 12-18 h., then they
are dried at 100-120.degree. C. during 2-6 h., and then they are
calcined at 500-600.degree. C. during 3-5 h, using a heating ramp
of 2.degree. C./min, to obtain gamma alumina. Based on the porosity
of the support, the required amount of a titanium precursor to
obtain 3-6 weight % titanium is incorporated in the support using
the incipient wetness impregnation method. The impregnation
solution is prepared with an organic solvent, preferably
isopropanol. The impregnated support is maintained at 20-25.degree.
C. for 12-18 h. and then is dried at 100-120.degree. C. and
calcined at 400-500.degree. C. to obtain the anatase phase of
titania, in this way the titania remains on the surface of the
gamma alumina. Finally, the titania/alumina
(TiO.sub.2/Al.sub.2O.sub.3) support is impregnated by incipient
wetness impregnation with active precursors of groups VIB and VIIIB
of the periodic table in a sequential or co-impregnation mode.
[0041] 2. In another method, the titanium precursor was
incorporated directly into a commercial boehmite followed by
peptization with inorganic acid and de-ionized water with
continuous mixing until a homogeneous paste of boehmite that can
adequately be transformed into extrudates is obtained. The
extrudates are left to mature at 20-25.degree. C. for 12-18 h then
are dried at 100-120.degree. C. for 2-6 h, and then they are
calcined at 500-600.degree. C. for 3-5 h, using a heating ramp of
2.degree. C./min. In this way a titania-alumina support in which
titania is incorporated to the structure of gamma alumina is
obtained. Finally, the titania-alumina support is impregnated by
the incipient wetness or by the spraying methods, in successive or
simultaneous mode with the metal precursors of the groups VIB and
VIIIB of the periodic table.
[0042] Concerning the above two methods of catalyst preparation it
is important to point out that: [0043] a) Any suitable inorganic
acid may be used in the synthesis of the support.
[0044] However, a preferred inorganic acid is nitric acid of a
concentration of 5-15 volume %. [0045] b) Likewise, any suitable
titanium precursor may be used for the synthesis of the support.
However, a preferred titanium precursor is titanium iso-propoxide.
[0046] c) The simultaneous impregnation (co-impregnation mode), is
performed with an aqueous basic solution (pH=9) that contains an
active metal of group VIB, preferably Mo, in the form of, for
example, ammonium heptamolybdate, and a precursor of any suitable
group VIII, preferably, for example, Ni in the form of hexahydrated
nickel nitrate. [0047] d) The successive impregnation of the
support involves first the impregnation of an active metal of group
VIB, preferably Mo in the form of ammonium heptamolybdate, using an
aqueous solution with basic pH (pH=9-9.5), with the respective
stages of maturing drying and calcination, followed by the
impregnation of a precursor of group VIII, preferably Ni, in the
form of hexahydrated nickel nitrate, at neutral pH.
[0048] The catalyst obtained using the processes of the present
invention consists of a support TiO.sub.2/Al.sub.2O.sub.3 or
TiO.sub.2--Al.sub.2O.sub.3 with a titanium concentration of 3-6 wt
%, in which the active metals are in concentrations of 8-10 wt % of
molybdenum oxide and 2-6 wt % of nickel oxide, based in the total
weight of the catalyst, amounts that have been found to produce an
optimum hydrodesulfurization activity with minimum metal
requirements.
[0049] In addition, the catalyst obtained with the procedures of
the present invention has a moderate acidity of 70 to 120 mg of
pyridine per gram of catalyst (70-120 mg Py/g cat), and well
defined textural properties: specific surface area (SSA) of 90 to
300 m2/g, an average pore diameter (APD) of 5 to 15 nm and a pore
volume (PV) of 0.2 to 0.7 cm3/g, as well as the following pore size
distribution: Less than 30% of its pore volume from pores of 0-5 nm
in diameter, from 55-80% of its pore volume supplied by pores of
5-10 nm of diameter, and less than 15% of its pore volume coming
from pores with diameters of more than 10 nm.
