U.S. patent application number 10/704784 was filed with the patent office on 2004-09-02 for exhaust gas treatment system and exhaust gas treatment method.
Invention is credited to Iida, Kozo, Kiyosawa, Masashi, Nojima, Shigeru.
Application Number | 20040168433 10/704784 |
Document ID | / |
Family ID | 32767813 |
Filed Date | 2004-09-02 |
United States Patent
Application |
20040168433 |
Kind Code |
A1 |
Nojima, Shigeru ; et
al. |
September 2, 2004 |
Exhaust gas treatment system and exhaust gas treatment method
Abstract
There is provided an exhaust gas treatment system for removing
nitrogen oxide and sulfur trioxide in exhaust gas by using a
catalyst characterized in that a SO.sub.3 reducing catalyst on the
upstream side and a denitrifying catalyst on the downstream side
are arranged in series with respect to the flow direction of
exhaust gas. Also, there is provided an exhaust gas treatment
method characterized by including a SO.sub.3 reducing process for
reducing SO.sub.3 using a SO.sub.3 reducing catalyst on the
upstream side and a denitrifying process for removing nitrogen
oxides using a denitrifying catalyst on the downstream side with
respect to the flow direction of exhaust gas.
Inventors: |
Nojima, Shigeru; (Hiroshima,
JP) ; Iida, Kozo; (Hiroshima, JP) ; Kiyosawa,
Masashi; (Nagasaki-ken, JP) |
Correspondence
Address: |
MYERS BIGEL SIBLEY & SAJOVEC
PO BOX 37428
RALEIGH
NC
27627
US
|
Family ID: |
32767813 |
Appl. No.: |
10/704784 |
Filed: |
November 10, 2003 |
Current U.S.
Class: |
60/301 ;
60/299 |
Current CPC
Class: |
B01D 53/8637 20130101;
B01D 53/8628 20130101 |
Class at
Publication: |
060/301 ;
060/299 |
International
Class: |
F01N 003/10 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 27, 2003 |
JP |
2003-051787 |
Claims
1. An exhaust gas treatment system for removing nitrogen oxide and
sulfur trioxide in exhaust gas by using a catalyst, characterized
in that a SO.sub.3 reducing catalyst on the upstream side and a
denitrifying catalyst on the downstream side are arranged in series
with respect to the flow direction of exhaust gas.
2. The exhaust gas treatment system according to claim 1,
characterized in that said SO.sub.3 reducing catalyst is a catalyst
in which Ru is carried as an active metal on a carrier.
3. The exhaust gas treatment system according to claim 1,
characterized in that the carrier used for said SO.sub.3 reducing
catalyst is at least one kind selected from a group consisting of
titania, alumina, zirconia, silica, and zeolite.
4. The exhaust gas treatment system according to claim 2,
characterized in that said SO.sub.3 reducing catalyst contains at
least one kind selected from a group consisting of Mo, W and V as a
co-catalyst in the carrier.
5. The exhaust gas treatment system according to claim 1,
characterized in that said denitrifying catalyst carries at least
one kind selected from a group consisting of Mo, W and V as an
active metal on a carrier containing titania.
6. The exhaust gas treatment system according to claim 1,
characterized in that both of said SO.sub.3 reducing catalyst and
said denitrifying catalyst are a catalyst formed into a honeycomb
shape.
7. An exhaust gas treatment method for removing nitrogen oxide and
sulfur trioxide in exhaust gas by using a catalyst, characterized
in that said treatment method includes a SO.sub.3 reducing process
for reducing SO.sub.3 using a SO.sub.3 reducing catalyst on the
upstream side and a denitrifying process for removing nitrogen
oxides using a denitrifying catalyst on the downstream side with
respect to the flow direction of exhaust gas.
8. The exhaust gas treatment method according to claim 7,
characterized in that said treatment method includes an NH.sub.3
adding process for adding ammonia NH.sub.3, which is a reducing
agent for nitrogen oxides and SO.sub.3, in a mole ratio of
NH.sub.3/NOx not lower than the equivalent at the preceding stage
of said SO.sub.3 reducing process.
9. The exhaust gas treatment method according to claim 7,
characterized in that the concentration of NH.sub.3 at the
downstream outlet of the SO.sub.3 reducing catalyst is 3 ppm or
higher in said SO.sub.3 reducing process.
