Molecular sieve abstract
A catalytic converter for treating exhaust gas from an internal
combustion engine containing a catalyst characterized by having
platinum or a platinum alloy dispersed predominantly on the exterior
surface of molecular sieve crystals. Also provided is a catalyst
for such a converter and processes for manufacture of such catalyst.
In addition, methods for treating exhaust gas from an internal combustion
engine to reduce the amounts of hydrocarbon, carbon monoxide and
nitrogen oxides emitted to the atmosphere are included.
Molecular sieve claims
We claim:
1. A process for making a catalyst containing at least one type
of molecular sieve crystals having noble metal dispersed on the
exterior surface of said molecular sieve crystals such that at least
90% of the noble metal is located within 500 .ANG. of the exterior
surface of said molecular sieve crystals comprising:
a) preparing an aqueous suspension of at least one type of molecular
sieve crystals and a noble metal reagent, said reagent being of
the type that, when suspended in water, will chemisorb onto the
exterior 500 .ANG. of said crystals;
b) adjusting the pH of the suspension to above about 7 with a material
that will decompose to yield gaseous products when its temperature
is raised to above about 150.degree. C.;
c) stirring the suspension until the molecular sieve crystals and
reagent are thoroughly mixed and the chemisorption has taken place;
d) coating a suitable substrate with the product of step (c) thereby
preparing a coated substrate having a coating thickness between
1-20 microns;
e) drying the coated substrate, and, thereafter,
f) calcining said coated substrate at a temperature between about
400.degree. C. to about 550.degree. C. for at least two hours.
2. The process of claim 1 wherein a second type of molecular sieve
crystal is added to the suspension after step (c) and before step
(d).
3. The process of claim 2 wherein, prior to the coating step, a
binder is added to the suspension, said binder being selected from
the group consisting of alumina, silica, alumina-silicates, titania,
magnesia, zirconia, beryllia, and mixtures thereof.
4. The process of claim 3 wherein the binder is milled alumina.
5. The process of claim 1 wherein the pH is adjusted with tetramethylammonium
hydroxide.
6. The process of claim 1 wherein the noble metal is in the form
of colloidal particles and is selected from the group consisting
of Pt, Pt alloyed with Rh, Ir, Pd, Ag, or Au, and mixtures thereof.
7. The process of claim 1 wherein the substrate is a monolith.
8. A process for making a catalyst containing at least one type
of molecular sieve crystals having noble metal uniformly dispersed
on the exterior surface of said molecular sieve crystals such that
at least 90% of the noble metal is located within 500 .ANG. of the
exterior surface of the crystals comprising:
a) preparing an aqueous suspension of at least one type of molecular
sieve crystals and an amount of a hydrophilic polymer having a density
of between about 0.8 and about 1.0 gm/cm.sup.3 said amount of hydrophilic
polymer being sufficient to fill the pores of said molecular sieve
crystals;
b) adding a noble metal reagent to the product of step (a);
c) adjusting the pH of the suspension to above about 7 with a material
that will decompose to yield gaseous products when its temperature
is raised above about 150.degree. C.;
d) stirring for at least one hour;
e) adding an aqueous suspension of binder to the product of step
(d);
f) stirring the product of step (e) for at least one hour;
g) coating a substrate with the product of step (f) thereby preparing
a coated substrate; and
h) drying and calcining said coated substrate.
9. The process of claim 8 wherein a second type of molecular sieve
crystal is added to the suspension after step (c) and before step
(d).
10. The process of claim 9 wherein the binder of step (e) is selected
from the group consisting of alumina, silica, alumina-silicates,
titania, magnesia, zirconia, beryllia, and mixtures thereof.
11. The process of claim 10 wherein the binder is milled alumina.
12. The process of claim 8 wherein the hydrophilic polymer is selected
from the group consisting of polyethylene glycol, polyvinyl glycol
and polyvinyl pyrollidone.
13. The process of claim 8 wherein the noble metal is in the form
of colloidal particles and is selected from the group consisting
of Pt, Pt alloyed with Rh, Ir, Pd, Ag, or Au, and mixtures thereof.
14. The process of claim 8 wherein the substrate is a monolith.
15. A process for making a catalyst containing at least one type
of molecular sieve crystals having noble metal predominantly on
the exterior surface of at least one type of said molecular sieve
crystals comprising:
a) preparing an aqueous suspension of at least one type of molecular
sieve crystals and colloidal particles of noble metal, the size
of said noble metal particles being at least twice the largest crystallographically-defined
pore diameter of the molecular sieve crystals;
b) adjusting the suspension pH to between about 7 and about 8.;
c) stirring for at least one hour;
d) adding an aqueous suspension of binder to the product of step
(d);
e) stirring the product of step (e) for at least one hour;
f) coating a substrate with the product of step (f) thereby preparing
a coated substrate; and
g) drying and calcining said coated substrate.
16. The process of claim 15 wherein a second type of molecular
sieve crystal is added to the suspension after step (c) and before
step (d).
17. The process of claim 16 wherein the binder is milled alumina.
18. The process of claim 15 wherein the binder of step (d) is selected
from the group consisting of alumina, silica, alumina-silicates,
titania, magnesia, zirconia, beryllia, and mixtures thereof.
19. The process of claim 15 wherein the pH of the suspension is
adjusted, in step (b), with tetramethylammonium hydroxide.
20. The process of claim 15 wherein the noble metal is in the form
of colloidal particles and is selected from the group consisting
of Pt, Pt alloyed with Rh, Ir, Pd, Ag, or Au, and mixtures thereof.
