U.S. patent application number 11/213498 was filed with the patent office on 2006-03-23 for catalyst and process for selective hydrogenation.
Invention is credited to David M. Lowe, Michel Molinier, John D.Y. Ou, Michael A. Risch, Anthony F. JR. Volpe, Jeffrey C. Yoder.
Application Number | 20060060505 11/213498 |
Document ID | / |
Family ID | 34591591 |
Filed Date | 2006-03-23 |
United States Patent
Application |
20060060505 |
Kind Code |
A1 |
Lowe; David M. ; et
al. |
March 23, 2006 |
Catalyst and process for selective hydrogenation
Abstract
A selective hydrogenation catalyst composition comprises a
rhodium component present in an amount such that the catalyst
composition comprises less than 3.0% of rhodium by weight of the
total catalyst composition; and an indium component present in an
amount such that the catalyst composition comprises at least 0.3%
and less than 5.0% of indium by weight of the total catalyst
composition.
Inventors: |
Lowe; David M.; (Sunnyvale,
CA) ; Molinier; Michel; (Houston, TX) ; Ou;
John D.Y.; (Houston, TX) ; Risch; Michael A.;
(Seabrook, TX) ; Volpe; Anthony F. JR.; (Santa
Clara, CA) ; Yoder; Jeffrey C.; (San Jose,
CA) |
Correspondence
Address: |
EXXONMOBIL CHEMICAL COMPANY
5200 BAYWAY DRIVE
P.O. BOX 2149
BAYTOWN
TX
77522-2149
US
|
Family ID: |
34591591 |
Appl. No.: |
11/213498 |
Filed: |
August 26, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10720617 |
Nov 24, 2003 |
|
|
|
11213498 |
Aug 26, 2005 |
|
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Current U.S.
Class: |
208/115 ;
502/235 |
Current CPC
Class: |
C07C 5/09 20130101; B01J
23/62 20130101; C07C 7/167 20130101; C07C 2523/62 20130101; C07C
5/08 20130101; C07C 7/163 20130101 |
Class at
Publication: |
208/115 ;
502/235 |
International
Class: |
C10G 11/08 20060101
C10G011/08; B01J 21/12 20060101 B01J021/12 |
Claims
1-21. (canceled)
22. A process for selectively removing alkynes or diolefins from a
feedstock also containing olefins, the process comprising
contacting the feedstock with hydrogen in the presence of a
catalyst composition made by the method comprising: (a) applying a
rhodium nitrate to an alumina, zirconia, or ceria-alumina support,
and (b) applying an indium formate or nitrate to the support; to
produce a catalyst composition which comprises 0.3-3.0% rhodium and
less than 5.0% indium by weight of the total catalyst composition
including the support.
23. A process for selectively removing C.sub.2 to C.sub.4 alkynes
or diolefins from a feedstock also containing C.sub.2 to C.sub.4
olefins, the process comprising contacting the feedstock with
hydrogen in the presence of a catalyst composition comprising a
rhodium component and an indium component, and the process
producing an olefin-enriched product stream containing less than 20
weight % of oligomers of said olefins.
24. The process of claim 23 and producing an olefin-enriched
product stream containing less than 10 weight % of oligomers of
said olefins.
25. A process for selectively removing alkynes or diolefins from a
feedstock also containing olefins, the process comprising
contacting the feedstock with hydrogen in the presence of a
catalyst composition comprising: (a) a rhodium component present in
an amount such that the catalyst composition comprises less than
3.0% of rhodium by weight of the total catalyst composition; and
(b) an indium component present in an amount such that the catalyst
composition comprises at least 0.3% and less than 5.0% of indium by
weight of the total catalyst composition.
26. The process of claim 25 wherein the alkynes or diolefins have 2
to 4 carbon atoms and the feedstock also contains C.sub.2 to
C.sub.4 olefins
27. The process of claim 25 wherein said contacting is conducted at
a temperature of from about 20.degree. C. to about 150.degree. C.,
a pressure of from about 690 kPa to about 4100 kPa, and a molar
ratio of hydrogen to alkynes and diolefins of from about 1 to about
1000.
28. The process of claim 25 wherein said contacting is conducted at
a temperature of from about 30.degree. C. to about 100.degree. C.,
a pressure of from about 1400 kPa to about 3400 kPa, and a molar
ratio of hydrogen to alkynes and diolefins of from about 1.1 to
about 800.
29. The process of claim 25 wherein at least one of the feedstock
and the hydrogen contains carbon monoxide in an amount up to 1
ppm.
30. The process of claim 25 wherein at least one of the feedstock
and the hydrogen contains carbon monoxide in an amount up to 0.5
ppm.
31. The process of claim 25 wherein said catalyst consists
essentially of (a) and (b).
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a divisional of U. S. patent
application Ser. No. 10/720,617 filed on Nov. 24, 2003, and is
related by subject matter to U.S. patent application Ser. No.
10/720,558, filed Nov. 24, 2003 (Attorney Docket 2003B124) and U.S.
patent application Ser. No. 10/720,607, filed Nov. 24, 2003
(Attorney Docket 2003B 126), the entire contents of which
applications are incorporated herein by reference.
FIELD
[0002] This invention relates to a catalyst and a process for the
selective hydrogenation of alkynes and diolefins to olefins.
BACKGROUND
[0003] Light olefins, such as ethylene, propylene and butylenes,
can be produced using various processes such as steam cracking,
fluid catalytic cracking, conversion of methanol to olefins,
paraffin dehydrogenation, alcohol dehydration, methane coupling and
Fischer Tropsch reactions. However, these processes often produce
varying levels of acetylenic or diene by-products, such as
acetylene, methyl acetylene (MA), propadiene (PD), butyne and
butadiene. These by-products must be removed from the light olefin
streams because they can act as poisons to the downstream
processing catalysts, such as polymerization catalysts. The
preferred method of removing these by-products is by selective
hydrogenation in which, for example, the acetylenes are converted
to ethylene, methyl acetylene and propadiene are converted to
propylene, and the butyne and butadiene are converted to
butylenes.
[0004] Currently, the commercial catalysts used for this selective
hydrogenation comprise nickel or palladium, such as palladium and
silver, on an alumina support. However, in addition to producing
the desired olefin products, these catalysts tend to generate
significant quantities of saturates (for example, ethane, propane
and butanes) as a result of over-hydrogenation and green oil
(olefin oligomers) as a result of competing oligomerization
reactions. Both of these by-products are undesirable in that they
reduce the selectivity to the required light olefins. However, the
green oil is particularly problematic in that it decreases the life
of the hydrogenation catalyst.
[0005] There is therefore a need for an improved catalyst for the
selective hydrogenation of alkynes and diolefins, wherein the
catalyst exhibits increased olefin selectivity and reduced
selectivity to saturates and oligomers, such as green oil, while
retaining high hydrogenation activity.