Description
RELATED APPLICATION
[0001] This application claims priority from Japanese Patent
Application No. 2003-051787 filed Feb. 27, 2003, the disclosure of
which is incorporated by reference herein in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to an exhaust gas treatment
system and an exhaust gas treatment method and, more particularly,
to an exhaust gas treatment method in which exhaust gas such as
nitrogen oxides and sulfur trioxide (SO.sub.3) exhausted from a
boiler or the like is removed by reduction using a catalyst.
BACKGROUND OF THE INVENTION
[0003] As a catalyst for removing sulfur trioxide (SO.sub.3) in
exhaust gas by reaction, catalysts in which ruthenium (Ru) is
carried on various carriers have been reported (see Japanese Patent
Provisional Publication No. 10-24963 (No. 24963/1998).
[0004] A SO.sub.3 reducing reaction using a ruthenium (Ru) carrying
catalyst converts sulfur trioxide (SO.sub.3) into sulfur dioxide
(SO.sub.2) using ammonia (NH.sub.3) as a reducing agent according
to the following reaction formula (1).
SO.sub.3+2NH.sub.3+O.sub.2.fwdarw.SO.sub.2+N.sub.2+3H.sub.2O
(1)
[0005] However, in the case where the aforementioned ruthenium (Ru)
carrying catalyst is used, in a system in which the concentration
of ammonia (NH.sub.3) is low, the reaction expressed by the above
formula (1) is extremely slow, so that there arises a problem in
that the reducing reaction does not proceed sufficiently.
[0006] On the one hand, combustion exhaust gas exhausted from a
coal-fired or oil-fired combustion boiler is a gas containing
nitrogen oxides. In order to discharge this gas, it is necessary to
remove nitrogen oxides in the exhaust gas. Therefore, a denitrifier
is provided on the downstream side of the combustion boiler so that
ammonia (NH.sub.3) is injected into the combustion exhaust gas
through an injection nozzle to be caused to react with nitrogen
oxides (NO, NO.sub.2) by reduction, by which the exhaust gas is
decomposed into nitrogen (N.sub.2) and water (H.sub.2O), which are
harmless. At this time, in a method in which nitrogen oxides are
removed from exhaust gas using a denitrifying catalyst, ammonia is
usually added to cause sufficient denitrifying reaction.
[0007] In a system for treating exhaust gas exhausted from a
combustion boiler, a technology in which sulfur trioxide (SO.sub.3)
is not caused to flow to equipment on the downstream side as far as
possible is demanded because SO.sub.3 contained in the exhaust gas
is responsible for corrosion and deterioration of equipment.
[0008] On the other hand, the aforementioned ruthenium (Ru)
carrying catalyst not only can remove sulfur trioxide (SO.sub.3) by
reduction, but also can reduce nitrogen oxides (NOx) in the exhaust
gas using ammonia (NH.sub.3) according to the following reaction
formula (2) to convert them into nitrogen gas (N.sub.2).
4NH.sub.3+4NO+O.sub.2.fwdarw.4N.sub.2+6H.sub.2O (2)
SUMMARY OF THE INVENTION
[0009] In view of the above situation, the inventors carried out
studies earnestly to develop a catalyst system and a treatment
method capable of efficiently removing nitrogen oxides (NOx) and
sulfur trioxide (SO.sub.3) by reaction at the same time in the
treatment of exhaust gas containing NOx and SO.sub.3.
[0010] As a result, the inventors found that the above problems can
be solved by using a catalyst system in which a SO.sub.3 reducing
catalyst and a denitrifying catalyst are arranged in series and
combined. The present invention was completed from the
above-described viewpoint.
[0011] The present invention provides an exhaust gas treatment
system for removing nitrogen oxide and sulfur trioxide in exhaust
gas by using a catalyst, characterized in that a SO.sub.3 reducing
catalyst on the upstream side and a denitrifying catalyst on the
downstream side are arranged in series with respect to the flow
direction of exhaust gas.