EXAMPLES
[0050] For the evaluation of the catalytic activities of the
hydrodesulfurization catalysts of the present invention, typical
micro-reaction and pilot plants were used. In both types of plants,
prior to the evaluation tests, experiments to determine the effect
of upward or downward flow in the reactor, different levels of
catalyst dilution with inert material were tested, as well as
different values for the operating variables such as liquid hourly
space velocity (LHSV), and reaction temperature. These experiments
allowed to establish the methodology for the evaluation of
catalysts summarized in FIG. 1.
[0051] FIG. 1 is an schematic representation of the methodology
used for the micro-reaction evaluation of the catalysts described
in the examples of the present invention. In step A, the reactor is
loaded with 10 mL of catalyst and 10 mL of inert material (SiC).
Stage B corresponds to the test of the equipment at a pressure 10%
higher than the one used in normal operation (P=1.1 P.sub.op) in
order to detect any leak in the experimental set up. Stage C
describes the sulfidation of the catalyst, performed with gasoil
from the atmospheric distillation of petroleum to which 1 wt %
dimethyl disulfide was added (1 wt. % DMDS+SRGO). The following
operating conditions were used for the sulfidation of the catalyst:
reaction temperature 320.degree. C., pressure 28 Kg/cm.sup.2, LHSV
2.00 h.sup.-1 and hydrogen/hydrocarbon ratio 2000 ft.sup.3/bbl.
Step D corresponds to the operation of the catalytic test that is
realized by a feeding to the reactor in ascending mode, the feed to
the reactor is a 50/50 wt % mixture of hydrotreated Maya crude
(HDT) and hydrodesulfurized diesel. The operating conditions in
stage D are as follows: temperature of 380.degree. C., pressure of
54 kg/cm.sup.2, hydrogen/hydrocarbon ratio of 2,000 ft.sup.3/bbl,
and LHSV of 1.0 h.sup.-1. In stage E the reaction takes place
during 120 h and during this time samples of product are taken
every 12 h. Finally, in stage F, analysis of the products from the
reactor is performed.
[0052] The best conditions found for the evaluation of catalysts at
micro plant and plant pilot are those presented in Table 1. At
pilot plant level the operating conditions for evaluation of the
catalysts are more severe than at micro-plant level, the run time
was increased to 200 h and the amounts of catalyst and inert
material were 100 and 50 mL respectively.
TABLE-US-00001 TABLE 1 Operating conditions of for the evaluation
of HDT catalysts Parameter Micro plant Pilot Plant Temperature,
.degree. C. 380 400 Space velocity (LHSV), h.sup.-1 1.0 1.0
Pressure, kg/cm.sup.2 54 70 Ratio H.sub.2/hydrocarbon, ft.sup.3/bbl
2,000 5,000 Catalyst Volume, mL 10 100 Inert material volume 10 50
(SiC), mL Run time, h 120 200
[0053] For the evaluation of the hydrodesulfurization catalysts at
microplant level a synthetic feed consisting of a 50/50 wt % of
heavy crude oil previously hydrotreated (HDT) and diesel
hydrodesulfurized diesel HDS), which led to a metal concentration
(Ni+V) lower than 150 ppm. For the evaluation of the catalysts at
pilot plant scale undiluted raw Maya HDT was used. The most
important properties of these fractions are shown in Table 2.
TABLE-US-00002 TABLE 2 Physical and chemical properties of the
feedstocks Micro Property plant Pilot Plant Elemental analysis C,
wt % 83.2 85.5 H, wt % 9.5 7.2 N, wt % 0.118 0.1852 S, wt % 0.648
1.217 Metals, ppm Ni 18.9 36.76 V 81.66 107.98 (Ni + V) 100.56
144.74 Asphaltenes, wt % 4.35 6.87 Physical properties Density,
20/4.degree. C. 0.87 0.87 Ramsbottom Carbon, wt % 5.54 8.0
[0054] Hydrodesulfurized diesel (diesel HDS) also was used to
prepare diesel contaminated with 1.0 wt % dimethyl disulfide (DMDS)
reactant grade with a purity of 97%, which was used for the
activation stage (sulfidation) of the catalyst.
[0055] The inert material used to dilute the catalytic bed was a
silicon carbide (SiC) of 60 mesh equivalent to a particle diameter
of 0.25 mm, and 30 mesh for the evaluation in pilot plant.