[0006] U.S Patent Application Publication No. 2002/0068843
discloses a catalyst for selectively hydrogenating acetylenic and
diolefinic compounds with low green oil formation, the catalyst
comprising the following active components loaded on a porous
inorganic support: (1) at least one of platinum, palladium, nickel,
ruthenium, cobalt, and rhodium; (2) at least one of silver, copper,
zinc, potassium, sodium, magnesium, calcium, beryllium, tin, lead,
strontium, barium, radium, iron, manganese, zirconium, molybdenum,
and germanium; (3) at least one rare earth metal selected from
scandium, yttrium and Lanthanides in Group IIIB of Periodic Table
of Elements; and (4) bismuth. Preferably, component (1) is platinum
or palladium component (2) is silver, potassium or sodium and
component (3) is lanthanum or neodymium.
[0007] U.S. Pat. No. 6,255,548 discloses a method for selectively
hydrogenating a feed comprising an acetylenic compound and/or a
diolefin in the presence of a catalyst comprising at least one
support, at least one Group VIII metal selected from nickel,
palladium, platinum, rhodium, ruthenium and iridium and at least
one additional element M selected from germanium, tin, lead,
rhenium, gallium, indium, thallium, gold, and silver, wherein the
catalyst is formed by introducing said additional element M into an
aqueous solvent in the form of at least one water-soluble
organometallic compound comprising at least one carbon-M bond. The
preferred Group VIII metals are nickel, palladium and platinum and
the preferred additional elements M are germanium, tin, gold, and
silver. There is no specific disclosure of a catalyst comprising
rhodium and indium and no indication is given as to the molar ratio
of the Group VIII metal to the additional element M, especially if
the Group VIII metal is rhodium and/or M is indium.
[0008] U.S. Pat. No. 5,877,363 discloses a process for the removal
of acetylenes and 1,2-butadiene from a C.sub.4 aliphatic
hydrocarbon stream by contacting the hydrocarbon stream with
hydrogen in a distillation column reactor containing a bed of
hydrogenation catalyst comprising a GroupVIII metal selected from
platinum, palladium, rhodium or mixtures thereof; optionally in
combination with a Group IB or Group VIB metal, and fractionally
distilling the reaction mixture to remove a heavier fraction and
removing a fraction overhead comprising substantially all of the
C.sub.4 compounds having reduced acetylenes and 1,2-butadiene
content. The preferred hydrogenation catalyst is palladium.
[0009] U.S. Pat. Nos. 5,356,851 and 5,364,998 disclose a catalyst
and a process for the selective hydrogenation of unsaturated
compounds, wherein the catalyst contains 0.1 to 10%, preferably 0.2
to 5%, of at least one Group VIII metal selected from nickel,
palladium, platinum, rhodium and ruthenium and 0.01 to 10%,
preferably 0.1 to 5%, of at least one Group IIIA metal selected
from gallium and indium. The molar ratio of Group IIIA metal to
Group VIII metal is between 0.2 and 5, preferably between 0.3 and
2. The metals are deposited on a catalyst support, such as silica,
alumina or silica-alumina, by (a) impregnating the support with a
solution of a Group IIIA metal compound precursor, then (b)
impregnating the product of (a) with a solution of a Group VIII
metal compound and then (c) calcining the product of (b) at 110 to
600.degree. C. The preferred Group VIII metals are nickel,
palladium and platinum. There is no specific disclosure of a
catalyst comprising rhodium and indium.
[0010] In U.S. Pat. No. 4,691,070 a catalyst for the hydrogenation
of a diolefin is disclosed in which palladium or a compound thereof
and at least one co-catalyst component selected from ruthenium,
rhodium, cobalt, and rhenium are supported each in the form of an
elemental metal or a metal compound on a non-acidic support.
[0011] A rhodium catalyst is disclosed in U.S. Patent No. 4,420,420
in which active rhodium metal is supported on a silica type or
titania type support, optionally together with one or more
co-catalysts including alkaline earth metals, such as calcium,
magnesium, barium and the like, noble metals, such as platinum,
palladium, iridium, ruthenium, gold and the like, iron, nickel,
cobalt, cerium and manganese.
SUMMARY
[0012] In one aspect, the present invention resides in a catalyst
composition comprising: [0013] (a) a rhodium component present in
an amount such that the catalyst composition comprises less than
3.0% of rhodium by weight of the total catalyst composition; and
[0014] (b) an indium component present in an amount such that the
catalyst composition comprises at least 0.3% and less than 5.0% of
indium by weight of the total catalyst composition.
[0015] In one embodiment, the catalyst composition comprises at
least 0.25% and less than 2.5%, for example at least 0.3% and less
than 1.5%, of rhodium by weight of the total catalyst composition.
In addition, the catalyst composition comprises at least 0.4% and
less than 4.0%, such as at least 0.5% and less than 3%, of indium
by weight of the total catalyst composition.
[0016] Conveniently, the molar ratio of the rhodium to indium in
the catalyst composition is about 0.2 to about 1.1, such as from
about 0.35 to about 0.75.
[0017] Conveniently, the catalyst composition also comprises a
support.
[0018] In a further aspect, the invention resides in a method for
making a catalyst composition, the method comprising: [0019] (a)
applying a rhodium compound to a support; and [0020] (b) applying
an indium compound to the support; to produce a catalyst
composition which comprises less than 3.0% rhodium and at least
0.3% and less than 5.0% of indium by weight of the total catalyst
composition including the support.
[0021] Conveniently, after at least one of (a) and (b), the support
is calcined at a temperature of about 100.degree. C. to about
600.degree. C.
[0022] In yet a further aspect, the invention resides in use of the
catalyst composition described above in a process for selectively
removing alkynes or diolefins, particularly alkynes or diolefins
having 2 to 4 carbon atoms, from a feedstock containing olefins,
particularly C.sub.2 to C.sub.4 olefins.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0023] The present invention relates to a novel catalyst
composition, its preparation and its use in the hydrogenation of
alkynes or diolefins or both in a feedstock containing other
unsaturated compounds, such as olefins. The catalyst comprises
indium and rhodium within particular weight ranges and is capable
of hydrogenating any alkynes and diolefins in the feedstock with
high selectivity to olefins and low selectivity to green oil
(oligomers) and saturates. A further benefit of the present
catalyst composition is the extension of catalyst lifetime and/or
operating cycle due to the reduction in green oil formation. In
addition, the catalyst of the invention has improved tolerance to
carbon monoxide impurities in the feedstocks and can, for example,
be employed with feedstocks containing carbon monoxide in amounts
up to 1 ppm, such as up to 0.5 ppm, for example up to 0.1 ppm.