21. The process of claim 15 wherein the substrate is a monolith.
Molecular sieve description
FIELD OF THE INVENTION
This invention relates to a catalytic converter containing therein
a catalyst having noble metal dispersed on the surface of molecular
sieve crystals. This invention further relates to a catalyst suitable
for such converter, a process for treating the exhaust gas from
an internal combustion engine, and processes for making a catalyst
having noble metal dispersed on the exterior surface of molecular
sieve crystals.
BACKGROUND OF THE INVENTION
Catalytic converters containing various catalysts have been employed
for years by automobile manufacturers to meet the ever-more-stringent
regulations on emissions of hydrocarbon, carbon monoxide, and particularly,
nitrogen oxides from internal combustion engines. Concurrently with
the promulgation of these ever-tightening regulations on emissions,
automotive engine manufacturers have worked to improve the fuel
economy of such engines. This effort has led to the development
of engines that operate with an excess of air beyond that which
is required to consume stoichiometrically the fuel admitted to such
engines ("lean-burn engines"). The advent of lean-burn
engines has, in turn, exacerbated the problem of reducing emission
of nitrogen oxides from internal combustion engines.
Various techniques have been developed to treat exhaust gas from
internal combustion engines. One approach has been to provide multiple
catalyst chambers in the exhaust system filled with different catalysts
suited to particular tasks, such as that taught by Takeshima, et
al. in U.S. Pat. No. 5233830.
Another approach is to provide a control system operating in conjunction
with a catalytic converter, such as taught by Hirota, et al. in
U.S. Pat. No. 5201802 and U.S. Pat. No. 5189876 and also by
Takeshima in U.S. Pat. No. 5029061.
Clearly, there is a need for a simple system capable of treating
exhaust gas from internal combustion engines, particularly the exhaust
gas from lean-burn engines. The present invention is such a system,
employing as it does a single catalytic converter having a single,
unique catalyst contained therein which is capable of reducing the
amount of hydrocarbon, carbon monoxide and, particularly, nitrogen
oxides contained in exhaust gas prior to such gas's discharge to
the atmosphere.
As stated above, the key element in such a system is the discovery
of a catalyst which is effective in oxidizing hydrocarbon and carbon
monoxide while being surprisingly effective at concurrently reducing
nitrogen oxides in the environment presented by exhaust gas from
internal combustion engines. Numerous inventions in this area have
been taught by others skilled in the art, but none of these resembles
more than superficially the catalyst of the present invention. For
instance, U.S. Pat. No. 5376610 (Takahata, et al.) teaches, as
part of a multi-catalyst system for exhaust gas purification, a
catalyst consisting of alumina, and optionally zeolite, with Pt
and/or Pd impregnated therein.
U.S. Pat. No. 5292991 (Lachman, et al.) teaches a catalyst consisting
of a mixture of alumina and zeolite on a substrate with noble metal
predominately dispersed on the alumina.
Patents have also been granted for catalysts intended for other
uses, and some of these more closely resemble, at least superficially,
the catalyst of the present invention. U.S. Pat. No. 5314854 (Galperin)
teaches a catalyst designed primarily for the dehydrocyclization
of paraffins to aromatics that consists of large pore molecular
sieves mixed with binder and formed into pellets, spheres, or other
such particles, said particles then having a surface-layer palladium
component and uniformly dispersed platinum.
U.S. Pat. No. 4992158 (Schweizer) teaches a catalyst for reforming
hydrocarbons having boiling points in the range of motor gasoline
that is characterized as L-type zeolite not fully impregnated with
Pt or Pd, using Pt- or Pd- acetylacetonate as the noble metal compound
to treat the L-zeolite.
U.S. Pat. No. 5017541 (Schmidt, et al.) teaches a catalyst for
the isomerization of alkanes consisting of particles of refractory
inorganic oxide having a slightly higher concentration of a metal
from the platinum group at the surface of such particles than at
their center. The width of the surface-enriched band is 100-150
.mu.m while the particles themselves have diameters of about 0.7-3.3
.mu.m.
Still more patents have been granted for the preparation of noble
metal/zeolite catalysts without regard to the use of same. U.S.
Pat. No. 4556646 (Bezman) teaches a method for the preparation
of a catalyst consisting of an inorganic oxide, a zeolite, and a
noble metal in which ammonium nitrate is employed as an impregnating
agent for Pd to produce a uniform distribution of the metal throughout
the catalyst particles. Data are presented showing that, if ammonium
nitrate is not used, Pd is concentrated in the outer shell of the
catalyst particles. In this case, however, the Pd is deposited on
the inorganic oxide as well as the zeolite, and the inventor suggests
that deposition of Pd in the outer shell is a condition to be avoided.
U.S. Pat. No. 4882307 (Tsao) teaches the use of various salts,
including sulfites, of cationic Pt complexes as an agent for the
deposition of Pt into zeolite as a way of yielding highly dispersed
Pt crystallites, after appropriate treatments.
U.S. Pat. No. 4683214 (Angevine, et al.) also teaches the use
of sulfite salts of cationic noble metal complexes as a means of
depositing noble metal on zeolite to yield, after appropriate treatment,
very highly dispersed metal crystallites.
And, finally, U.S. Pat. No. 5290534 (Tsao) teaches that when
a noble metal precursor is placed into a reactor during the production
or synthesis of ZSM-18 substantially all of the noble metal remains
on the outside of the synthesized ZSM-18. No indication is given
that this is a desirable result, however, since the point of this
invention is to provide a method of removing organic material blocking
the pores of a zeolite.
SUMMARY OF THE INVENTION
It is a feature of the invention to provide superior catalytic
converters for removing NO.sub.x from the exhaust of internal combustion
engines that are operating with the air-to-fuel ratio in the lean
range, that is, where the amount of oxygen supplied is greater than
the stoichiometric amount needed to support combustion.