[0056] The activity of the catalysts of the present invention was
first evaluated at microreaction level, using the following
operating conditions: reaction temperature 380.degree. C., space
velocity (LHSV) of 1.0 h.sup.-1, pressure of 54 kg/cm.sup.2 and
H.sub.2/hydrocarbon ratio of 2,000 ft.sup.3/bbl, with a run time of
120 h.
[0057] The catalyst that presented the best results in the
evaluation at microplant level was also evaluated at pilot plant
scale at 400.degree. C. reaction temperature, space velocity (LHSV)
of 1.0 h.sup.-1, pressure of 70 kg/cm.sup.2 and a
H.sub.2/hydrocarbon ratio of 5,000 ft.sup.3/bbl, with a run time of
200 hours.
[0058] The following examples illustrate the present invention.
Example 1
[0059] In this example three commercial boehmites Catapal C-1,
Catapal C-200 of Condea Vista and Versal 300 of Roche are used.
[0060] For the preparation of catalysts A3 and B2, Catapal C-1 and
Versal 300 boehmites were used respectively. Part of the boehmite
was used as binder to which the required amount of an aqueous
solution with 10 wt % nitric acid (HNO.sub.3) was added.
Afterwards, little by little, the rest of the boehmite (filler) and
deionized water were added until a homogenous paste was obtained.
This paste was extruded with a piston to obtain cylindrical pellets
of 1/16'' of diameter. The extrudates were let to age for 12 to 18
hours, and then they were dried at 100-120.degree. C. during 2-6
hours and subsequently calcined at 500-550.degree. C. for 4 hours
using a heating ramp of 2.degree. C./min to obtain a gamma alumina
support.
[0061] For catalyst C2 a mechanical mixture of Catapal C-1 (70 wt %
was prepared) and Catapal C-200 (30 wt %) boehmites was prepared
following the same previous procedure. Later these supports were
impregnated by successive impregnation, first with ammonium
heptamolybdate (HMA) and then with nickel nitrate to obtain a metal
content of 10 wt %, and 4.3 wt % of Ni. The resulting solids were
left to age for 12-18 hours, and then they were dried at
100-120.degree. C. and calcined using a heating ramp of 2.degree.
C./min up to 120.degree. C. at which temperature they remained for
2 hours, then rising the temperature up to 300.degree. C. were they
remained for 2 hours, and finally up to 450.degree. C. where they
remained for 4 hours.
[0062] The textural properties of these three catalysts (A3, B2 and
C2) are shown in Table 3 where it is observed that such properties
are totally different.
TABLE-US-00003 TABLE 3 Textural properties of the catalysts
obtained by means of the process 1) of the present invention
(Example 1) Textural Properties PVD (Volume %) SSA PV APD 5-10
10-25 Catalyst (m.sup.2/g) (mL/g) (nm) <5 nm >25 A3 162 0.4
9.2 20.4 75.1 3.5 1.0 B2 195 0.6 13.0 3.8 51.5 41.3 3.4 C2 127 0.3
10.0 8.6 84.3 4.9 2.2 SSA = specific surface area, PV = Pore
volume, APD = Average pore diameter, PVD = Pore volume
distribution.
[0063] In Table 3, it is observed that although catalyst B2 is the
one that has the greater SSA, PV and APD, catalyst A3 displays
acceptable intermediate values. Also, catalyst A3 presents/displays
a greater population of pores in the range <10 nm (95.5% of the
volume), making evident that 75.1% of the volume is supplied by
pores in the range 5-10 nm.
[0064] The hydrodesulfurization activity of catalysts A3, B2 and
C2, at a 120 hour run time, is shown in FIG. 2.
[0065] FIG. 2 is a graph of the results of the effect of type of
boehmite on the activity and stability of the catalysts obtained by
means of process 1) of the present invention. In this graph, it is
observed that catalyst A3 is the one that presents the greater
initial activity, 81.6% conversion of HDS at a run time of 6 h, and
diminishes its activity until it stabilizes at 36 h run time, where
a conversion of 47% HDS is obtained. This conversion value is
similar to the one reached by catalyst B2 and slightly superior to
the one displayed by catalyst C2.
Example 2
[0066] In this example, the same commercial boehmite Catapal C-1
considered in Example 1 was used. The support and catalyst were
also prepared in similar way as in example 1, only that the
contents of Mo and Ni were different.