[0024] As used herein, the term "acetylene" includes the
hydrocarbon C.sub.2H.sub.2 as well as other acetylenic
hydrocarbons, such as methyl acetylene (MA). The term "ethylene
product stream" includes streams containing the hydrocarbon
C.sub.2H4 as well as streams containing other mono- and
diolefinically unsaturated hydrocarbons. It will be appreciated,
however, that while the catalysts are often discussed in terms of
selectively hydrogenating acetylene, MA, propadiene (PD) and
optionally, butadiene (BD) in a stream that is predominantly
ethylene, propylene and/or butylenes, they are not necessarily
limited to the treatment of streams that contain ethylene or
propylene or butene, but are expected to find applicability to the
selective hydrogenation of other unsaturated compounds in streams
of other chemical content as well.
Catalyst Composition
[0025] The present catalyst composition comprises rhodium and
indium as active components, which may be combined with a support.
In general, the rhodium and indium components will be present in
the catalyst composition in elemental form, but one or both of
these components may also be present at least partly in other
forms, such as oxide, hydride or sulfide forms.
[0026] In particular, the catalyst composition includes a rhodium
component which is present in the catalyst composition in an amount
such that the catalyst composition comprises less than 3.0%, for
example at least 0.25% and less than 2.5%, such as at least 0.3%
and less than 1.5%, of rhodium by weight of the total catalyst
composition.
[0027] In addition, the catalyst composition includes an indium
component which is present in the catalyst composition in an amount
such that the catalyst composition comprises at least 0.3% and less
than 5.0%, for example at least 0.4% and less than 4.0%, such as at
least 0.5% and less than 3%, of indium by weight of the total
catalyst composition.
[0028] All weight percentages for the metal components of the
catalyst composition are based on the amount of elemental metal
present by weight of the total catalyst composition, including any
binder or support.
[0029] Other catalytically active metal components may also be
present in the catalyst composition but, provided the indium and
rhodium are present in the amounts discussed above, the present
catalyst composition is found to exhibit improved performance in
the selective hydrogenation of alkynes and diolefins without the
need for additional catalytically active metals.
[0030] In addition to the active metal components discussed above,
the catalyst composition may comprise a support or binder material.
Suitable support materials comprise carbon, silicon carbide,
silicon nitride, boron nitride, magnesium silicate, bentonite,
zeolites, metal alloys, zirconia, alumina, silica, silica-alumina,
ceria-alumina, aluminates (such as aluminates of Groups 1 and 2 and
of the Periodic Table of Elements) and magnesium oxide-silicon
oxide mixtures. Preferred support materials include zirconia,
alumina and ceria-alumina. The binder or support material
conveniently comprises from about 75 wt % to about 99.9 wt %, such
as from about 92.5 wt % to about 99.5 wt %, of the entire catalyst
composition.
[0031] The active metal components may be substantially uniformly
distributed throughout the support, can be located within a thin
layer at the support surface (commonly referred to as eggshell),
can be located at the center of the support (commonly referred to
as eggyolk), or can be concentrated between the outer edge and the
center of the support (commonly referred to as eggwhite).
Preferably, the metal components are concentrated in a thin layer
(not more than 1000 microns, conveniently not more than 500
microns, such as not more than 300 microns, for example not more
than 100 microns deep) on the surface of the support.
Method of Making the Catalyst Composition
[0032] The catalyst composition can be prepared by a variety of
different procedures. One suitable procedure is impregnation in
which a support, such as alumina, is contacted with an aqueous or
organic solution of a compound (such as a nitrate, sulfate, halide
or acetate) of the chosen metal or metals (rhodium and/or indium),
the solution volume being about equal to or in excess of the
retention volume of the support. Contact between the support and
the solution is normally maintained for about 0.01 to about 24
hours, such as about 0.05 to about 4 hours, whereafter the
impregnated support is dried and normally calcined. Such a
procedure can be used to add rhodium and indium to the support in a
single operation or alternatively separate impregnations can be
used to apply rhodium and indium successively to the support.
[0033] Alternatively, at least one of the metal components can be
applied to the support by mixing a slurry or solution of a compound
of the chosen metal or metals with a slurry of a particulate
support in a liquid, such as water. After mixing, the resultant
slurry may be treated, such as by heating or vacuum drying, to
partially or completely remove the liquid, whereafter the treated
support may, if necessary, be filtered, then washed with distilled
water, dried and calcined as in the case of the impregnation
procedure.
[0034] As a further alternative, at least one of the metal
components can be applied to the support by precipitation. For
example, a liquid solution, such as an aqueous solution, comprising
a source of ions of one of the active components can be subjected
to conditions sufficient to cause precipitation of the component as
a solid from solution, such as by the addition of a precipitating
reagent to the solution. Conveniently, the precipitation is
conducted at a pH above 7. For example, the precipitating agent may
be a base such as sodium hydroxide or ammonium hydroxide.
[0035] In addition, both of the rhodium and indium components can
be applied to the support simultaneously by co-precipitation. For
example, a first liquid solution comprising a source of rhodium
ions can be combined with a second liquid solution comprising a
source of indium ions. This combination of two solutions can take
place under conditions sufficient to cause co-precipitation of both
components onto the support from the liquid medium. Alternatively,
the source of rhodium ions and the source of indium ions may be
combined into a single solution. This solution may then be
subjected to conditions sufficient to cause co-precipitation of the
solid components onto the support, such as by the addition of a
precipitating reagent to the solution.
[0036] Although any compound of the desired metal can be used to
apply the different catalyst components to the support, it is found
that in the case of rhodium, the preferred compound used to apply
the rhodium to the support is rhodium nitrate, whereas in the case
of indium, the preferred compounds are indium nitrate and indium
formate.
[0037] After applying the metal components to the support, the
support is normally calcined, such as in air, at between about
100.degree. C. and about 600.degree. C., for example at between
about 110.degree. C. and about 500.degree. C. Where the metal
components are applied to the support in consecutive steps, a
separate calcination step can be conducted after each metal
application step or a single calcination step can be conducted
after all the metal components have been applied to the
support.
[0038] Finally, the catalyst composition is conveniently heated in
a reducing atmosphere, such as an atmosphere containing about 5 to
about 30 mol % hydrogen, with the remainder being an inert gas,
such as nitrogen, at a temperature of about 100.degree. C. to about
600.degree. C., such as about 300.degree. C. to about 500.degree.
C., to further increase the activity of the catalyst. Such a
reduction step can be performed in addition to, or in place of, the
calcination step(s) referred to above.
Selective Hydrogenation Process
[0039] The catalyst composition of the invention is capable of
hydrogenating alkynes and diolefins in a feedstock that also
contains olefins with high selectivity to olefins and low
selectivity to green oil (olefin oligomers) and saturates. In
particular, when used to selectively hydrogenate C.sub.2 to C.sub.4
alkynes and/or diolefins in a feedstock also containing C.sub.2 to
C.sub.4 olefins, the present catalyst composition typically
achieves an alkyne conversion in excess of 80%, such as in excess
of 90%, with an olefin selectivity in excess of 45%, such as in
excess of 70%, by weight of the total product and a green oil
selectivity of less than 20%, for example less than 15%, such as
less than 10%, by weight of the total product. The reduction in
green oil formation should also result in an extension of catalyst
lifetime and/or operating cycle.