This invention provides for a catalytic converter suitable for
treating exhaust gas from an internal combustion engine, and particularly
for treating the gas from a lean-burn motor vehicle engine. The
catalytic converter of the present invention comprises an exhaust
gas processing vessel of suitable size and shape that is adapted
to receive exhaust directly from the engine. Contained in this vessel
is an effective amount of a catalyst coating uniformly dispersed
on a suitable substrate. The substrate, in turn, is adapted to fit
within the vessel in such a way as to assure that the exhaust gas
adequately and effectively contacts the catalyst coating on the
substrate.
The catalyst coating for use in this invention is characterized
as containing molecular sieve crystals on the surface of which has
been uniformly dispersed a catalytically effective amount of a noble
metal, preferably platinum or a platinum alloy. The molecular sieve
crystals on which the noble metal has been dispersed have diameters
within a range of about 0.5 to about 50 .mu.m. The noble metal is
dispersed on the surface of the molecular sieve crystals in such
a manner as to locate at least 90% of the noble metal within 50
nm (500 .ANG.) of the exterior surface of the crystals.
This invention also provides a catalyst for such a catalytic converter
and processes for making such catalyst. In one process for making
the catalyst according to this invention such that the noble metal
is dispersed predominately on the exterior surface of the molecular
sieve crystals, the first step is to prepare an aqueous suspension
of the molecular sieve crystals and a noble metal reagent that will
chemisorb onto the exterior 50 nm (500 .ANG.) of the said crystals.
Depending on the noble metal reagent used, bonding of the reagent
to the sieve will be either covalent or ionic. If the reagent chosen
forms a covalent bond, it is important that the molecular sieve
crystals used in this process be modified to have a very thin film
of aluminum oxide on their exterior surfaces. The choice of method
for forming this thin alumina film depends on the Si/Al ratio of
the zeolitic precursor. Sufficient acid or base may be added to
the suspension to adjust the pH to between about 7-8. Any pH adjustment
should be done using a material that will decompose to yield gaseous
products when its temperature is raised above about 150.degree.
C. If the reagent chosen forms an ionic bond to the sieve, no modification
to the zeolite to form a thin alumina film is necessary, but the
pH of the aqueous suspension of molecular sieve crystals and noble
metal reagent should be above 10 and the chosen reagent must be
a cationic noble-metal complex whose kinetic radius of its smallest
conformation is larger than the largest crystallographically-defined
pore of the zeolite chosen. Appropriate noble metal reagents of
the type that form a covalent bond that, when suspended in water,
will chemisorb onto the exterior 50 nm (500 .ANG.) of said crystals
include Pt sulfite and [N(C.sub.2 H.sub.5).sub.4 ].sub.2
[Pt(OH).sub.6 ]. Appropriate noble metal reagents of the type that
form an ionic bond that, when suspended in water, will chemisorb
onto the exterior 50 nm (500 .ANG.) of said crystals, include [Pt(NH.sub.2
CH.sub.2 CH.sub.2 NH.sub.2).sub.2 ][OH].sub.2 and [Pt(NH.sub.2 CH.sub.2
CH.sub.2 NH.sub.2).sub.2 ][CO.sub.3 ]. After adequate stirring the
suspension is coated onto a suitable substrate, dried and calcined
at a temperature sufficient to decompose the base reagent material.
Alternatively, a catalyst containing molecular sieve crystals of
at least one type having noble metal dispersed predominantly on
the exterior surface of the crystals can be made by a process in
which the first step is to prepare an aqueous suspension of the
crystals with a hydrophilic polymer having a density between about
0.8 and about 1.0 gm/cm.sup.3 the amount of polymer used being
sufficient to fill the pores of the molecular sieve crystals used.
Thereafter a suitable noble metal reagent (which need not be chemisorbing)
is added to the suspension, the pH adjusted to between about 7 and
8 and the suspension then coated on a suitable substrate, dried
and calcined. In the process of heating, the material used to adjust
the pH and the hydrophilic polymer are completely burned off and
vaporized, thereby leaving the noble metal dispersed uniformly on
the first 50 nm (500 .ANG.) of the molecular sieve crystals.
A third method for making a catalyst containing molecular sieve
crystals of at least one type having noble metal dispersed predominantly
on the exterior surface of the crystals employs the use of colloidal
particles of platinum or a platinum alloy of a size substantially
greater, by at least a factor of two, than the largest crystallographically
defined pore diameter of the molecular sieve crystals onto which
the noble metal is to be deposited.
Finally, this invention provides processes for treating exhaust
gas from an internal combustion engine using the catalytic converter
and catalyst of the present invention.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a micrograph of the powder used to coat the monolith
in one embodiment of the present invention.
FIG. 2 is a micrograph of a thin section of the inside, together
with portions of their exterior edges, of two molecular sieve crystals
taken from the coating of a catalyst prepared by one of the methods
presented herein but using a platinum reagent that does not chemisorb
onto the exterior surface of molecular sieve crystals. This catalyst
is typical of platinum-containing molecular sieve catalysts that
have been suggested in the prior art for use in treating exhaust
gas from an internal combustion engine.
FIG. 3 presents data comparing the performance (shown as NO.sub.x
conversion) of the present invention against that of a typical catalytic
converter using a typical catalyst when used to treat exhaust gas
from the same lean-burn diesel engine.
FIG. 4 presents data comparing the performance (shown as NO.sub.x
conversion) of three catalysts of the present invention against
that of a similar catalyst prepared without using the process taught
by the present invention.
FIG. 5 presents data comparing the performance (shown as NO.sub.x
conversion) of the present invention against that of a typical catalytic
converter using a catalyst similar to that taught in Lachman '991
when used to treat exhaust gas from the same lean-burn diesel engine.