[0067] The supports were impregnated using the incipient wetness
method. This method is used when there is affinity among the metal
complexes/solvent with the support matrix, leading to appropriate
high diffusion of the catalytic agents, up to the saturation of the
support pores.
[0068] The properties of catalysts C1, B1, and A3 from Example 1
are shown in Table 4.
TABLE-US-00004 TABLE 4 Physical and chemical properties of the
catalysts obtained using process 1) of the present invention
(Example 2) Catalysts C1 B1 A3 Chemical properties Mo, wt. % 12.0
12.0 10.0 Ni, wt. % 12.0 8.0 4.3 Ni/(Ni + Mo) 0.5 0.4 0.3 Textural
properties SSA, m.sup.2/g 140 146 162 PV, mL/g 0.29 0.31 0.38 APD,
nm 7.9 7.9 9.2 PSD, Volume % <5, nm 26.8 22.6 20.4 5-10, nm 69.6
75.1 75.1 10-25, nm 2.0 1.5 3.3 25-50, nm 1.1 0.5 0.7 >50, nm
0.5 0.3 0.5 SSA = specific Surface Area, PV = Pore Volume, APD =
Average Pore Diameter, PSD = Pore Size Distribution
[0069] Table 4 shows that catalyst A3 has similar textual
properties even though it has lower Mo and Ni contents (10 and 4.3
weight % respectively). Compared with catalysts B1 and C1, which
have similar textural properties, catalyst A3 is the one that
presents the best textural properties. The pore size distribution
of catalysts A3 and B1 is similar in the interval of 5-10 nm (75.1%
volume), while for C1 is slightly lower (69.6% volume) in the same
range.
[0070] The hydrodesulfurization activity of catalysts A3, B1 and C1
are presented in FIG. 3 up to 120 hour time-on-stream.
[0071] FIG. 3 shows results of the variation in the metal content
on the activity and stability of the catalysts obtained by means of
the process 1 of the present invention. It is observed that
although catalyst A3 contains a lower amount of metals (10 wt % Mo
and 4.3 wt % Ni), it is the one that presented a greater initial
activity (81.6% HDS), compared to catalysts B1 and C, which
displayed an initial HDS activity of 60.6 and 46.5% respectively.
The activity of catalyst A3 stabilizes after 36 h of
time-on-stream, reaching a HDS conversion of around 47%, similar to
the one presented by B1 and slightly superior to the C1.
[0072] The results in Table 4 and FIG. 3 indicate that there must
be an optimum metal content to obtain good activity and stability
of the catalyst because when the metal content is increased the
catalyst activity does not increases accordingly.
Example 3
[0073] A gamma alumina support was prepared with same preparation
method as in Example 1 and 2 using Catapal C-1 as a base material.
This support was impregnated by the incipient wetness impregnation
method with a solution of titanium isopropoxide in isopropanol to
obtain 5 weight % titanium in the support. The titania impregnated
support was aged, dried, and calcined as reported in the Example 1,
to obtain anatase titanium oxide on the alumina support. To prepare
catalyst C3 the titanium-modified support was impregnated with Mo
and Ni as described in Example 1, and the steps of aging, drying,
and calcination were the same as those described in Examples 1 and
2.
[0074] The properties catalyst C3 as well as those of catalyst A3
from Example 1 are shown in Table 5.
TABLE-US-00005 TABLE 5 Properties of the catalysts obtained by
means of the process 1) of the present invention (Example 3)
Chemical content, Textural properties wt. % SSA PV APD Catalysts Ti
Mo Ni (m.sup.2/g) (mL/g) (nm) A3 10.0 4.3 162 0.38 9.2 C3 5.0 10.0
4.3 144 0.32 8.9 SSA = specific Surface Area, PV = Pore Volume, APD
= Average Pore Diameter, PSD = Pore Size Distribution
[0075] Table 5 shows that the textural properties of catalysts A3
and C3 are different. The SSA, PV and APD of catalyst C3 are lower
compared to catalyst A3. The lower values obtained for catalyst C3
are due to the incorporation of Ti to the Al.sub.2O.sub.3
support.
[0076] The HDS activity of catalysts A3 and C3 at 120 h
time-on-stream are shown in FIG. 4.