[0040] The selective hydrogenation of acetylene, methyl acetylene
(MA), propadiene (PD), and/or butadiene (BD) is typically carried
out in one of four unit types: [0041] (a) Front-End Selective
Catalytic Hydrogenation Reactors, where the feed is composed of
C.sub.3 and lighter hydrocarbons, or C.sub.2 and lighter
hydrocarbons. In the case of raw gas applications, other components
such as butadiene, ethyl acetylene, dimethyl acetylene, vinyl
acetylene, cyclopentadiene, benzene, and toluene can also be
present. [0042] (b) Back-End Selective Catalytic Hydrogenation
Reactors, where the feed is composed of an ethylene-rich stream.
[0043] (c) MAPD Selective Catalytic Hydrogenation Reactors, where
the feed is composed of a propylene-rich stream. [0044] (d) BD
Selective Catalytic Hydrogenation Reactors, where the feed is
composed of a butylene-rich stream.
[0045] The operating parameters of an alkyne/alkadiene selective
hydrogenation process are not narrowly critical and can be
controlled in view of a number of interrelated factors including,
but not necessarily limited to, the chemical composition of the
feedstock, the control systems and design of a particular plant,
etc. (i.e., different reactor configurations including front-end,
back-end, MAPD, and BD converters as mentioned briefly above). In
general, however, suitable operating parameters include a
temperature of from about 20.degree. C. to about 150.degree. C.,
such as from about 30.degree. C. to about 100.degree. C., a
pressure of from about 100 psig to about 580 psig (690 kPa to 4100
kPa), such as from about 200 psig to about 440 psig (1400 kPa to
3400 kPa), a H.sub.2/C.sub.2H.sub.2 molar feed ratio of from about
1 to about 1000, such as from about 1.1 to about 800 and, assuming
the reaction is in the vapor phase, a GHSV from about 100 to about
20,000, such as from about 500 to about 15,000 or, if the reaction
is in the liquid phase, an LHSV of 0.1 to 100, such as from 1 to
25.
[0046] The following descriptions serve to give some sense of how
the inventive process may be practiced in the different commercial
units.
[0047] In the case of a front-end (FE) selective hydrogenation
reactor, the inlet operating temperature may range from about 30 to
about 150.degree. C., such as from about 50 to about 100.degree. C.
Representative operating pressures may range from about 100 psig to
about 500 psig (about 690 to 3,500 kPa), such as from about 200
psig to about 400 psig (about 1400 to 2800 kPa). The GHSV may range
from about 5000 to about 20,000, such as from about 8000 to about
15,000. Further, the H.sub.2 partial pressure may range from about
25 psig to about 175 psig (about 172 to 1200 kPa), such as from
about 50 psig to about 140 psig (about 345 to 965 kPa). The
feedstreams in FE selective hydrogenation processes typically
contain at least about 20% ethylene, and less than 1% acetylene,
with the balance comprising ethane, methane, hydrogen and small
amounts of similarly light components. (All percentages are mole%
unless otherwise noted). Depending upon the process configuration
of the plant, this feed stream can also contain C.sub.3 components
such as methyl acetylene, propadiene, propylene, and propane. Still
heavier components such as 1,3 butadiene; 1,2 butadiene; ethyl
acetylene; dimethyl acetylene; vinyl acetylene; cyclopentadiene;
benzene; toluene and mixtures thereof may also be present as a
result of certain process configurations.
[0048] In the case of a back-end selective hydrogenation reactor,
the inlet operating temperature may range from about 30 to about
150.degree. C., such as from about 40 to about 90.degree. C.
Representative operating pressures may range from about 100 psig to
about 500 psig (about 690 to 3,500 kPa), such as from about 200
psig to about 400 psig (about 1400 to 2800 kPa). The GHSV may range
from about 1000 to about 10,000, such as from about 3000 to about
8000. Further, the H.sub.2/C.sub.2H.sub.2 molar feed ratio may
range from about 0.5 to about 20, such as from about 1.0 to about
1.5. The feedstreams in back-end selective hydrogenation processes
may contain about 2% acetylene, about 70% ethylene, and the balance
of other C.sub.2 compounds.
[0049] In the case of a methyl acetylene/propadiene (MAPD)
selective hydrogenation reactor, operation can be conducted in
either the liquid or vapor phase. In the case of liquid phase
operation, the inlet operating temperature may range from about 20
to about 100.degree. C., such as from about 30 to about 80.degree.
C. Representative operating pressures may range from about 150 psig
to about 600 psig (about 1000 to 4100 kPa), such as from about 250
psig to about 500 psig (about 1700 to 3400 kPa). The LHSV may range
from about 0.1 to about 100, such as from about 1 to about 10. In
the case of the vapor phase operation, the inlet operating
temperature may range from about 20 to about 600.degree. C., such
as from about 200 to about 400.degree. C. Representative operating
pressures may range from about 150 psig to about 600 psig (about
1000 to 4100 kPa), such as from about 250 psig to about 500 psig
(about 1700 to 3400 kPa). The GHSV may range from about 100 to
about 20,000, such as from about 500 to about 5000. Further, the
H.sub.2/C.sub.2H.sub.2 molar feed ratio may range from about 0.5 to
about 20, such as from about 1 to about 10. The feedstreams in MAPD
selective hydrogenation processes may contain at least 80%
propylene, and less than 10% of a compound selected from the group
consisting of methyl acetylene, propadiene, and mixtures
thereof.
[0050] In the case of a butadiene (BD) selective hydrogenation
reactor, operation can be conducted in either the liquid or vapor
phase. In the case of liquid phase operation, the inlet operating
temperature may range from about 20 to about 120.degree. C., such
as from about 40 to about 100.degree. C. Representative operating
pressures may range from about 150 psig to about 600 psig (about
1000 to 4100 kPa), such as from about 200 psig to about 400 psig
(about 1400 to 2800 kPa). The LHSV may range from about 0.1 to
about 100, such as from about 1 to about 25. In the case of the
vapor phase operation, the inlet operating temperature may range
from about 20 to about 600.degree. C., such as from about 50 to
about 200.degree. C. Representative operating pressures may range
from about 150 psig to about 600 psig (about 1000 to 4100 kPa),
such as from about 250 psig to about 500 psig (about 1700 to 3400
kPa). The GHSV may range from about 100 to about 20,000, such as
from about 500 to about 5000. Further, the H.sub.2/C.sub.2H.sub.2
molar feed ratio may range from about 0.5 to about 20, preferably
from about 1 to about 10. The feedstreams in BD selective
hydrogenation processes may contain at least 90% butylene, and
greater than 0.2% butadiene.
[0051] The invention will now be more particularly described with
reference to the following Examples.
