Technical Field
[0001] The present invention relates to a three-way catalyst for purifying exhaust gases
from internal combustion engines such as automobile engines, and more particularly
to an exhaust gas purifying catalyst capable of suppressing hydrogen sulfide (H
2S) emissions.
Background Art
[0002] Nowadays, a three-way catalyst is widely used as a catalyst for purifying NO
x (nitrogen oxides), CO carbon monoxide and HC (hydrocarbons) in exhaust gases from
automobiles or the like. The three-way catalyst comprises a porous oxide supports
such as alumina, ceria, zirconia and a ceria-zirconia solid solution, and a noble
metal such as platinum (Pt), rhodium (Rh) and palladium (Pd) loaded on the supports,
and simultaneously purifies HC and CO by oxidation and NO
x by reduction. Since these reactions proceed most efficiently in an atmosphere including
approximately equivalent amounts of oxidizing components and reducing components,
in an automobile to which a three-way catalyst is installed, the air/fuel ratio is
controlled so that an air-fuel mixture is burned at or near the theoretical air/fuel
ratio, i.e., the stoichiometric point (A/F = about 14.6 ±0.2).
[0003] The three-way catalyst, however, has a problem that when the exhaust gas atmosphere
becomes reductive, sulfur oxides in the exhaust gases are reduced into and emitted
as H
2S. Japanese Examined Patent Publication (KOUKOKU) No.
H08-015,554 discloses the use of nickel or copper oxides as components of a three-way catalyst.
The nickel or copper oxides oxidize SO
2 into SO
3 or SO
4 in an oxidizing atmosphere and store sulfur components as sulfides such as Ni
2S
3 in a reducing atmosphere, whereby H
2S emissions can be suppressed.
[0004] However, since nickel or copper is an environmentally hazardous substance, the use
of nitrogen or copper in a catalyst for purifying exhaust gases from automobiles is
getting inhibited. Therefore, consideration is given to the use of bismuth oxides,
which exhibit a similar effect of suppressing H
2S emissions to those of nickel or copper oxides. A Bi-containing catalyst, however,
has a problem that bismuth components scatter at elevated temperatures and the effect
of suppressing H
2S emissions is not retained for a long time.
[0005] By the way, Japanese Examined Patent Publications (KOUKOKU) Nos.
H02-020,561,
H05-081,521, and
S61-020,342 disclose Bi-containing catalysts. These catalysts, however, aim to oxidize H
2S in oxidizing atmospheres. Therefore, when the air/fuel ratio is controlled as in
the cases of automobiles, there is a fear that H
2S is emitted in stoichiometric or reducing atmospheres. These patent documents do
not refer to the catalytic effects in the stoichiometric or reducing atmospheres and
do not disclose or suggest the use of these catalysts as three-way catalysts, which
are also used in the stoichiometric or reducing atmospheres.
[0006] US 6,022,826 describes a catalyst for oxidizing carbon monoxide in a gas stream, which contains
a combination of a platinum component and one or more bismuth oxides in amounts sufficient
to convert carbon monoxide to carbon dioxide in the presence of oxygen.
[0007] US 6,350,421 describes a nitrogen oxide storage material, which contains at least one storage
component for nitrogen oxides in the form of an oxide, mixed oxide, carbonate or hydroxide
of the alkaline earth metals magnesium, calcium, strontium and barium, and the alkali
metals potassium and caesium, on a high surface area support material.
[0008] GB 1384248 describes a process of treating internal combustion engine exhaust gases to remove
nitrogen oxides, which involves passing the gases in a first stage over a catalyst
having primarily an oxidation activity until a substantial proportion of oxygen has
been reacted and then in a second stage over a catalyst having primarily a reduction
activity until nitrogen oxides are substantially decomposed.
[0009] US 6,616,904 describes materials for removing the nitrogen oxides NO and NO
2 present in exhaust gases. The materials are mixed oxides in which the metals A and
B are octahedrally coordinated and are arranged to form the ilmenite structure ABO
3.
[0010] US 5,120,695 describes a one-piece catalyst for purifying exhaust gases in honeycomb form having
a leading-edge portion containing a catalyst for selective reduction of nitrogen oxides
by ammonia gas and a trailing-edge portion containing an oxidation catalyst.