[0012] In the present invention, the SO.sub.3 reducing catalyst is
preferably a catalyst in which Ru is carried as an active metal on
a carrier. The carrier used for the SO.sub.3 reducing catalyst
preferably contains at least one kind selected from a group
consisting of titania, alumina, zirconia, silica, and zeolite. The
SO.sub.3 reducing catalyst can contain at least one kind selected
from a group consisting of Mo, W and V as a co-catalyst in the
carrier. The denitrifying catalyst can use a catalyst that carries
at least one kind selected from a group consisting of Mo, W and V
as an active metal on a carrier containing titania. The shapes of
the SO.sub.3 reducing catalyst and the denitrifying catalyst are
not subject to any special restriction, and both of these catalysts
can be, for example, a catalyst formed into a honeycomb shape.
[0013] Also, the present invention provides an exhaust gas
treatment method for removing nitrogen oxide and sulfur trioxide in
exhaust gas by using a catalyst, characterized in that the
treatment method includes a SO.sub.3 reducing process for reducing
SO.sub.3 using a SO.sub.3 reducing catalyst on the upstream side
and a denitrifying process for removing nitrogen oxides using a
denitrifying catalyst on the downstream side with respect to the
flow direction of exhaust gas. The treating method in accordance
with the present invention preferably includes an NH.sub.3 adding
process for adding ammonia NH.sub.3, which is a reducing agent for
nitrogen oxides and SO.sub.3, in a mole ratio of NH.sub.3/NOx
favorably not lower than the equivalent at the preceding stage of
the SO.sub.3 reducing process. Also, the concentration of NH.sub.3
at the downstream outlet of the SO.sub.3 reducing catalyst is
preferably 3 ppm or higher in the SO.sub.3 reducing process.
[0014] According to the treatment method and treatment system in
accordance with the present invention, in the treatment of exhaust
gas containing nitrogen oxides (NOx) and sulfur trioxide
(SO.sub.3), NOx and SO.sub.3 can be removed by reduction
efficiently at the same time. Therefore, in the exhaust gas
treatment using the system in accordance with the present
invention, in particular, equipment on the downstream side of the
denitrifier is less liable to be deteriorated or damaged, so that
this treatment system has an advantage that the maintenance of the
whole system is easy and the long-term use is ensured.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 are a block diagram showing one example of a system
incorporating an exhaust gas treatment system in accordance with
the present invention.
[0016] The reference numerals shown in these figures are defined as
follows: 1, boiler; 2, SO.sub.3 reducing catalyst; 3, denitrifier;
4, air preheater; 5, dust collector; 6, gas-gas heater (heat
exchanger); 7, desulfurizer; 8, stack.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0017] An embodiment of an exhaust gas treatment system and an
exhaust gas treatment method in accordance with the present
invention will be described. The present invention is not subject
to any restriction by the embodiment described below.
[0018] Exhaust Gas Treatment Method
[0019] In the exhaust gas treatment method in accordance with the
present invention, a SO.sub.3 reducing process is conducted on the
upstream side and a denitrifying process is conducted on the
downstream side with respect to the flow direction of exhaust gas
containing nitrogen oxides. At the preceding stage of the SO.sub.3
reducing process, ammonia NH.sub.3, which is a reducing agent for
nitrogen oxides and SO.sub.3 in exhaust gas, is added by an
NH.sub.3 adding process. In the NH.sub.3 adding process, ammonia
should be added to the exhaust gas in a mole ratio NH.sub.3/NOx of
ammonia to nitrogen oxides NOx preferably not lower than the
equivalent (not lower than 1), further preferably not lower than
1.2. Since the concentration of ammonia added to the exhaust gas is
high at the preceding stage of the process in which reducing
reaction takes place, the SO.sub.3 reducing process is first
conducted in a state in which the concentration of ammonia is
high.
[0020] In the SO.sub.3 reducing process, SO.sub.3 is reduced by a
SO.sub.3 reducing catalyst, described later. By using NH.sub.3 as a
reducing agent, the SO.sub.3 reducing catalyst concurrently carries
out three reactions: (1) SO.sub.3 reducing reaction, (2)
denitrifying reaction, and (3) NH.sub.3 decomposing reaction.