[0052] In the Examples, the following definitions are employed:
C.sub.2H.sub.2 Conversion: ( C 2 .times. H 2 ) in - ( C 2 .times. H
2 ) out ( C 2 .times. H 2 ) in 100 ##EQU1## C.sub.2H.sub.4 (Gain)
Selectivity: ( C 2 .times. H 2 ) in - ( C 2 .times. H 2 ) out - C 2
.times. H 6 .times. .times. produced - .times. ( 2 C 4 .times.
.times. produced ) + ( 3 C 6 .times. .times. produced ) ( C 2
.times. H 2 ) in - ( C 2 .times. H 2 ) out 100 ##EQU2##
C.sub.2H.sub.6 Selectivity: C 2 .times. H 6 .times. .times.
produced ( C 2 .times. H 2 ) in - ( C 2 .times. H 2 ) out 100
##EQU3## Green-Oil Selectivity: ( 2 C 4 .times. .times. produced )
+ ( 3 C 6 .times. .times. produced ) ( C 2 .times. H 2 ) in - ( C 2
.times. H 2 ) out 100 ##EQU4##
EXAMPLE 1 (Comparative)
[0053] This example illustrates the performance of a current state
of the art commercial Pd-based catalyst. The catalyst, G-58C, was
obtained from Sud-Chemie, Inc. and comprised 0.03 wt % Pd and 0.18
wt % Ag on alumina. The catalyst was evaluated under the following
conditions: temperature=100.degree. C., pressure=300 psig,
GHSV=4500, H.sub.2/C.sub.2H.sub.2 feed ratio=1.1. The hydrocarbon
feed contained nominally 1.65 mole % acetylene and 70 mole %
ethylene, with balance being nitrogen. Impurities that may be
present in the feed include carbon monoxide (<0.5 ppm), mercury,
arsine, phosphorus (<5 ppb), sulfur (<1 ppm), oxygen (<1
ppm), water (<10 ppm), acetone (<10 ppm) and methanol (<2
ppm). Test results are given in Table 1 below. TABLE-US-00001 TABLE
1 C.sub.2H.sub.2 conv H.sub.2 conv C.sub.2H.sub.4 select
C.sub.2H.sub.6 select Green Oil Catalyst (%) (%) (%) (%) select (%)
G58-C 84.8 100 60.1 15.3 24.6
EXAMPLE 2
[0054] 10 g of theta-alumina (SBa-90 supplied by Sasol) were mixed
with 50 ml of deionized water and a slurry was obtained. Then 0.189
gm Rh(NO.sub.3).sub.3.2H.sub.2O was dissolved in 80 ml deionized
water and was mixed with 0.314 g In(NO.sub.3).sub.3.xH.sub.2O
dissolved in 50 ml deionized water. The solution containing both
metals was added to the alumina slurry and, after 1 hour stirring,
the slurry was gently heated until most of the water was removed.
The resulting paste was dried in a vacuum oven for 2 hours at
100.degree. C., whereafter the remaining powder was calcined in air
for 2 hours at 120.degree. C. and then for 4 hours at 450.degree.
C. The resultant catalyst composition was then reduced at
350.degree. C. for 5 hours in a helium atmosphere containing 5 mol
% hydrogen.
[0055] The final catalyst contained 0.6 wt % rhodium and 1.2 wt %
indium and had a rhodium to indium molar ratio of 0.5. When the
catalyst was used to treat the same hydrocarbon feed under the same
conditions as Example 1, the results summarized in Table 2 were
obtained. TABLE-US-00002 TABLE 2 C.sub.2H.sub.2 H.sub.2
C.sub.2H.sub.4 C.sub.2H.sub.6 conv conv select select Green Oil
Catalyst (%) (%) (%) (%) select (%) 0.6 wt % Rh/1.2 wt % In 79.5
100 55.9 37.1 7
[0056] It will be seen that, although the acetylene conversion and
ethylene selectivity in Examples 1 and 2 were very similar, the
catalyst of Example 2 reduced the production of green oil by a
factor of about 3.5.
EXAMPLE 3 to 5
[0057] The process of Example 2 was repeated with varying amounts
of the rhodium and indium precursors and with the reduction
temperature increased to 450.degree. C. to prepare three additional
Rh/In catalysts having the following compositions: [0058] Example
3=0.6 wt % Rh and 1.2 wt % In, [0059] Example 4=1.2 wt % Rh and 2.4
wt % In, [0060] Example 5=2.4 wt % Rh and 4.8 wt % In.
[0061] When the catalysts were used to treat the same hydrocarbon
feed under the same conditions as Example 1, the results shown in
Table 3 were obtained. TABLE-US-00003 TABLE 3 C.sub.2H.sub.2 conv
H.sub.2 conv C.sub.2H.sub.4 select C.sub.2H.sub.6 select Green Oil
Example (%) (%) (%) (%) select (%) 3 93.4 100 64.3 29.7 6.1 4 81.0
100 45.2 48.2 6.6 5 73.3 100 30.7 62.9 6.4
[0062] It will be seen from Table 3 that, as the rhodium content
increased from 0.6 wt % to 2.4 wt % and the indium content
increased from 1.2 wt % to 4.8 wt %, the acetylene conversion and
the ethylene selectivity decreased rapidly.
EXAMPLE 6 to 22
[0063] A series of catalysts each containing 0.6 wt % indium and
1.2 wt % rhodium were prepared using different rhodium and indium
precursor salts and different supports. In each case, a mixed
solution containing both rhodium and indium ions was prepared and
was used to impregnate the support using an incipient wetness
technique. The impregnation was conducted agitating the support
with the mixed indium-rhodium solution in a vial by vibration for
30 minutes at room temperature (25.degree. C.). After impregnation,
the support was dried at 120.degree. C. for 3 hours and then
calcined in air at 450.degree. C. for 4 hours. The calcined
catalyst was then subjected to reduction in a stream of 5% H.sub.2
in N.sub.2 at 450.degree. C. for 5 hours.
[0064] When sulfate precursor salts were employed, the rhodium
component was obtained by diluting rhodium (III) sulfate (Aldrich,
8 wt % rhodium) with deionized water to 2.48 wt % rhodium, whereas
the indium component was obtained by adding solid indium sulfate
(Aldrich, 2.15 g) to 6.49 g deionized water and 0.46 g concentrated
sulfuric acid to afford an 8.13 wt % indium solution. When nitrate
precursor salts were employed, the rhodium component was obtained
by diluting rhodium nitrate (Strem chemicals, 10.01 wt % solution)
with deionized water to 3.51 wt % rhodium, whereas the indium
component was obtained by dissolving solid indium nitrate
trihydrate (Prochem) in sufficient deionized water to give a
solution containing 8.13 wt % indium. When chloride precursor salts
were employed, the rhodium component was obtained by dissolving
solid rhodium chloride hydrate (Alfa, 1.0953 g) in 20.42 g
deionized water to afford a 2.50 wt % rhodium solution, whereas the
indium component was obtained by dissolving solid indium chloride
tetrahydrate (Aldrich, 4.37 g) in 12.57 g deionized water to afford
a 9.98 wt % indium solution.