[0011] EP 0714692 A1 describes a catalyst for the purification of diesel engine exhaust gas, which comprises
a three-dimensional structure coated with (A) a platinum and/or palladium-carrying
refractory inorganic oxide powder obtained by depositing platinum and/or palladium
and the catalytically active oxide of at least one metal selected from the group consisting
of tungsten, antimony, molybdenum, nickel, vanadium, manganese, iron, bismuth, cobalt,
zinc, and alkaline earth metals on (a) a first refractory inorganic oxide powder and
(B) a catalyst composition formed of (b) a second refractory inorganic oxide powder
and having said platinum and/or palladium contained therein in an amount in the range
of from 5 to 50% by weight, based on the amount of (a) said first refractory inorganic
oxide powder.
Disclosure of the invention
[0012] The present invention has been made in view of the abovementioned problems. It is
an object of the present invention to provide an exhaust gas purifying catalyst which
can reduce scattering of bismuth and can retain the effect of suppressing H
2S emissions for a long time.
[0013] The present inventor has conceived that scattering of Bi components can be suppressed
by employing a Bi-Ti composite oxide at a predetermined ratio in a conventional three-way
catalyst.
[0014] A three-way exhaust gas purifying catalyst according to the present invention comprises
a support substrate, and a catalyst layer formed on the support substrate and including
a noble metal, a porous oxide, and a bismuth and titanium composite oxide, and the
ratio R of the molar amount of bismuth loaded per unit volume of the support substrate
to the molar amount of titanium loaded per unit volume of the support substrate satisfies
0.3 ≤ R ≤ 1.5. More preferably, the ratio R of the molar amount of bismuth loaded
per unit volume of said support substrate to the molar amount of titanium loaded per
unit volume of said support substrate satisfies 0.5 ≤ R ≤ 1.3.
[0015] It is preferable that the molar amount of bismuth loaded per unit volume of the support
substrate is not less than 0.2 mol/liter and not more than 0.5 mol/liter. More preferably,
the molar amount of bismuth loaded per unit volume of said support substrate is not
less than0.2 mol/liter and not more than 0.4 mol/liter.
[0016] According to the three-way exhaust gas purifying catalyst of the present invention,
scattering of bismuth contained in the Bi-Ti composite oxide can be suppressed by
satisfying 0.3 ≤ R ≤ 1.5, where R is the ratio of the molar amount of Bi loaded per
unit volume of the support substrate to the molar amount of Ti loaded per unit volume
of the support substrate. As a result, the effect of suppressing H
2S emissions of the exhaust gas purifying catalyst can be retained for a long time.
[0017] Besides, H
2S emission suppression and bismuth scattering suppression can be realized simultaneously
by making the molar amount of Bi per unit volume of the support substrate not less
than 0.2 mol/liter and not more than 0.5 mol/liter. As a result, the effect of suppressing
H
2S emissions can be retained at a high level for a long time.
Brief Description of the Drawings
[0018] Figure 1 is a graph showing the Bi residual ratio as a function of the Bi content
per unit volume of a support substrate.
[0019] Figure 2 is a graph showing the Bi residual ratio as a function of the Bi/Ti ratio,
that is, the ratio R of the molar amount of Bi loaded per unit volume of a support
substrate to the molar amount of Ti loaded per unit volume of the support substrate.
[0020] Figure 3 is a graph showing H
2S emissions as a function of the Bi content per unit volume of a substrate.
[0021] Figure 4 is a graph showing CO-NO
x cross conversion efficiency as a function of the Bi content per unit volume of a
substrate.
Best Modes for Carrying Out the Invention
[0022] The exhaust gas purifying catalyst of the present invention comprises a support substrate
and a catalyst layer, and the catalyst layer is formed on the support substrate and
includes a noble metal, a porous oxide and a Bi-Ti composite oxide. In other words,
the catalyst layer includes a Bi-Ti composite oxide in addition to a conventional
three-way catalyst, as mentioned before.