DETAILED DESCRIPTION OF THE INVENTION
The catalytic converter of the present invention comprises a vessel
and a catalyst contained in the vessel.
Vessel
The exhaust gas processing vessel may be any suitable shape and
configuration, with cylindrical or "flattened" cylindrical
(i.e., an extended oval) being the preferred shapes, that provides
a substantially uniform distribution of exhaust gas throughout and
an efficient flow over the catalyst to be contained therein. The
vessel should have sufficient void volume to contain a catalyst
sized so that the gas hourly space velocity ("GHSV") over
the catalyst is no greater than about 150000 hr.sup.-1 when the
engine producing the exhaust gas to be treated is operating at its
maximum sustainable load. The vessel should be fitted at its inlet
end with a tubular conduit adapted to receive exhaust from the engine
exhaust manifold, and at its outlet end with a tubular conduit adapted
to transmit treated exhaust to a muffler or directly to the atmosphere.
Materials of construction of the vessel and inlet and outlet conduits
are well known to those skilled in the art and may be of any metal
or composite able to withstand temperatures of up to about 1200.degree.
C. with minimal corrosion from the compounds normally contained
in internal combustion engine exhaust gas.
Catalyst
The catalyst is comprised of a substrate on which has been suitably
applied an effective amount of a catalytically active coating containing
at least one type of molecular sieve crystals, with platinum or
a platinum alloy uniformly dispersed on the exterior surface of
such crystals. The coating may also contain a binder and one or
more types of molecular sieve crystals.
Substrate
The substrate may be any of the shapes employed by those skilled
in the art such as extrudates, spheres, beads, tablets, and the
like, but monoliths, either metallic or ceramic, are preferred.
The substrate should be inert in the sense that it does not react
with the coating or with the exhaust gas to which it is exposed
during engine operation.
If a monolith is employed as the substrate, it should be sized
and shaped so that it fits within the vessel and leaves no gaps
between the vessel interior wall and the outside surface of the
monolith which might result in blow-by of the exhaust gas past the
monolith (i.e., bypassing of the catalyst). Ceramic monoliths, if
employed, should be provided with a mat-mount between the exterior
surface of the monolith and the vessel wall, as is customary in
the industry, to cushion vibration during engine operation and also
to prevent blow-by of the engine exhaust gas past the catalyst.
Metallic monoliths should be attached to the vessel wall, as is
customary. There should be provided sufficient monolith to result
in a GHSV as defined above in the discussion on Vessel.
Coating
The coating is comprised of suitable molecular sieve crystals,
onto the exterior surface of which crystals a catalytically effective
amount of platinum or a platinum alloy has been dispersed in a manner
such that at least 90% of the platinum or platinum alloy is deposited
within the exterior 500 .ANG. of the surface of such crystals. An
inorganic oxide binder may be included in the coating, but it is
an important aspect of this invention that little of the platinum
or platinum alloy be deposited on such inorganic oxide binder. If
a binder is employed it is important that the binder and molecular
sieve crystals be thoroughly mixed so that the crystals are uniformly
dispersed throughout the coating.
The coating should be uniformly applied to the substrate. The coating's
thickness should be no more than about 200 microns and no less than
about 1 micron, with a coating thickness averaging between about
20 microns and 40 microns being preferred. Any method known to those
skilled in the art including, without limitation, immersion of the
substrate in an aqueous suspension of the desired coating or spraying
of the suspension onto the substrate, may be employed to achieve
the desired coating thickness and uniformity of application. The
preferred method of application onto monoliths is "piston coating",
which involves placing the monolith above a reservoir containing
an amount of the coating, compressing the coating up into the monolith
with a piston, withdrawing the piston to permit the coating to drain
back into the reservoir, and then immediately clearing the channels
of the monolith with a slotted knife that emits compressed air.
This method is particularly useful when applying coatings containing
large mass fractions of molecular sieves since the sieve density
is quite low.
Following application of the coating to the substrate, the coated
substrate is dried and then calcined at a temperature of between
about 400 and about 550.degree. C. for 2 to 4 hours.
Molecular sieve
Only a single type of molecular sieve crystal is necessary as the
catalyst support in the present invention. Any type of molecular
sieve having an average pore size between about 0.4 nm (4 .ANG.)
and about 1 nm (10 .ANG.) may be used, with the preferred type being
USY having a pore size being between 0.7 nm (7 .ANG.) and 0.8 nm
(8 .ANG.). The size of the crystals, regardless of the type chosen,
should be between 0.5 and 50 microns, however, and a crystal size
between about 1 and about 2 microns is preferred. If noble metal
is to be deposited by covalent chemisorption, the silica/alumina
ratio should be between about 10 and about 100000 preferably between
about 10 and about 100. If noble metal is to be deposited by ionic
chemisorption, the silica/alumina ratio should be between about
20 and about 100000 preferably between about 20 and about 100.
If the method to be used for noble metal deposition is covalent
chemisorption, the molecular sieve should be modified to establish
a thin alumina film on its exterior surfaces, either by steaming
to mildly de-aluminate sieve crystals having a low Si/Al ratio or
by treatment with an aqueous solution of very small pseudo-boehmite
crystallites for sieves with a high Si/Al ratio. Optionally, the
sieve crystals may be treated to expose acid sites on the crystal
surface.
Some applications, however, such as those in which it is desirable
to adsorb hydrocarbon during cold start of an engine, might benefit
from incorporation into the coating a second, or even a third, type
of sieve having characteristics desirable to that application. For
instance, in a catalytic converter is intended for treatment of
diesel exhaust, it might be desirable to employ two types of sieve,
one with an average pore size less than 6 .ANG. on which platinum
or a platinum alloy has been dispersed and another (with an average
pore size greater than 0.6 .mu.m) which is capable of adsorbing
the large hydrocarbon molecules present in the exhaust gas from
such diesel engines. This larger-pore sieve would not necessarily
require platinum or a platinum alloy dispersed thereon since conversion
of hydrocarbon, carbon monoxide, and nitrogen oxides would be catalyzed
primarily by the smaller-pore sieve.