[0065] Details of the impregnations are set out below.
[0066] In Example 6, the support was Norton SA6175 alumina which
had been heat treated at 975.degree. C. for 15 minutes to convert
gamma phase to theta phase. The prepared rhodium sulfate solution
(167.3 .mu.L) and indium sulfate solution (89.5 .mu.L) were mixed
with deionized water (343.2 .mu.L) and this mixed rhodium-indium
solution (120 .mu.L) was added to 148 mg of the alumina in a
vial.
[0067] In Example 7, the alumina of Example 6 was used as the
support and a rhodium-indium solution (120 .mu.L) obtained by
mixing the prepared rhodium nitrate solution (121.6 .mu.L) and
indium nitrate solution (62.3 .mu.L) with deionized water (416.1
.mu.L) was added to 148 mg of the alumina in a vial.
[0068] In Example 8, the support was Aerolyst 350 silica supplied
by Degussa and was used as received. The prepared rhodium chloride
solution (125.8 .mu.L) and indium chloride solution (55.0 .mu.L)
were mixed with deionized water (314.1 .mu.L) and this mixed
rhodium-indium solution (99 .mu.L) was added to 108 mg of the
silica in a vial.
[0069] In Example 9, the silica of Example 8 was used as the
support and a rhodium-indium solution (99 .mu.L) obtained by mixing
the prepared rhodium sulfate solution (122.1 .mu.L) and indium
sulfate solution (65.3 .mu.L) with deionized water (307.8 .mu.L)
was added to 108 mg of the silica in a vial.
[0070] In Example 10, the silica of Example 8 was again used as the
support and a rhodium-indium solution (99 .mu.L) obtained by mixing
the prepared rhodium nitrate solution (88.8 .mu.L) and indium
nitrate solution (45.5 .mu.L) with deionized water (360.8 .mu.L)
was added to 108 mg of the silica in a vial.
[0071] In Example 11, the support was Norton XZ16052 zirconia and
was used as received. The prepared rhodium chloride solution (365.8
.mu.L) and indium chloride solution (160.0 .mu.L) were mixed with
deionized water (74.2 .mu.L) and this mixed rhodium-indium solution
(120 .mu.L) was added to 314 mg of the zirconia in a vial.
[0072] In Example 12, the zirconia of Example 11 was used as the
support and a rhodium-indium solution (120 .mu.L) obtained by
mixing the prepared rhodium sulfate solution (355.0 .mu.L) and
indium sulfate solution (189.9 .mu.L) with deionized water (55.1
.mu.L) was added to 314 mg of the zirconia in a vial.
[0073] In Example 13, the zirconia of Example 11 was again used as
the support and a rhodium-indium solution (120 .mu.L) obtained by
mixing the prepared rhodium nitrate solution (355.0 .mu.L) and
indium nitrate solution (189.9 .mu.L) with deionized water (55.1
.mu.L) was added to 314 mg of the zirconia in a vial.
[0074] In Example 14, the support was Aerolyst 7708 titania
supplied by Degussa and was used as received. The prepared rhodium
chloride solution (268.0 .mu.L) and indium chloride solution (117.2
.mu.L) were mixed with deionized water (17.4 .mu.L) and this mixed
rhodium-indium solution (80 .mu.L) was added to 230 mg of the
titania in a vial.
[0075] In Example 15, the titania of Example 14 was used as the
support and a rhodium-indium solution (80 .mu.L) obtained by mixing
the prepared rhodium sulfate solution (260.0 .mu.L) and indium
sulfate solution (139.1 .mu.L) with deionized water (3.34 .mu.L)
was added to 230 mg of the titania in a vial.
[0076] In Example 16, the titania of Example 14 was again used as
the support and a rhodium-indium solution (80 .mu.L) obtained by
mixing the prepared rhodium nitrate solution (189.0 .mu.L) and
indium nitrate solution (96.8 .mu.L) with deionized water (116.7
.mu.L) was added to 230 mg of the titania in a vial.
[0077] In Example 17, the support was zirconia-silica (MA1030Zr1)
supplied by PQ Corporation and was used as received. The prepared
rhodium chloride solution (107.2 .mu.L) and indium chloride
solution (46.9 .mu.L) were mixed with deionized water (407.2 .mu.L)
and this mixed rhodium-indium solution (112 .mu.L) was added to 92
mg of zirconia-silica in a vial.
[0078] In Example 18, the zirconia-silica of Example 17 was used as
the support and a rhodium-indium solution (112 .mu.L) obtained by
mixing the prepared rhodium sulfate solution (104.0 .mu.L) and
indium sulfate solution (55.7 .mu.L) with deionized water (401.6
.mu.L) was added to 92 mg of zirconia-silica in a vial.
[0079] In Example 19, the zirconia-silica of Example 17 was again
used as the support and a rhodium-indium solution (112 .mu.L)
obtained by mixing the prepared rhodium nitrate solution (75.6
.mu.L) and indium nitrate solution (38.7 .mu.L) with deionized
water (446.9 .mu.L) was added to 92 mg of zirconia-silica in a
vial.
[0080] In Example 20, the support was titania-silica supplied by PQ
Corporation and was used as received. The prepared rhodium chloride
solution (122.3 .mu.L) and indium chloride solution (53.5 .mu.L)
were mixed with deionized water (344.2 .mu.L) and this mixed
rhodium-indium solution (104 .mu.L) was added to 105 mg of
titania-silica in a vial.
[0081] In Example 21, the titania-silica of Example 20 was used as
the support and a rhodium-indium solution (104 .mu.L) obtained by
mixing the prepared rhodium sulfate solution (118.7 .mu.L) and
indium sulfate solution (63.5 .mu.L) with deionized water (337.8
.mu.L) was added to 105 mg of titania-silica in a vial.
[0082] In Example 22, the titania-silica of Example 20 was used as
the support and a rhodium-indium solution (104 .mu.L) obtained by
mixing the prepared rhodium sulfate solution (118.7 .mu.L) and
indium sulfate solution (63.5 .mu.L) with deionized water (337.8
.mu.L) was added to 105 mg of titania-silica in a vial.
[0083] When the resultant catalysts were used to treat the same
hydrocarbon feed under the same conditions as Example 1, the
results shown in Table 4 were obtained.