[0023] Examples of the porous oxide include alumina, silica, titania, ceria, zirconia, and
a composite oxide containing a plurality of these such as a ceria-zirconia solid solution,
and one or more of these oxides can be employed. It is preferable to include at least
activated alumina, which has a large specific surface area. If an oxide having oxygen
storage and release capacity, such as a ceria-zirconia solid solution, is employed,
variations in the exhaust gas atmosphere can be restrained and three-way activity
is further improved.
[0024] It is known that, when a Bi-containing composite oxide is added to a conventional
three-way catalyst, the Bi-containing composite oxide can suppress H
2S emissions by oxidizing SO
2 into SO
3 or SO
4 in an oxidizing atmosphere and storing sulfur components as sulfides in a reducing
atmosphere. As mentioned before, however, bismuth components scatter at elevated temperatures.
The present inventor has found that scattering of bismuth can be suppressed by employing
a composite oxide of bismuth and another element which forms a compound with bismuth,
and that a significant advantage is obtained especially when titanium is used as another
element which forms a compound with bismuth.
[0025] The Bi-Ti composite oxide is an oxide mainly containing both a Bi ion and a Ti ion,
but may include other metals such as tin (Sn) and zinc (Zn). When the ratio R of the
molar amount of Bi loaded per unit volume of the support substrate to the molar amount
of Ti loaded per unit volume of the support substrate (hereinafter simply referred
to as "R") satisfies 0.3 ≦ R ≦ 1.5, scattering of bismuth, which tends to occur during
the use at elevated temperatures, can be suppressed effectively. Therefore, the effect
of suppressing H
2S emissions can be retained for a long time. In contrast, when R is outside the above
range, the effect of suppressing bismuth from scattering deteriorates drastically
and, as a result, the effect of suppressing H
2S emissions deteriorates by a long-term use. When R satisfies 0.5 ≦ R ≦1.3, scattering
of bismuth can be suppressed more effectively.
[0026] Moreover, as for the Bi content, it is preferable that the molar amount of Bi loaded
per unit volume of the support substrate is not less than 0.2 mol/liter and not more
than 0.5 mol/liter. When the molar amount of Bi is in this range, H
2S emissions can be effectively suppressed. Therefore, H
2S emission suppression and bismuth scattering suppression can be realized simultaneously,
and the effect of suppressing H
2S emissions can be retained at a high level for a long time.
[0027] It is more preferable that the molar amount of Bi loaded per unit volume of the support
substrate is not less than 0.2 mol/liter and not more than 0.4 mol/liter. When the
molar amount of Bi loaded is in this range, H
2S emissions can be suppressed while retaining the three-way activity of a conventional
three-way catalyst.
[0028] The Bi-Ti composite oxide can be physically mixed with the porous oxide, but can
also be added by a sol-gel coprecipitation process or the like. For example, a Bi-Ti
composite oxide can be obtained by separating precipitate from an aqueous solution
of such a water-soluble chemical compound as a nitrate including at least bismuth
and titanium, loading the precipitate on alumina powder or the like and then calcining
the resultant.
[0029] The noble metal used here catalyzes the oxidation of HC and CO or the reduction of
NO
x, and suitable examples of the noble metal include platinum (Pt), rhodium (Rh) and
palladium (Pd). It is also preferable to use platinum, which shows strong oxidizing
activity, and rhodium, which shows strong reducing activity, in combination. Although
some of the noble metal can be loaded on the Bi-Ti composite oxide, most of the noble
metal is desirably loaded on the porous oxide.
[0030] The noble metal loading can be at the same level as in conventional three-way catalysts
and can be appropriately determined in accordance with desired performance. The preferred
noble metal loading depends on the kinds of noble metals, but is 0.1 to 10 g per liter
of the catalyst layer.
[0031] The exhaust gas purifying catalyst of the present invention comprises a support substrate
on which a catalyst layer is formed. The support substrate employed can be a conventional
substrate such as ceramic and metal honeycomb structure. Formation of the catalyst
layer on the support substrate can be carried out, for example, by wash coating a
slurry including a porous oxide and a Bi-Ti composite oxide on a honeycomb structure,
calcining the coated structure so as to form a coating layer, and loading a noble
metal on the coating layer by adsorption (wet impregnation) or water absorption (incipient
wetness impregnation).