SO.sub.3+2NH.sub.3+O.sub.2.fwdarw.SO.sub.2+N.sub.2+3H.sub.2O
(1)
4NH.sub.3+4NO+O.sub.2.fwdarw.4N.sub.2+6H.sub.2O (2)
2NH.sub.3+3/2O.sub.2.fwdarw.N.sub.2+3H.sub.2O (3)
[0021] Thus, the SO.sub.3 reducing catalyst not only removes sulfur
trioxide (SO.sub.3) by reduction, but also reduces nitrogen oxides
(NOx) in the exhaust gas using ammonia (NH.sub.3) to convert into
nitrogen gas (N.sub.2).
[0022] In the SO.sub.3 reducing process, the concentration of
NH.sub.3 at the downstream outlet of the SO.sub.3 reducing catalyst
should preferably be 3 ppm or higher, further preferably be 10 ppm
or higher. If the concentration of NH.sub.3 is too low, the
reducing agent runs short in a downstream denitrifying process, so
that sufficient denitrifying action cannot be brought about.
[0023] Next, on the downstream side of the SO.sub.3 reducing
process, the denitrifying process is conducted. In the denitrifying
process, nitrogen oxides are removed using a denitrifying catalyst,
described later, according to the following formula (2) or the
like.
4NH.sub.3+4NO+O.sub.2.fwdarw.4N.sub.2+6H.sub.2O (2)
[0024] For an exhaust gas containing a large quantity of SOx, for
example, in a system having no SO.sub.3 reducing process, SO.sub.2
oxidizing reaction is produced by a denitrifying catalyst according
to the following formula (4), so that the concentration of SO.sub.3
increases further in some cases. For this reason as well, a method
in which SO.sub.3 is not yielded in exhaust gas as far as possible
is needed. According to the treatment method in accordance with the
present invention, SO.sub.3 can be removed effectively on the
upstream side of the denitrifying process.
SO.sub.2+1/2O.sub.2.fwdarw.SO.sub.3 (4)
[0025] Generally, in the treatment method for exhaust gas exhausted
from various types of combustion equipment such as a boiler, the
exhaust gas exhausted from the boiler is sent to a denitrifying
catalyst, and a denitrifying process is conducted. In the
denitrifying process, ammonia NH.sub.3 added on the upstream side
of the denitrifying catalyst is used as a reducing agent.
[0026] In the denitrifying process in accordance with the present
invention, the SO.sub.3 reducing process is usually provided on the
upstream side of the denitrifying process, so that denitrification
is carried out by using ammonia added at the preceding stage of the
SO.sub.3 reducing process. However, a predetermined quantity of
ammonia may be added as necessary at the following stage of the
SO.sub.3 reducing process and at the preceding stage of the
denitrifying process. In the exhaust gas after the denitrifying
process, both NOx and SO.sub.3 are removed by reduction, and the
added NH.sub.3 is also removed after acting as a reducing
agent.
[0027] As described above, in the present invention, for the
exhaust gas flowing from the denitrifying process, both NOx and
SO.sub.3 are removed by reduction, so that corrosion caused by
SO.sub.3 is restrained even if the exhaust gas is caused to pass
through the downstream equipment such as a dust collector and a wet
type desulfurizer. Generally, between the denitrifying process and
the desulfurizing process using a wet type desulfurizer, a heating
process using a heater or steam, a dust collecting process using an
electric dust collector, a heat recovery process using a gas
heater, and the like process are included.
[0028] Exhaust Gas Treatment System
[0029] FIG. 1 shows one example of an exhaust gas treatment system
incorporating an exhaust gas treatment system in accordance with
the present invention. Hereunder, the whole of the exhaust gas
treatment system in accordance with the embodiment shown in FIG. 1
will be described in detail with reference to the accompanying
drawing.
[0030] In the present invention, a SO.sub.3 reducing catalyst on
the upstream side and a denitrifying catalyst on the downstream
side are provided in series with respect to the flow direction of
exhaust gas containing nitrogen oxides.
[0031] In the system shown in FIG. 1, on the downstream side of a
boiler 1, a SO.sub.3 reducing catalyst 2, a denitrifier 3, an air
heater (A/H) 4, which is heating means, a dust collector 5, a heat
exchanger (GGH) 6 for recovering heat energy, a wet type
desulfurizer (desulfurizing absorption tower) 7, a heat exchanger
(GGH) 6 for reheating, and a stack 8 are arranged in that order.