[0084] The results in Table 4 show that nitrate precursors
consistently produce significantly better catalysts than chloride
and sulfate precursors and that alumina and zirconia are superior
supports to silica, titania, silica-zirconia and titania-silica
supports. The negative values in Table 4 are the result of the
equations referred to above and used to calculate conversion and
selectivity. Thus it will be appreciated that experimental error in
measuring species concentrations can lead to the calculation of
negative values in the above equations when conversions are
extremely low. TABLE-US-00004 TABLE 4 C.sub.2H.sub.2 conv H.sub.2
conv C.sub.2H.sub.4 select C.sub.2H.sub.6 select Green Oil Example
Precursors Support (%) (%) (%) (%) select (%) 6 Sulfates Alumina
26.3 34.9 20.3 62.0 17.7 7 Nitrates Alumina 83.8 93.4 59.7 34.7 5.7
8 Chlorides Silica 0.8 1.0 29.6 64.4 6.0 9 Sulfates Silica -0.7
-0.1 129.8 -29.8 6.0 10 Nitrates Silica -0.7 1.9 150 -50 -21.2 11
Chlorides Zirconia 46.3 63.0 21.9 63.9 14.2 12 Sulfates Zirconia
8.2 12.0 -17.5 90.7 26.7 13 Nitrates Zirconia 51.4 76.8 7.8 79.2
13.1 14 Chlorides Titania 7.5 8.7 35.5 47.0 17.5 15 Sulfates
Titania 8.0 10.9 20.2 66.2 13.6 16 Nitrates Titania 20.0 23.5 50.6
40.8 8.5 17 Chlorides Zirconia-Silica 0.8 1.1 55.6 44.4 0 18
Sulfates Zirconia-Silica 0.3 0.9 -50.0 150.0 18.0 19 Nitrates
Zirconia-Silica 1.5 2.2 63.6 33.1 3.3 20 Chlorides Titania-Silica
0.9 1.4 28.8 64.2 7.0 21 Sulfates Titania-Silica 0.3 2.4 -50 150.0
27.1 22 Nitrates Titania-Silica -0.3 2.4 150 -50.0 -50.0
EXAMPLES 23 to 28
[0085] A series of catalysts each containing 0.6 wt % indium and
1.2 wt % rhodium were prepared using different rhodium and indium
precursor salts and a ceria/alumina support (Norpro,
50%CeO.sub.2/Al.sub.2O.sub.3, 135 m.sup.2/g, pore volume=0.51
mL/g). In each case, a solution containing the rhodium precursor
was first impregnated onto the support using an incipient wetness
technique and then a solution containing the indium precursor was
used to impregnate the support using the same incipient wetness
technique as outlined below.
[0086] When nitrate precursor salts were employed, the rhodium
component was obtained by diluting rhodium nitrate (Strem
chemicals, 10.01 wt % solution) with deionized water to 3.51 wt %
rhodium, whereas the indium component was obtained by dissolving
solid indium nitrate trihydrate (Prochem) in sufficient deionized
water to give a solution containing 110.0 wt % indium. When a
rhodium oxoacetate precursor was used, this was prepared by adding
hexa(acetato)-.mu.-oxotris(aqua)trirhodium(III) acetate (Alfa, 0.88
g) added to 2.08 g glacial acetic acid and 1.32 g deionized water,
whereafter the resultant mixture was shaken until all solid
dissolved and then diluted with a further 9.54 g deionized water to
afford a 2.47 wt % Rh solution. When a rhodium acetylacetate
precursor was used, this was prepared by dissolving rhodium
(2,4-pentanedionate), i.e., rhodium(acetylacetonate), (Aldrich) in
a mixture of methanol and 2,4-pentanedione such that the
concentrations were 1.62 wt % rhodium and 23.0 wt %
2,4-pentanedione. An indium formate precursor was synthesized by
refluxing indium hydroxide (Alfa, 3.20 g) with 60.72 g formic acid
(Aldrich) in a round bottom flask with stirring overnight to obtain
a homogeneous, colorless solution. The solvent was then evaporated
by boiling the solution to leave an off-white solid, whereafter the
resultant solid indium formate was dissolved in a mixture of formic
acid and water such that the indium concentration was 2.1 wt % and
the concentration of formic acid was about 60 %.
[0087] Details of the catalyst preparations are set out below.
[0088] In Example 23, the prepared rhodium nitrate solution (226.8
.mu.L) was mixed with deionized water (523.2 .mu.L) and the diluted
rhodium nitrate solution (125 .mu.L) was added to 230 mg of
ceria-alumina and agitated by vibration for 30 minutes at room
temperature. The obtained material was dried at 120.degree. C. for
3 hours and then calcined in air at 450.degree. C. for 4 hours.
Following calcination, the obtained agglomerated solid was gently
broken up with a spatula. The prepared indium nitrate solution
(117.6 .mu.L) was mixed with deionized water (632.4 .mu.L). This
diluted indium nitrate solution (125 .mu.L) was added to the
calcined product of the first impregnation and agitated by
vibration for 30 minutes at room temperature. The obtained material
was dried at 120.degree. C. for 3 hours and then calcined in air at
450.degree. C. for 4 hours. The calcined catalyst was then
subjected to reduction in a stream of 5% H.sub.2 in N.sub.2 at
450.degree. C. for 5 hours.
[0089] In Example 24, the prepared indium formate solution (716.9
.mu.L) was mixed with deionized water (33.1 .mu.L) and the diluted
indium formate solution (125 .mu.L) was added to the calcined
product of the first impregnation of Example 23 and agitated by
vibration for 30 minutes at room temperature. The obtained material
was dried at 120.degree. C. for 3 hours and then calcined in air at
450.degree. C. for 4 hours. The calcined catalyst was then
subjected to reduction in a stream of 5% H.sub.2 in N.sub.2 at
450.degree. C. for 5 hours.
[0090] In Example 25, the prepared rhodium(oxo)acetate solution
(322.3 .mu.L) was mixed with deionized water (427.7 .mu.L). This
diluted rhodium(oxo)acetate solution (125 .mu.L) was added to 230
mg of ceria-alumina and agitated by vibration for 30 minutes at
room temperature. The obtained material was dried at 120.degree. C.
for 3 hours and then calcined in air at 450.degree. C. for 4 hours.
Following calcination, the obtained agglomerated solid was gently
broken up with a spatula. The prepared indium nitrate solution
(117.6 .mu.L) was mixed with deionized water (632.4 .mu.L). This
diluted indium solution (125 .mu.L) was added to the calcined
product of the first impregnation and agitated by vibration for 30
minutes at room temperature. The obtained material was dried at
120.degree. C. for 3 hours and then calcined in air at 450.degree.
C. for 4 hours. The calcined catalyst was then subjected to
reduction in a stream of 5% H.sub.2 in N.sub.2 at 450.degree. C.
for 5 hours.
[0091] In Example 26, the prepared indium formate solution (716.9
.mu.L) was mixed with deionized water (33.1 .mu.L) and the diluted
indium formate solution (125 .mu.L) was added to the calcined
product of the first impregnation of Example 25 and agitated by
vibration for 30 minutes at room temperature. The obtained material
was dried at 120.degree. C. for 3 hours and then calcined in air at
450.degree. C. for 4 hours. The calcined catalyst was then
subjected to reduction in a stream of 5% H.sub.2 in N.sub.2 at
450.degree. C. for 5 hours.