[0032] It is also possible to prepare catalyst powder formed by loading a noble metal on
a porous oxide beforehand, mix a Bi-Ti composite oxide with this catalyst powder and
form a coating layer with the mixture.
[0033] It is to be noted that the exhaust gas purifying catalyst of the present invention
is not limited to the above modes of carrying out the present invention. For example,
if required, another substance can be added in order to add another function to the
catalyst layer, as long as no damage is given to the advantages of the exhaust gas
purifying catalyst of the present invention.
[Preferred Embodiments]
[0034] Hereinafter, examples of the exhaust gas purifying catalyst of the present invention
will be described concretely with comparative examples.
<Formation of Exhaust Gas Purifying Catalysts>
[0035] Exhaust gas purifying catalyst samples 1 to 15 were formed by the following procedures.
[Sample 1]
[Preparation of a Slurry]
[0036] A slurry S was prepared by mixing 75 parts by weight of a Ce-Zr solid solution (the
molar ratio of CeO
2 : ZrO
2 : Y
2O
3 = 65 : 30 : 5), 120 parts by weight of activated alumina, an alumina binder (3 parts
by weight of alumina hydrate, 44 parts by weight of a 40% aluminium nitrate aqueous
solution) and a predetermined amount of pure water and milling the mixture.
[Formation of a Catalyst Coating Layer]
[0037] A honeycomb substrate having a cell density of 400 cpsi (cells per square inch),
a wall thickness of 100 µm, a diameter of 103 mm, a length of 130 mm, and a volume
of 1.1 liter was prepared and wash coated with the slurry S. The coated substrate
was dried at 120°C and then calcined at 650°C for three hours, thereby forming a catalyst
coating layer.
[0038] Next, the substrate having the catalyst coating layer was immersed in an aqueous
rhodium nitrate solution of a predetermined concentration so as to adsorb and load
rhodium. After removed from the solution, the piece was dried at 120 °C and then calcined
at 500°C for one hour, thereby loading rhodium. Moreover, the piece was immersed in
a platinum dinitrodiammine solution of a predetermined concentration so as to adsorb
and load platinum. After removed from the solution, the piece was dried at 120°C and
then calcined at 500°C for one hour, thereby loading platinum. The noble metal loading
was 0.2 g rhodium and 1.0 g platinum per liter of the substrate.
[Sample 2]
[0039] Sample 2 was prepared in a similar way to Sample 1, except that 23 parts by weight
of bismuth oxide was added to the slurry S.
[Sample 3]
[0040] Sample 3 was prepared in a similar way to Sample 1, except that 46 parts by weight
of bismuth oxide was added to the slurry S.
[Sample 4]
[0041] Sample 4 was prepared in a similar way to Sample 1, except that 69 parts by weight
of bismuth oxide was added to the slurry S.
[Sample 5]
[0042] Bi-Ti composite oxide powder was prepared by impregnation of anatase titania powder
with an aqueous bismuth nitrate solution so as to contain bismuth nitrate at the molar
ratio R of Bi to Ti = 1, drying and then calcining the resultant at 600 °C for two
hours. Sample 5 was prepared in a similar way to Sample 1, except that 27 parts by
weight of this Bi-Ti composite oxide powder (27 parts by weight of the total of bismuth
oxide and titanium oxide; the same applies to the following) was added to the slurry
S.
[Sample 6]
[0043] Sample 6 was prepared in a similar way to Sample 1, except that 54 parts by weight
of the Bi-Ti composite oxide powder was added to the slurry S.
[Sample 7]
[0044] Sample 7 was prepared in a similar way to Sample 1, except that 108 parts by weight
of the Bi-Ti composite oxide powder was added to the slurry S.
[Sample 8]
[0045] Sample 8 was prepared in a similar way to Sample 1, except that 216 parts by weight
of the Bi-Ti composite oxide powder was added to the slurry S.
[Sample 9]
[0046] Sample 9 was prepared in a similar way to Sample 1, except that 270 parts by weight
of the Bi-Ti composite oxide powder was added to the slurry S.