Binder
As is the case with many catalysts, it is sometimes desirable to
incorporate with the zeolite another material resistant to the temperatures
and other conditions encountered in the environment to which the
catalyst is to be exposed. Often, these materials are inactive,
thereby serving as diluents so that the desired conversion can be
obtained economically without employing other means for controlling
the rate of reaction. At other times, a binder may serve to improve
the adhesion of the zeolite-containing coating to the substrate.
Binders useful for compositing with the zeolites of this invention
include inorganic oxides such as alumina, silica, alumina-silicates,
titania, magnesia, zirconia, beryllia, and mixtures thereof, with
alumina, titania, and zirconia being preferred, and with milled
alumina being particularly preferred.
The relative proportions of finely divided zeolite crystals and
inorganic oxide binder may vary widely with the zeolite content
ranging from about 1 to about 90 weight percent, and more usually
in the range of about 10 to about 50 weight percent of the composite.
Noble Metal
Platinum used alone is the preferred noble metal for use in this
invention. In addition, however, platinum alloyed with rhodium,
iridium, palladium, silver, or gold may be employed as the noble
metal.
Preparation of Catalyst
The key element of the present invention is that the platinum or
the platinum alloy be dispersed predominantly on the exterior surface
of the zeolite crystals chosen for the particular application, and
preferably so that a very high proportion, above 90%, of the platinum
or the platinum alloy is sited within 50 nm (500 .ANG.) of the exterior
crystal surfaces. It has been discovered that there are a number
of methods of dispersing platinum or a platinum alloy on zeolite
in a suitable manner. These methods involve contacting a suspension
of a platinum or a platinum alloy salt with the zeolite crystals
on which the platinum or a platinum alloy is to be dispersed in
the absence of any other type of zeolite crystals or any inorganic
oxide binder which is or are to be included in the catalyst.
One such method employs, as the depositing agent for platinum or
a platinum alloy, compounds that will chemisorb predominantly on
and near the exterior surface of the zeolite crystals by forming
either a covalent or an ionic bond between the noble metal and the
zeolite. This method is particularly preferred. Compounds that form
a covalent bond include Pt sulfite, [N(C.sub.2 H.sub.5).sub.4 ].sub.2
[Pt(OH).sub.6 ], and Pt ethanolamine, with Pt sulfite being preferred;
compounds that form an ionic bond include [Pt(NH.sub.2 CH.sub.2
CH.sub.2 NH.sub.2).sub.2 ][OH].sub.2 and [Pt(NH.sub.2 CH.sub.2 CH.sub.2
NH.sub.2).sub.2 ][CO.sub.3 ]. The Pt sulfite employed in this invention
should be a non-cationic square-planner Pt complex in which each
Pt has two Pt-S bonds and whose charge is believed to be between
-4 and zero, depending on pH.
Another method involves pretreatment of the zeolite crystals on
which platinum or a platinum alloy is to be dispersed with a sufficient
amount of hydrophilic polymer prior to exposure of the crystals
to a platinum or a platinum alloy salt suspended in water. The hydrophilic
polymer should be applied so as to fill up or block a sufficient
number of the zeolite pores to intrusion of platinum species or
a platinum alloy colloid into the crystal interior. The hydrophilic
polymer will be subsequently removed completely from the catalyst
during calcining of the finished catalyst. Some hydrophilic polymers
suitable for this purpose include polyethylene glycol, polyvinyl
glycol and polyvinyl pyrollidone, with polyethylene glycol being
particularly preferred.
A third method employs, as the depositing agent for platinum or
a platinum alloy, metallic colloidal particles of platinum or a
platinum alloy of a size substantially greater, by at least a factor
of two, than the largest crystallographically defined pore diameter
of the molecular sieve crystals onto which the noble metal is to
be deposited.
A fourth method, involving placing a noble metal precursor into
the reactor during the production or synthesis of a zeolite, is
taught in U.S. Pat. No. 5290534 (Tsao).
Preparation Using Pt Reagents that Chemisorb onto Zeolite Crystal
Exterior Surface
In this preferred method of preparation, an amount of platinum
or a platinum alloy reagent capable of being chemisorbed onto the
exterior of molecular sieve crystals is mixed with an aqueous suspension
of the type and size of molecular sieve crystals to be employed
in the catalyst.
If the reagent chosen forms a covalent bond with the zeolite, it
is important that the molecular sieve crystals used in this process
be modified to have a very thin film of aluminum oxide on their
exterior surfaces. The choice of method for forming this thin alumina
film depends on the Si/Al ratio of the zeolitic precursor. For molecular
sieves that have Si/Al ratios less than about 12 such as Zeolite
Y, the requisite alumina film can be established by de-aluminating
the zeolitic precursor to some degree by exposure to steam. For
molecular sieves with Si/Al ratios greater than about 12 such as
MFI-38 that do not have sufficient constituent aluminum to permit
formation by de-alumination of a useful alumina film while retaining
high acid site concentration, the requisite alumina film can be
established by treating the zeolitic precursor with an aqueous solution
of very small crystallite boehmite. The boehmite crystallites used
to promote formation of this thin alumina film should be less than
about 4 nm in size, with crystallites of between 2.5 nm and 3.5
nm being preferred. The solution employed should be such that significant
aggregation of the crystals has not occurred. Sols that are essentially
colorless and transparent but nevertheless contain alumina equivalent
to over 5 wt. % alumina have not had significant agglomeration of
the boehmite crystallites. The use of this procedure results in
the exterior surfaces of the zeolite being derivatized, with a thin
(approx. 3 to 5 nm) alumina film deposited thereon.