[0092] In Example 27, methanol (25 .mu.L) was added to 230 mg of
ceria-alumina to allow for particle wetting. The prepared
rhodium(acetylacetonate) solution was warmed above 50.degree. C.
until it became homogeneous and then 85.2 .mu.L was added to the
prepared ceria-alumina and agitated by vibration. Another 50 .mu.L
of methanol was added to the sample and vibration was continued for
30 minutes. The obtained material was dried at 120.degree. C. for 3
hours and then calcined in air at 450.degree. C. for 4 hours.
Following calcination, the obtained agglomerated solid was gently
broken up with a spatula. The prepared indium nitrate solution
(117.6 .mu.L) was mixed with deionized water (632.4 .mu.L). This
diluted indium solution (125 .mu.L) was added to the calcined
product of the first impregnation and agitated by vibration for 30
minutes at room temperature. The obtained material was dried at
120.degree. C. for 3 hours and then calcined in air at 450.degree.
C. for 4 hours. The calcined catalyst was then subjected to
reduction in a stream of 5% H.sub.2 in N.sub.2 at 450.degree. C.
for 5 hours.
[0093] In Example 28, the prepared indium formate solution (716.9
.mu.L) was mixed with deionized water (33.1 .mu.L) and the diluted
indium formate solution (125 .mu.L) was added to the calcined
product of the first impregnation of Example 27 and agitated by
vibration for 30 minutes at room temperature. The obtained material
was dried at 120.degree. C. for 3 hours and then calcined in air at
450.degree. C. for 4 hours. The calcined catalyst was then
subjected to reduction in a stream of 5% H.sub.2 in N.sub.2 at
450.degree. C. for 5 hours.
[0094] When the resultant catalysts were used to treat the same
hydrocarbon feed under the same conditions as Example 1, the
results shown in Table 5 were obtained. TABLE-US-00005 TABLE 5
C.sub.2H.sub.2 conv H.sub.2 conv C.sub.2H.sub.4 select
C.sub.2H.sub.6 select Green Oil Example (%) (%) (%) (%) select (%)
23 76.2 87.8 54.4 39.4 6.1 24 79.5 95.5 48.9 44.2 6.9 25 30.2 52.3
-19.7 105.3 14.4 26 38.1 57.0 10.3 78.5 11.1 27 20.9 28.0 22.6 64.3
13.1 28 20.6 27.8 19.0 65.9 15.1
[0095] The results in Table 5 show that ceria-alumina is a useful
support material and that nitrate appears to be the best precursor
for rhodium and nitrates and formates are good precursors for
indium.
EXAMPLES 9 to 47
[0096] The sequential impregnation procedure and the rhodium and
indium precursors of Examples 23 to 28 were used with the supports
employed in Examples 6 to 16 to produce the following
catalysts:
[0097] Example 29=0.6wt % Rh (from nitrate)/1.2wt % In (from
formate) on Al.sub.2O.sub.3
[0098] Example 30=0.6wt % Rh (from oxoacetate)/1.2wt % In (from
nitrate) on Al.sub.2O.sub.3
[0099] Example 31=0.6wt % Rh (from oxoacetate)/1.2wt % In (from
formate) on Al.sub.2O.sub.3
[0100] Example 32=0.6wt % Rh (from chloride)/1.2wt % In (from
nitrate) on Al.sub.2O.sub.3
[0101] Example 33=0.6wt % Rh (from nitrate)/1.2wt % In (from
nitrate) on SiO.sub.2
[0102] Example 34=0.6wt % Rh (from nitrate)/1.2wt % In (from
formate) on SiO.sub.2
[0103] Example 35=0.6wt % Rh (from oxoacatetate)/1.2wt % In (from
nitrate) on SiO.sub.2
[0104] Example 36=0.6wt % Rh (from oxoacatetate)/1.2wt % In (from
formate) on SiO.sub.2
[0105] Example 37=0.6wt % Rh (from chloride)/1.2wt % In (from
formate) on SiO.sub.2
[0106] Example 38=0.6wt % Rh (from nitrate)/1.2wt % In (from
nitrate) on ZrO.sub.2
[0107] Example 39=0.6wt % Rh (from nitrate)/1.2wt % In (from
formate) on ZrO.sub.2
[0108] Example 40=0.6wt % Rh (from oxoacatetate)/1.2wt % In (from
nitrate) on ZrO.sub.2
[0109] Example 41=0.6wt % Rh (from oxoacatetate)/1.2wt % In (from
formate) on ZrO.sub.2
[0110] Example 42=0.6wt % Rh (from chloride)/1.2wt % In (from
formate) on ZrO.sub.2
[0111] Example 43=0.6wt % Rh (from nitrate)/1.2wt % In (from
nitrate) on TiO.sub.2
[0112] Example 44=0.6wt % Rh (from nitrate)/1.2wt % In (from
formate) on TiO.sub.2
[0113] Example 45=0.6wt % Rh (from oxoacatetate)/1.2wt % In (from
nitrate) on TiO.sub.2
[0114] Example 46=0.6wt % Rh (from oxoacatetate)/1.2wt % In (from
formate) on TiO.sub.2
[0115] Example 47=0.6wt % Rh (from chloride)/1.2wt % In (from
formate) on TiO.sub.2
[0116] When the resultant catalysts were used to treat the same
hydrocarbon feed under the same conditions as Example 1, the
results shown in Table 6 were obtained. TABLE-US-00006 TABLE 6
C.sub.2H.sub.2 conv H.sub.2 conv C.sub.2H.sub.4 select
C.sub.2H.sub.6 select Green Oil Example (%) (%) (%) (%) select (%)
29 79.3 88.3 56.4 35.0 8.6 30 28.9 45.5 1.2 86.8 12.0 31 41.5 54.7
33.7 57.9 8.4 32 7.6 9.9 36.7 54.7 8.5 33 3.4 1.6 90.9 7.9 1.1 34
5.0 4.4 59.6 34.8 5.6 35 2.2 2.3 54.6 38.7 6.8 36 2.7 3.2 38.3 55.0
6.6 37 1.5 1.4 60.0 36.8 3.2 38 66.0 82.8 36.1 53.5 10.4 39 87.9
96.1 61.1 32.9 6.0 40 48.6 82.0 -15.7 104.1 11.6 41 69.3 88.9 37.1
55.2 7.7 42 30.7 39.7 30.6 57.0 12.4 43 26.2 29.6 54.0 37.3 8.7 44
26.2 27.6 60.9 31.6 7.5 45 16.6 18.3 56.8 35.9 7.3 46 17.3 19.1
57.6 35.9 6.5 47 7.8 8.2 58.2 34.2 7.7
[0117] The results in Table 6 show that alumina and zirconia are
superior support materials to silica and titania and that nitrate
appears to be the best precursor for rhodium and nitrates and
formates are good precursors for indium.
[0118] While the present invention has been described and
illustrated by reference to particular embodiments, those of
ordinary skill in the art will appreciate that the invention lends
itself to variations not necessarily illustrated herein. For this
reason, reference should be made solely to the appended claims for
purposes of determining the true scope of the present
invention.
* * * * *