The SO.sub.3 reducing catalyst 2 is provided on the downstream side
of the boiler 1 and on the upstream side of the denitrifier 3. On
the upstream side of the SO.sub.3 reducing catalyst 2, NH.sub.3
adding means 9 for adding ammonia, which serves as a reducing
agent, is provided.
[0032] In the system in accordance with the present invention
exemplified in FIG. 1, as the NH.sub.3 adding means 9 provided on
the upstream side of the SO.sub.3 reducing catalyst 2, equipment
formed by, for example, a reducing agent injection pipe or a
plurality of spray nozzles is used. As a method for injecting a
reducing agent containing ammonia, there is available a method in
which the reducing agent is vaporized, and the vaporized reducing
agent is diluted by adding air, inert gas, water vapor, etc. before
the reducing agent is added to the exhaust gas. At this time, it is
effective to arrange the nozzles so that the reducing agent flows
uniformly to the SO.sub.3 reducing catalyst and the denitrifying
catalyst. In some cases, a plurality of nozzles are arranged
perpendicularly to the gas flow.
[0033] As the SO.sub.3 reducing catalyst 2 used in this system, any
catalyst can be used if it has a SO.sub.3 reducing function. For
example, a catalyst in which Ru is carried as an active metal on a
carrier can be cited. The kind of carrier used for the SO.sub.3
reducing catalyst is not subject to any special restriction, but
the carrier is preferably at least one kind selected from a group
consisting of titania, alumina, zirconia, silica, and zeolite.
Also, the SO.sub.3 reducing catalyst can contain at least one kind
selected from a group consisting of Mo, W and V as a co-catalyst in
the carrier as necessary.
[0034] The shape of the SO.sub.3 reducing catalyst is not subject
to any special restriction. For example, a honeycomb-shaped
catalyst, a catalyst formed by stacking the honeycomb-shaped
catalysts, a catalyst formed by filling particulate catalysts, and
the like can be used. In particular, a honeycomb-shaped catalyst is
preferably used.
[0035] As a denitrifying catalyst used in the denitrifier 3 of this
system, a catalyst formed by carrying at least one kind selected
from a group consisting of Mo, W and V as an active metal on a
carrier containing titania can be used preferably. In addition, a
catalyst in which an active metal of at least one kind selected
from a group consisting of Pt, Pd, Ir, Ru, Cu, Co, Fe, Ag, Mn, Ni,
Zn and In is contained in the carrier of at least one kind selected
from a group consisting of Al.sub.2O.sub.3, SiO.sub.2, ZrO.sub.2,
TiO.sub.2, metallosilicate, and zeolite can be used.
[0036] The shape of the nitrifying catalyst is not subject to any
special restriction. For example, a honeycomb-shaped catalyst, a
catalyst formed by stacking the honeycomb-shaped catalysts, a
catalyst formed by filling particulate catalysts, and the like can
be used. In particular, a honeycomb-shaped catalyst is preferably
used.
[0037] In the treatment system in accordance with the present
invention, as described above, the SO.sub.3 reducing catalyst 2 on
the upstream side and the denitrifying catalyst system 3 on the
downstream side are arranged in series with respect to the flow of
exhaust gas. On the downstream side of the catalyst system in which
these two types of catalysts are combined with each other, various
types of equipment as shown in FIG. 1 are provided according to the
treatment of exhaust gas.
[0038] In the system shown in FIG. 1, the air heater (A/H) 4, which
is heating means, and the dust collector 5 are provided on the
downstream side of the denitrifier 3. The dust collector 5 is not
subject to any special restriction if it can collect dust roughly
before the exhaust gas is introduced into the desulfurizing
absorption tower 7.
[0039] On the downstream side of the dust collector 5, the heat
exchanger (GGH) 6 for recovering heat energy and the desulfurizer
(desulfurizing absorption tower) 7 are provided. The desulfurizer 7
is not subject to any special restriction. For example, a wet type
desulfurizer generally used for flue gas treatment or a
desulfurizer in which a cooling tower is provided at the preceding
stage of an absorption tower is used. As the desulfurizer 7, an
ordinary wet type desulfurizer can be used. As an absorbent used
for wet desulfurization, aqueous solution of absorbent (alkali
absorbent) of calcium carbonate, calcium oxide, calcium hydroxide,
sodium carbonate, sodium hydroxide, and the like can be cited.