If the reagent chosen forms an ionic bond with the zeolite, it
is important that the zeolite chosen have a Si/Al ratio above about
20 and that the pH of the aqueous suspension of zeolite be above
10 prior to the addition of the noble metal compound, to deprotonate
the siliceous exterior surface of the zeolite.
The amount of noble metal reagent added should be determined by
the noble metal loading desired in the catalyst to be prepared.
The range of noble metal loadings should be between 0.05% and 10%
of sieve weight, with the preferred range being between about 1
and about 3 weight % of sieve weight.
If the reagent chosen forms a covalent bond with the zeolite, sufficient
base is then added to the suspension to adjust its pH to between
about 7 and 8. The base employed should be one that will decompose
to yield gaseous products when its temperature is raised above about
150.degree. C., and the preferred base is tetramethylammonium hydroxide.
If the reagent chosen forms an ionic bond with the zeolite, no further
pH adjustment is required because the aqueous suspension of zeolite
should already be at a pH above 10. The suspension is then stirred
long enough to allow the noble metal reagent to be chemisorbed onto
the molecular sieve crystals, a period of at least one hour.
If another type of molecular sieve crystals is to be included in
the catalyst being prepared, an aqueous suspension of this second
type of molecular sieve is then added to the suspension already
prepared. Along with this second type of molecular sieve, or instead
of it if only one type of molecular sieve is to be included in the
catalyst, an aqueous suspension of a suitable binder, preferably
one such as alumina, titania, or zirconia, may optionally be added
to the mixture already prepared. The entire mixture is then stirred
for a period of time sufficient to thoroughly mix the compounds
that have been included in the suspension.
The suspension as prepared is then applied to a substrate, preferably
a monolith, by any of the methods known to those skilled in the
art, and preferably by piston coating, to achieve the desired thickness
of coating disposed on the substrate. It is then dried and calcined
by any of a number of methods known to those skilled in the art.
Preparation Using Hydrophilic Polymer
In this method of catalyst preparation, a hydrophilic polymer is
employed to fill the pores of the molecular sieve crystals prior
to application of platinum or a platinum alloy to the crystals,
thereby preventing the platinum or a platinum alloy from being deposited
other than on the surface of the crystals.
Suitable hydrophilic polymers will be any such polymer having a
density of between about 0.8 and 1.0 gm./cm..sup.3 and that completely
volatilizes at calcining temperatures. Preferred polymers for this
application include, without limitation, polyethylene glycol, polyvinyl
glycol and polyvinyl pyrollidone. Polyethylene glycol is particularly
preferred.
In this method of catalyst preparation then, an amount of hydrophilic
polymer sufficient to fill the pores of the molecular sieve crystals,
without overfilling thereby leaving polymer on the surface of the
crystals, is added to an aqueous suspension of the molecular sieve
to be used, and the suspension is stirred for a period of at least
30 minutes to promote adsorption of the polymer in the pores of
the crystals. A suitable method for determining the amount of polymer
to apply is:
1) the pore volume per unit mass of the molecular sieve to be employed
is measured;
2) a concentrated solution of a hydrophilic polymer is prepared
and the density of the solution is determined;
3) the quantity of the hydrophilic polymer solution to be added
to the molecular sieve is set so that the product of the mass of
the sieve to be treated times the sieve's pore volume per unit mass
of sieve times the density of the hydrophilic polymer solution divided
by the mass of polymer solution is between 1 and 0.25.
Following adsorption of the polymer into the crystal pores, a quantity
of de-ionized water may be added to the solution to yield an appropriate
coating precursor.
Any platinum or a platinum alloy reagent known to those skilled
in the art is then added to the suspension in an amount determined
to provide the desired platinum or platinum alloy loading on the
final catalyst, in a similar manner to the method described above.
The remainder of this procedure is the same as for the procedure
above using those platinum or platinum-alloy reagents that chemisorb
preferentially on the surface of the molecular sieve crystals.
Preparation Using Colloidal Particles of Noble Metal
This method of preparation is superficially similar to the method
described above using Pt reagents that chemisorb onto the exterior
surface of molecular sieve crystals, although the nature of the
chemical interactions resulting in deposition of the colloidal metal
onto the zeolite is believed to be different.
An aqueous suspension of colloidal particles of platinum or a platinum
alloy is added to an aqueous suspension of molecular sieve crystals.
It is necessary that the size of the colloidal particles be at least
twice the largest crystallographically-defined pore diameter of
the molecular sieve crystals so that the colloidal particles cannot
enter the crystal pores, and are therefore adsorbed on the surface
of the crystals. The pH may optionally be adjusted to promote chemisorption
of the colloidal metal onto the molecular sieve. The remainder of
this procedure is the same as for the procedure above using those
platinum or platinum-alloy reagents that chemisorb preferentially
on the surface of the molecular sieve crystals.
EXAMPLE 1
This example describes the preparation of a catalyst of the present
invention in which Pt is covalently chemisorbed on the sieve exterior
surface.
An aqueous suspension of ultra-stable Y molecular sieve that had
been partially de-aluminated by exposure to steam was prepared and
sufficient Pt sulfite was added to yield molecular sieve crystals
having about 2 wt. % Pt on sieve. Sufficient tetramethylammonium
hydroxide was added to raise the pH to about 7 and the suspension
was then stirred for several hours to permit chemisorption reactions
between the Pt sulfite and the molecular sieve crystals to occur.