[Sample 10]
[0047] Bi-Ti composite oxide powder was prepared by impregnation of anatase titania powder
with an aqueous bismuth nitrate solution so as to contain bismuth nitrate at the molar
ratio R of Bi to Ti = 4, drying and then calcining the resultant at 600 °C for two
hours. Sample 10 was prepared in a similar way to Sample 1, except that 96 parts by
weight of this Bi-Ti composite oxide powder was added to the slurry S.
[Sample 11]
[0048] Bi-Ti composite oxide powder was prepared by impregnation of anatase titania powder
with an aqueous bismuth nitrate solution so as to contain bismuth nitrate at the molar
ratio R of Bi to Ti = 2, and drying and then calcining the resultant at 600 °C for
two hours. Sample 11 was prepared in a similar way to Sample 1, except that 100 parts
by weight of this Bi-Ti composite oxide powder was added to the slurry S.
[Sample 12]
[0049] Bi-Ti composite oxide powder was prepared by impregnation of anatase titania powder
with an aqueous bismuth nitrate solution so as to contain bismuth nitrate at the molar
ratio R of Bi to Ti = 1.33, drying and then calcining the resultant at 600 °C for
two hours. Sample 12 was prepared in a similar way to Sample 1, except that 104 parts
by weight of this Bi-Ti composite oxide powder was added to the slurry S.
[Sample 13]
[0050] Bi-Ti composite oxide powder was prepared by impregnation of anatase titania powder
with an aqueous bismuth nitrate solution so as to contain bismuth nitrate at the molar
ratio R of Bi to Ti = 1, drying and then calcining the resultant at 600 °C for two
hours. Sample 13 was prepared in a similar way to Sample 1, except that 108 parts
by weight of this Bi-Ti composite oxide powder was added to the slurry S.
[Sample 14]
[0051] Bi-Ti composite oxide powder was prepared by impregnation of anatase titania powder
with an aqueous bismuth nitrate solution so as to contain bismuth nitrate at the molar
ratio R of Bi to Ti = 0. 5, drying and then calcining the resultant at 600 °C for
two hours. Sample 14 was prepared in a similar way to Sample 1, except that 132 parts
by weight of this Bi-Ti composite oxide powder was added to the slurry S.
[Sample 15]
[0052] Bi-Ti composite oxide powder was prepared by impregnation of anatase titania powder
with an aqueous bismuth nitrate solution so as to contain bismuth nitrate at the molar
ratio R of Bi to Ti - 0.33, drying and then calcining the resultant at 600 °C for
two hours. Sample 15 was prepared in a similar way to Sample 1, except that 140 parts
by weight of this Bi-Ti composite oxide powder was added to the slurry S.
[0053] The Bi content, the Ti content and the Bi/Ti ratio R of each sample are shown in
Table 1.
[Table 1]
| |
Bi Content
(mol/liter) |
Ti Content
(mol/liter) |
Bi/Ti Ratio |
H2S Emission
(ppm) |
Bi Residual
Ratio (%) |
CO-NOx Cross
Conversion (%) |
| Sample 1 |
0 |
0 |
- |
300 |
- |
96.7 |
| Sample 2 |
0.05 |
0 |
- |
25 |
34 |
96.4 |
| Sample 3 |
0.1 |
0 |
- |
15 |
27 |
94.7 |
| Sample 4 |
0.3 |
0 |
- |
8 |
18 |
91.0 |
| Sample 5 |
0.05 |
0.05 |
1 |
54 |
95 |
96.5 |
| Sample 6 |
0.1 |
0.1 |
1 |
36 |
93 |
95.7 |
| Sample 7 |
0.2 |
0.2 |
1 |
24 |
94 |
95.0 |
| Sample 8 |
0.4 |
0.4 |
1 |
21 |
93 |
93.7 |
| Sample 9 |
0.5 |
0.5 |
1 |
19 |
85 |
93.0 |
| Sample 10 |
0.2 |
0.05 |
4 |
21 |
22 |
- |
| Sample 11 |
0.2 |
0.1 |
2 |
20 |
23 |
- |
| Sample 12 |
0.2 |
0.15 |
1.33 |
24 |
78 |
- |
| Sample 13 |
0.2 |
0.2 |
1 |
23 |
95 |
- |
| Sample 14 |
0.2 |
0.4 |
0.5 |
26 |
90 |
- |
| Sample 15 |
0.2 |
0.6 |
0.33 |
25 |
60 |
- |
<Examination and Evaluation>
[Bi Scattering Test]
[0054] Each of the above Samples 1 to 15 was disposed in an exhaust line of an engine bench
equipped with a 4.3-liter V-type 8-cylinder engine and aged at a catalyst bed temperature
of 850°C for 50 hours at an air/fuel ratio frequency of 1 Hz between A/F = 15 and
A/F = 14. After this aging, each of the samples was dismantled and subjected to elemental
analysis of the Bi content, and the Bi contents were compared between before and after
aging. The ratio of the Bi content after aging to that before aging is shown as "Bi
residual ratio" in Table 1, Figures 1 and 2, in which the numerals indicate sample
numbers.