[0040] In the system shown in FIG. 1, which uses a wet
desulfurization method, the heat exchanger 6 for reheating is
provided on the downstream side of the desulfurizing absorption
tower 7, and the exhaust gas is discharged to the air through the
stack 8 after passing through these types of equipment. In the heat
exchanger 6 for reheating, the combustion exhaust gas whose
temperature has been decreased is heated by heat energy recovered
by the heat exchanger 6 for heat recovery at the preceding stage of
the desulfurizer 7. Usually, the heat exchanger for heat recovery
and the heat exchanger for reheating are formed by a gas heater of
a system in which heat energy is exchanged by using a heat medium
as a medium, and may be a separate system or may be a gas-gas
heater for directly effecting heat exchange if they can cool and
heat the exhaust gas, respectively.
[0041] In the above-described system shown in FIG. 1, on the
downstream side of the catalyst system in which the SO.sub.3
reducing catalyst 2 and the denitrifying catalyst 3 are combined
with each other, since nitrogen oxides and SO.sub.3 component
contained in the exhaust gas have been removed with high
efficiency, corrosion and deterioration of equipment are
restrained, and hence system control and trouble can be
reduced.
[0042] The exhaust gas to be treated by the treatment system in
accordance with the present invention is boiler exhaust gas
generated in a thermal electric power station, a factory, etc. in
which a fuel containing sulfur and mercury, such as coal and heavy
oil, is burned or heating furnace exhaust gas generated in a metal
factory, an oil refinery, a petrochemical plant, etc. The treatment
system in accordance with the present invention is suitable for a
large quantity of exhaust gas containing carbon dioxide, oxygen,
SOx, soot, or water.
[0043] Hereunder, the present invention will be described in more
detail with reference to examples. The present invention is not
limited to these examples.
EXAMPLE 1 (PREPARATION OF CATALYSTS)
[0044] (Honeycomb Catalysts 1 to 10)
[0045] Aqueous solution of ruthenium chloride (RuCl.sub.3) was
impregnated into and carried on particles of compound 1: TiO.sub.2
(MC-90 manufactured by Ishihara Sangyo Kaisha, Ltd.), compound 2:
.gamma.-Al.sub.2O.sub.3 (manufactured by Sumitomo Chemical Co.,
Ltd.), compound 3: SiO.sub.2 (manufactured by Fuji Silysia Chemical
Ltd.), compound 4: zirconia (manufactured by Nikki Chemical Co.,
Ltd.), compound 5: silicalite (manufactured by Mobil Corp.),
compound 6: TiO.sub.2-WO.sub.3 (weight ratio 90:10), compound 7:
TiO.sub.2-WO.sub.3 (weight ratio 80:20), compound 8:
TiO.sub.2-WO.sub.3-V.sub.2O.sub.5 (weight ratio 90:9:1), compound
9: TiO.sub.2-MoO.sub.3-V.sub.2O.sub.5 (weight ratio 90:9:1), and
compound 10: TiO.sub.2-SiO.sub.2 (weight ratio 90:10) so that the
carrying amount of Ru per particle was 0.5%, and firing was
accomplished in the air at 500.degree. C. for about 5 hours after
evaporation to dryness. As a result, powder catalysts 1-10 were
obtained.
[0046] The powder catalysts 1-10 were put in water, and slurried by
ball mill grinding. The slurries 1-10 were applied to and carried
on a honeycomb (Ap: 445 m.sup.2/m.sup.3) of TiO.sub.2-WO.sub.3
(weight ratio 90:10) with a pitch of 7.0 mm and a wall thickness of
1.0 mm in an amount of 200 g/m.sup.2 per honeycomb surface area, by
which honeycomb catalysts 1-10 were obtained.