Then a milled suspension of Condea SCFA-90 consisting predominately
of .theta.-alumina, was added without the normal addition of acid
that partially peptizes the alumina. The mixture was then stirred
for several hours, dried and calcined.
A sample of this material was analyzed by cutting thin sections
of particles contained in the sample. FIG. 1 is a micrograph of
these particles. It is clear from this figure that Pt is not found
throughout the bulk of the molecular sieve crystals; rather, Pt
does occur at the exterior surface of the molecular sieve crystals,
appearing as dark particles.
EXAMPLE 2
(Comparative)
This example describes the preparation of a catalyst that has been
suggested in the prior art for use in treating exhaust gas from
an internal combustion engine.
A catalyst sample was prepared using the same method as employed
in Example 1 except that [Pt(NH.sub.3).sub.4 ][OH].sub.2 was used
as the platinum reagent instead of Pt sulfite. Again, a sample of
this material was analyzed by cutting thin sections of particles
contained in the sample. FIG. 2 is a micrograph of these particles.
In this figure is shown dark particles through the bulk of the sieve
crystals. An arrow points to a film on the surface of the crystal.
It should be noted that no platinum is present on this film; rather,
the platinum is present in regions away from the edges. The possibility
that those platinum particles are at the exterior surface can be
dismissed since, in the regions where platinum is seen, the exterior
surface has been cut away.
EXAMPLE 3
(Comparative)
This example compares the performance (as measured by NO.sub.x
conversion) of the catalyst prepared by the process described in
Example 1 against that of the system prepared in Example 2.
Catalytic converters were manufactured using the suspensions prepared
in Examples 1 and 2 applied to equivalent size and type monoliths
followed by drying and calcining. One converter at a time was connected
to the exhaust pipe of a Peugeot IDI, turbocharged U60 engine. Catalyst
inlet temperature was varied at constant speed (1540 rpm) by variation
of the load placed on the engine, i.e., as load increased, inlet
temperature increased. Diesel fuel was injected into the exhaust
gas between the engine outlet and the converter inlet to adjust
the hydrocarbon/NO.sub.x ratio to 10 at each load set point. NO.sub.x
concentrations were determined using a chemiluminescent NO.sub.x
analyzer.
The results of this test are shown in FIG. 3. NO.sub.x conversion
versus converter inlet temperature is plotted for each of the converters,
with the performance of the converter using the catalyst prepared
as in Example 1 shown as solid circles, .circle-solid., and that
of the converter using the system prepared as in Example 2 as solid
squares, .box-solid.. It is clear that the converter of the present
invention demonstrates far superior NO.sub.x conversion compared
to the converter using a typical catalyst formulation. NO.sub.x
conversion begins at a lower temperature, reaches a higher maximum,
and continues at a higher level over the entire temperature range
of interest.
EXAMPLE 4
This example describes preparation of catalysts of the present
invention in which Pt is covalently chemisorbed on the sieve exterior
surface. It illustrates a variant of the method described in Example
1 that is useful where the zeolite employed has a high Si/Al ratio.
Three suspensions, each containing 20 grams of a molecular sieve
with the MFI structure and a Si/Al ratio of 19 in 100 grams of de-ionized
water, were prepared. Two grams of Condea Tondersol 10/2 a very
fine, 10 wt. % dispersion of pseudo-boehmite in water, was added
to the first suspension, 10.5 grams to the second and 22.2 grams
to the third. Catalytic coating precursors containing 1%, 5% and
10% added Al.sub.2 O.sub.3 respectively, were produced. After stirring
for 5 minutes, each mixture was quantitatively transferred to a
steam evaporator and the water evaporated away over a period of
three hours. The resulting solids were then separately calcined
at 500.degree. C. for 4 hours. Then, 10 gram samples of each of
these solids were suspended in 50 grams of de-ionized water. To
each suspension about 2 grams of a 9.94% Pt sulfite aqueous solution
was added, making three suspensions differing only in alumina content.
After stirring for one hour, each was filtered and the resultant
solid calcined at 500.degree. C. for 4 hours.
A fourth sample of catalyst was prepared according to the procedure
described above, but without the addition of Condea Tondersol 10/2.
The chemical compositions of the resulting catalysts are shown
in Table 1
TABLE 1 ______________________________________ MFI-1% MFI-5% MFI-10%
Designation: MFI Al.sub.2 O.sub.3 Al.sub.2 O.sub.3 Al.sub.2 O.sub.3
______________________________________ Added Al.sub.2 O.sub.3 :
None 1% 5% 10% Al, %: 2.458 2.982 4.352 7.493 Si, %: 42.233 42.646
41.931 38.737 Pt, %: 0.142 0.193 0.557 1.360 ______________________________________
It should be noted that the platinum content of the samples increases
in rough proportion to the added alumina. Since the alumina is size-excluded
from the zeolite and therefore resides on exterior surfaces of the
MFI crystals, the Pt is supported on alumina that is supported on
the zeolite, in rough analogy to the Pt-Y material prepared in Example
1.
EXAMPLE 5
The effectiveness for NO.sub.x reduction of the four catalysts
prepared in Example 4 is compared in this example.
In turn, a 1 gram sample of each of the materials was loaded into
a quartz reactor which was placed in a furnace and subjected to
the following program. A gas consisting of 1000 ppm NO.sub.x, 300
ppm CO, 8% H.sub.2 O, 8% CO.sub.2 500 ppm octane, 20 ppm SO.sub.2
12% O.sub.2 and the balance N.sub.2 was passed over the sample
at a flow rate of 5 liters per minute. The inlet temperature to
the reactor was increased from about 50.degree. C. to 550.degree.
C. at a rate of 7.degree. C. per minute, then held constant for
one hour, and finally cooled rapidly until the reactor temperature
returned to 50.degree. C. The heating, holding and cooling regimen
was then repeated.