[0077] FIG. 4 presents the results of the effect of the
incorporation of titanium to the alumina support on the activity
and stability of the catalysts obtained by means of process 1) of
the present invention. In this graph catalyst C3, which contains 5
weight % titanium, is the one that showed a better stability
maintaining an HDS conversion of approximately 63% from 36 to 120 h
time-on-stream. Catalyst A3, without Ti, although its activity was
initially similar to catalyst C3, presents greater deactivation
reaching an HDS conversion of approximately 47% after 36 h
time-on-stream.
Example 4
[0078] For this example, a boehmite Catapal C-1 was also used. A
titanium modified alumina support was prepared by using process 2)
of the present invention. The boehmite was dried during 2-5 h at a
temperature of 100-120.degree. C. to eliminate the humidity that
could exist in the sample, later, it was impregnated with a
titanium isopropoxide/isopropanol solution to obtain a support
containing 5 wt % titanium, the isopropanol volume used depends on
the porosity factor of the boehmite, which in this case was of 0.6
mL/g. Thus a TiO.sub.2--Al.sub.2O.sub.3 support was obtained. The
steps of ageing, drying, and calcination were made as in the
previous examples. Later, the support was impregnated with HMA and
nickel nitrate similarly as in the preceding examples, originating
catalyst B3.
[0079] The textural properties of catalyst B3 as well as those of
catalyst C3 from the Example 3 are shown in Table 6.
TABLE-US-00006 TABLE 6 Textural properties of the catalysts
obtained by the process of the present invention (Example 4)
Catalysts C3 B3 Textural properties SSA, m.sup.2/g 144 166 PV, mL/g
0.32 0.26 APD, nm 8.9 6.2 PVD, % Vol. <5, nm 20.1 80.4 5-10, nm
75.3 12.5 10-25, nm 3.1 5.0 25-50, nm 0.2 1.9 >50, nm 1.0 0.3
SSA = Specific surface area, PV = Pore volume, APD = Average pore
diameter, PVD = Pore volume distribution.
[0080] It is observed in Table 6 that catalyst C3 presents a
smaller SSA (144 m.sup.2/g) unlike catalyst B3 (166 m.sup.2/g),
whereas the PV and APD are greater for catalyst C3 (0.32 mL/g and
8.9 nm respectively) than those presented by catalyst B3. Also, the
pore size distribution of catalyst C3 is mainly concentrated in the
interval of 5-10 nm (75.3% of the total pore volume), whereas
catalyst B3 exhibits 80.4% in the interval of pores <5 nm.
[0081] The hydrodesulfurization activity of catalysts C3 and B3, at
120 h time-on-stream is shown in FIG. 5.
[0082] FIG. 5 shows the results of the effect of the method of
titanium incorporation on the activity and stability of the
catalysts obtained by means of the processes of the present
invention. In this Figure, it is observed that the method of
incorporation of titanium is very important; catalysts C3 and B3
show the same titanium content (5 wt %). The catalyst C3, where the
titanium was impregnated on the surface of the Al.sub.2O.sub.3
support (TiO.sub.2/Al.sub.2O.sub.3), presented an initial activity
at 6 h of time-on-stream of 82.9% of HDS and a stable operation
from 36 h up to 120 h of time-on-stream at 59.5% of HDS, in
contrast to catalyst B3, where the titanium was added to the
boehmite by mechanical mixing (TiO.sub.2--Al.sub.2O.sub.3), for
which the initial activity was 59.0% of HDS and decreases to 34% of
HDS at 120 h of time-on-stream.
[0083] Clearly, catalyst C3 shows a better initial activity and
stability than catalyst B3, because it possesses a greater
percentage of pores in the interval from 5 to 10 nm (75.3%
volume).