[0047] (Honeycomb Catalyst 11)
[0048] As the denitrifying catalyst, a honeycomb catalyst (pitch:
7.0 mm, wall thickness: 1.0 mm, Ap: 445 m.sup.2/m.sup.3) consisting
of TiO.sub.2-WO.sub.3-V.sub.2O.sub.5 (weight ratio 91:8.8:0.2) was
use
EXAMPLE 2 (EXHAUST GAS TREATMENT TEST A)
[0049] Catalyst systems were formed by combining honeycomb
catalysts 1-10 (SO.sub.3 reducing catalyst) prepared in example 1
and honeycomb catalyst 11 (denitrifying catalyst) with each other,
and exhaust gas treatment tests were conducted under the conditions
described below.
[0050] [Test Conditions]
[0051] The gas composition was 150 ppm NOx, 2900 ppm SOx (including
80 ppm SO.sub.3), 180 ppm NH.sub.3, 1.3% O.sub.2, 10% H.sub.2O, 10%
CO.sub.2, the balance being N.sub.2.
[0052] The test conditions were as follows: temperature:
380.degree. C., superficial velocity: 3.3 mN/s, gas quantity: 30
m.sup.3N/s, catalyst formation: 50 mm square.times.800 mm
(preceding stage: one SO.sub.3 reducing catalyst, following stage:
one denitrifying catalyst), and GHSV: 15000 h.sup.-1 at outlet of
SO.sub.3 reducing catalyst, 5000 h.sup.-1 at outlet of denitrifying
catalyst (AV: 34 m.sup.3/m.sup.2.multidot.h at outlet of SO.sub.3
reducing catalyst, 11 m.sup.3/m.sup.2.multidot.h at outlet of
denitrifying catalyst).
[0053] Table 1 gives exhaust gas treatment performance at a total
GHSV of 5000 h.sup.-1 in the case where honeycomb catalysts 1-10
serving as the SO.sub.3 reducing catalyst and honeycomb catalyst 11
serving as the denitrifying catalyst were arranged in series. The
concentration of NOx was measured by the chemiluminescence method,
the concentration of NH.sub.3 was measured by ion chromatography,
and the concentration of SO.sub.3 was measured by arsenazo III
method using a spiral tube. The NOx removal efficiency and SO.sub.3
reduction amount were calculated by the following formulae.
NOx removal efficiency (%)=(1-outlet NOx/inlet NOx).times.100
SO.sub.3 reduction amount (ppm)=inlet SO.sub.3-outlet SO.sub.3
[0054] The target performance of this exhaust gas treatment test
was set so as to be a target that satisfies all of the following
performances.
[0055] NOx removal efficiency: 85% or higher
[0056] SO.sub.3 reduction amount: 0 ppm or larger (SO.sub.3 is
reduced)
[0057] Leak of NH.sub.3: 15 ppm or less
1TABLE 1 Exhaust gas treatment performance of combined catalysts
NOx SO.sub.3 Leak Preceding-stage catalyst removal reduction of
(coated carrier: SO.sub.3 Following-stage cataly efficiency amount
NH.sub.3 Test reducing catalyst) (denitrifying catalyst) (%) (ppm)
(ppm) 1 Catalyst 1 Catalyst 11 89 6 10 (TiO.sub.2 carrier)
(TiO.sub.2--WO.sub.3--V.sub.2O.sub.5) 2 Catalyst 2 Catalyst 11 90 6
9 (Al.sub.2O.sub.3 carrier) 3 Catalyst 3 Catalyst 11 90 7 9
(SiO.sub.2 carrier) 4 Catalyst 4 Catalyst 11 89 8 10 (ZrO.sub.2
carrier) 5 Catalyst 5 (Silicalite carrie Catalyst 11 90 7 9 6
Catalyst 6 Catalyst 11 95 7 7 (TiO.sub.2--WO.sub.3 carrier) 7
Catalyst 7 Catalyst 11 96 7 7 (TiO.sub.2--WO.sub.3 carrier) 8
Catalyst 8 Catalyst 11 96 6 5 (TiO.sub.2--WO.sub.3--V.sub.2O.sub.3
carrier) 9 Catalyst 9 Catalyst 11 96 7 8
(TiO.sub.2--WO.sub.3--MoO.sub.3 carrier) 10 Catalyst 10 Catalyst 11
93 7 8 (TiO.sub.2--SiO.sub.2 carrier)
[0058] From the above results, it was confirmed that the catalyst
systems in tests 1 to 10, in which the SO.sub.3 reducing catalyst
is provided at the preceding stage and the denitrifying catalyst is
provided at the following stage, are effective for denitrification,
SO.sub.3 reduction, and decrease in leak of NH.sub.3, and in
particular, these catalyst systems are promising for achieving
SO.sub.3 reduction.