FIG. 4 shows NO.sub.x conversion as a function of catalyst inlet
temperature during the first temperature ramp for each of the samples.
The data obtained during the second ramp were essentially identical.
The catalyst designated MFI, having no added alumina, shows modest
performance. Maximum NO.sub.x conversion is about 36%. NO.sub.x
conversion for the catalyst designated MFI-1%Al.sub.2 O.sub.3 increases
to 50%, and the range of temperature over which significant conversion
occurs, the "conversion window", is considerably broader
than for the MFI catalyst. The modest increase in Pt content (0.19%
vs. 0.15%) is quite effective at improving NO.sub.x conversion.
This is as expected for platinum situated on the exterior surfaces
of the molecular sieve. The additional alumina, and consequent increases
in Pt chemisorption, associated with the other two samples produces
modest incremental improvement.
EXAMPLE 6
This and the following example describe preparation of catalysts
of the present invention using colloidal Pt particles to deposit
Pt on the sieve exterior surface.
20 grams of NH.sub.4 -Beta zeolite were suspended in 200 grams
of de-ionized water. To this suspension, 22.3 grams of a stable
aqueous Pt colloid solution prepared by PGP Industries, Inc. that
contains 1.83 wt. % of Pt colloid particles roughly 2 .mu.m. in
size were added. The suspension was then stirred for 2 hours and
filtered. The filter cake was dried at 100.degree. C. for about
60 hours. Analysis of a sample of the filter cake showed that the
Pt content of fine powder was 1.29%. Transmission Electron Microscopic
(TEM) examination of thin sections of the catalyst revealed homogeneously
distributed, apparently non-faceted Pt particles about 2 nm in size.
Since the largest micro-pore opening in Beta is about 0.7 nm, it
can be concluded that the Pt is on the exterior surface of the Beta.
Relatively high concentration of Pt occurs apparently due to the
disordered, mesoporous texture of Beta that results in a relatively
high exterior surface area.
EXAMPLE 7
A sample of catalyst was prepared using the same procedure as Example
6 except that the zeolite used was H-MFI. TEM examination revealed
the same structure as the catalyst in Example 6 but the resulting
catalyst had a Pt content of only 0.06%. The lower Pt content is
due to the nature of the MFI crystals which are about 1 micron in
size with very little surface area available for metal deposition.
Since very little surface area is available for physical adsorption,
and apparently there is not a strong driving force for chemisorption
with this procedure, only a small amount of Pt is deposited. Since
the largest micro-pore opening in MFI is about 0.55 nm, it can be
concluded that the Pt is on the exterior surface of the MFI.
EXAMPLE 8
This example describes preparation of catalysts of the present
invention
using bulky Pt complexes to deposit Pt on the sieve exterior surface
by ionic chemisorption.
A solution of bis(ethylenediamine)Pt(II) hydroxide containing 5.92
wt. % Pt was supplied by PGP. Three solutions were prepared, each
containing 6.895 grams of the PGP solution diluted with 185 grams
of de-ionized water. To each of the solutions 20 grams of a molecular
sieve with the MFI structure and a Si/Al ratio of 19 were added.
The pH of the resulting solutions was about 6. Tetraethylammonium
hydroxide was added to the solutions to raise the pH of one sample
to 8.5 another to 9.0 and the third to 11.0. The solutions were
stirred overnight, then filtered and calcined in air for 4 hours
at 400.degree. C.
Samples of fine powder from each catalyst were embedded in epoxy,
thin-sectioned and examined by TEM, which revealed Pt particles
from 10 to 50 nm. The particles decreased in size with increasing
pH of the synthesizing solution, which is consistent with generation
of the largest number of adsorption sites on the siliceous surface
of MFI at highest pH. As in Example 7 due to the large size of
the Pt complex relative to the zeolite pore size, it can be concluded
that the Pt is on the exterior surface of the MFI.
EXAMPLE 9
(Comparative)
An aqueous suspension of Condea SCFA-90 alumina was mixed with
Pt sulfite for a period of time sufficient to result in chemisorption
of the platinum. The suspension was then mixed with ultra-stable
Y molecular sieve that had been partially dealuminated by exposure
to steam. However, since the Pt had already chemisorbed onto the
alumina, essentially no Pt was deposited onto the zeolite. The mixture
was wash-coated onto a monolithic substrate and then manufactured
into a catalytic converter. This procedure is the preferred procedure
taught by Lachman '991. The volumetric concentrations of Pt, alumina,
and molecular sieve were about the same as in the catalyst of Example
1.
The performance of this catalytic converter was then compared to
that of the converter of Example 3 made from the suspension of Example
1. One converter at a time was connected to the exhaust pipe of
a Peugeot IDI, turbocharged U60 engine. Catalyst inlet temperature
was varied at constant speed (1540 rpm) by variation of the load
placed on the engine, i.e., as load increased, inlet temperature
increased. Diesel fuel was injected into the exhaust gas between
the engine outlet and the converter inlet to adjust the hydrocarbon/NO.sub.x
ratio to 10 at each load set point. NO.sub.x concentrations were
determined using a chemiluminescent NO.sub.x analyzer.
The results of this test are shown in FIG. 5. NO.sub.x conversion
versus converter inlet temperature is plotted for each of the converters,
with the performance of the converter using the catalyst prepared
as in Example 3 (using the suspension of Example 1) shown as solid
circles, .circle-solid., and that of the converter using the system
prepared as in this Example 9 as solid squares, .box-solid.. It
is clear that the converter of the present invention demonstrates
far superior NO.sub.x conversion compared to the converter using
a catalyst formulation similar to that taught by Lachman. |