[H2S Emission Test]
[0055] Each of the abovementioned Samples 1 to 15 was installed as an underfloor catalyst
in an automobile equipped with a 2.4-liter inline 4-cylinder engine and a test run
was carried out for one hour while keeping combustion and driving modes at a running
speed of 40 km/hr so as to have an underfloor catalyst bed temperature of 600 to 650
°C. Next, with the throttle fully open, the automobile was accelerated up to a speed
of 110km/hr in ten seconds, kept at this speed for ten seconds, and then decelerated
and stopped in twenty seconds and kept idling for ten seconds from the stop.
[0056] The H
2S concentration in the exhaust gas during idling was measured and its peak concentration
is shown in Table 1 and Figure 3, in which the numerals indicate sample numbers.
[Conversion Efficiency Tests]
[0057] Each of the above Samples 1 to 9 was aged in the same way as in the above Bi scattering
test. After this aging, each of the above Samples 1 to 9 was disposed as an underfloor
catalyst in an automobile equipped with a 2.4-liter inline 4-cylinder engine, and
while combustion conditions were varied to sweep the air/fuel ratio between A/F =
13.5 and A/F = 15.5, inlet and outlet catalyst exhaust gas conversion efficiencies
of CO and NO
x were measured. The inlet exhaust gas temperature of the sample catalysts was 400
°C. The conversion efficiency at the cross point of the CO conversion curve and the
nO
x conversion curve is called as "CO-NO
x cross conversion". The CO-NO
x cross conversion is shown in Table 1 and Figure 4, in which the numerals indicate
sample numbers.
[Evaluation]
[0058] It is apparent from the graph of Figure 1 that the composite oxide containing both
Ti and Bi exhibits a higher Bi residual ratio after aging than the Ti-free composite
oxide. It is also apparent from the graph of Figure 2 that Samples 12 to 15, in which
the Bi/Ti ratio R satisfies 0.3 ≦ R ≦ 1.5, are excellent in the effect of suppressing
Bi from scattering. Especially, the catalysts in which the ratio R satisfies 0.5 ≦
R ≦ 1.3 are more excellent in the effect of suppressing Bi from scattering.
[0059] As seen from the graph of Figure 3, when the Bi content is not less than 0.2 mol/liter
and not more than 0.5 mol/liter, the effect of suppressing H
2S emissions is high. Moreover, as seen from the graph of Figure 4, when the Bi content
is not less than 0.2 mol/liter and not more than 0.4 mol/liter, H
2S emissions can be suppressed while retaining three-way activity.
[0060] While preferred embodiments have been shown and described, various modifications
and substitutions may be made thereto.
[0061] Accordingly, it is to be understood that the present invention has been described
by way of illustration only, and such illustrations and embodiments as have been disclosed
herein are not to be construed as limiting to the claims.
[0062] The exhaust gas purifying catalyst of the present invention is useful as a three-way
catalyst for automobile engines. The application, however, is not limited to automobile
engines and can be used for other internal combustion engines where combustion is
controlled at or near the stoichiometric atmosphere.