Example 5
[0084] The TiO.sub.2/Al.sub.2O.sub.3 support used to prepare
catalyst C3, was also used to prepare the catalyst of this example
(D3). Catalyst D3 was synthesized by simultaneous impregnation of
the support with a solution prepared in the following way: in a
three-neck flask continuously and vigorously stirred, the required
amount of an aqueous solution of NH.sub.4OH, 3:1
H.sub.2O/NH.sub.3OH, was placed adding slowly the ammonium
heptamolybdate (NH.sub.4).sub.6Mo.sub.7O.sub.24.4H.sub.2O, until a
colorless transparent solution having pH=9-9.5 was obtained. After,
the required volume of water to fill the pores of the support was
added. Immediately after the nickel nitrate
Ni(NO.sub.3).sub.2.6H.sub.2O(NNi) is added slowly, giving as result
a solution of intense blue color with a Mo content of 10 wt % and
4.3 wt % of Ni. The properties of these catalysts are given in
Table 7.
TABLE-US-00007 TABLE 7 Textural properties of the catalysts
obtained by the processes of the present invention (Example 5)
Catalyst C3 D3 Textural properties SSA, m.sup.2/g 144 152 PV, mL/g
0.32 0.33 APD, nm 8.9 8.6 PSD, volume % <5, nm 20.1 27.1 5-10,
nm 75.3 68.7 10-25, nm 3.1 3.1 25-50, nm 0.2 0.7 >50, nm 1.0 0.4
SSA = Specific surface area, PV = Pore volume, APD = Average pore
diameter, PSD = Pore volume distribution.
[0085] Table 7 shows that catalyst D3 has a higher SSA (152
m.sup.2/g) than catalyst C3 (144 m.sup.2/g), whereas the PV and the
APD are similar, the PSD slightly changes i.e. the interval of
pores <5 nm is 20.1% of the total volume for catalyst C3 while
it is 27.1% for catalyst D3. The opposite trend was observed for
the pores in the 5-10 nm range, in this case the percent volume is
greater for catalyst C3 (75.3% volume) respect to catalyst D3
(68.7% volume); in the remaining intervals the pore volume
distributions are similar.
[0086] The hydrodesulfurization activities of catalysts C3 and D3
are shown in FIG. 6 at 120 h of time-on-stream.
[0087] FIG. 6 shows the results of the effect of the impregnation
method of molybdenum and nickel, simultaneous or successive, on the
activity and stability of the catalysts obtained by means of the
processes of the present invention. It is observed in this figure
that catalysts C3 and D3 show a similar behavior, although the
catalyst C3, which was impregnated sequentially first Mo and then
Ni, followed by the drying and calcination steps, displayed a
higher initial activity of 82.9% of HDS conversion at 6 h run time,
while catalyst D3 displayed an activity of 74% HDS conversion. Both
catalysts became stable at 36 h of time-on-stream giving an HDS
conversion of 59.5% for the catalyst C3 and 58.1% for catalyst
D3.
[0088] In other words, catalyst C3 showed a slightly better initial
activity and stability than catalyst D3, because it has higher
percentage of pores in the interval from 5 to 10 nm (75.3%
volume).
Example 6
[0089] According to the positive results obtained in the evaluation
of catalyst C3 at micro-plant scale after 120 hours of
time-on-stream, this catalyst was evaluated at pilot plant scale
during 200 h of time-on-stream. The reaction conditions were
mentioned previously (Table 2). The behavior of catalyst C3 at
pilot plant scale is presented in FIG. 7.
[0090] FIG. 7 shows the results of activity and stability of
catalyst C3 of the present invention evaluated at pilot plant
scale. The formulation of catalyst C3 exhibited the best activity
in the micro plant tests, therefore it was decided to evaluate this
catalyst at pilot plant scale, using a feedstock containing the
most refractory sulfur compounds. In FIG. 7 it is observed that
catalyst C3 presents constant stable behavior from 12 h up to 200 h
time-on-stream, which was the duration of the test, maintaining an
HDS conversion level of 40%. In the same figure the behavior of
catalyst C3 in the HDM, HDN, and HDAs reactions is also observed.
The HDM and HDN reactions presented the same stability maintaining
a conversion of 20% from 6 h up to 120 h. The HDAs reaction
exhibits a high initial activity at 6 h (higher than 60% HDAs)
compared to the HDS, HDN and HDM reactions, however, the HDAs
conversion drops quickly from 60.4% to 20.4%.
[0091] While advantageous embodiments have been chosen to
illustrate the invention, it will be understood by those skilled in
the art that various changes and modifications can be made therein
without departing from the scope of the invention as defined in the
appended claims.
* * * * *