EXAMPLE 3 (PREPARATION OF CATALYST)
[0059] Various tests were conducted based on test 6 having high
performance in the above-described tests on catalyst system.
[0060] Honeycomb Catalysts 12-14)
[0061] Honeycomb catalysts 12 and 13 were prepared by the same
preparation method as that for SO.sub.3 reducing catalyst 6
(honeycomb catalyst 6) in example 1 except that slurries that
carried 0.3% and 1% Ru, in place of 0.5% Ru, on TiO.sub.2-WO.sub.3
carrier of compound 6 were prepared.
[0062] Also, honeycomb catalyst 14 was prepared by the same
preparation method as that for SO.sub.3 reducing catalyst 6
(honeycomb catalyst 6) in example 1 except that slurry 6 was
applied to the honeycomb in an amount of 100 g/m.sup.2 per
honeycomb surface area in place of 200 g/m.sup.2.
EXAMPLE 4 (EXHAUST GAS TREATMENT TEST B)
[0063] Exhaust gas treatment tests (tests 11, 12 and 13) were
conducted in the same way as test 6 in example 2 on catalyst
systems in which each one of the honeycomb catalysts 12, 13 and 14
(SO.sub.3 reducing catalysts) and one denitrifying catalyst 11 were
combined with each other. Further, an exhaust gas treatment test
(test 14) was conducted in the same way as described above on a
catalyst system in which two honeycomb catalysts 6 (SO.sub.3
reducing catalysts) and one denitrifying catalyst 11 were combined
with each other.
[0064] Table 2 gives the results of tests on the above-described
catalyst systems.
2TABLE 2 Exhaust gas treatment performance of various combined
catalysts SO.sub.3 Leak Preceding-stage NOx reduction of catalyst
(SO.sub.3 Following-stage cataly removal amount NH.sub.3 Test
reducing catalyst) (denitrifying catalyst) efficiency (%) (ppm)
(ppm) 11 Catalyst 11 (Ru(0.3)/ Catalyst 11 95 6 8
TiO.sub.2--WO.sub.3), one (TiO.sub.2--WO.sub.3--V.sub.2O.sub.5) 12
Catalyst 12 (Ru(1.0)/ Catalyst 11 96 10 5 TiO.sub.2--WO.sub.3), one
13 Catalyst 13 (Ru(0.5)/ Catalyst 11 95 7 7 TiO.sub.2--WO.sub.3:
100 g/m.sup.2 coated), one 14 Catalyst 6, two Catalyst 11, 91 12 1
one
[0065] From the above test results, it was confirmed that even when
the Ru carrying amount or the coating amount of SO.sub.3 reducing
catalyst is changed, the catalyst systems in test 11 to 13 are
effective for denitrification, SO.sub.3 reduction, and decrease in
leak of NH.sub.3, and in particular, these catalyst systems are
promising for achieving SO.sub.3 reduction. Also, it was confirmed
that even when the arrangement ratio of SO.sub.3 reducing catalyst
to denitrifying catalyst is changed, the catalyst system in test 14
achieves the target performance in terms of SO.sub.3 reduction
etc.
EXAMPLE 5 (EXHAUST GAS TREATMENT TEST C)
[0066] The activity evaluation was carried out under the following
test conditions based on the catalyst combination and test
conditions of test 6 that had exhibited high performance in the
above-described tests on catalyst system.
[0067] Test 15 . . . An activity evaluation test was conducted by
the same method as that of test 6 except that the concentration of
NH.sub.3 in the gas at the inlet of catalyst was 153 ppm in place
of the 180 ppm in test 6 in example 2.
[0068] Test 16 . . . An activity evaluation test was conducted by
the same method as that of test 6 except that the concentration of
SO.sub.3 in the gas at the inlet was 50 ppm in place of the 80 ppm
in test 6 in example 2.
[0069] Test 17 . . . An activity evaluation test was conducted by
the same method as that of test 6 except that the concentration of
NOx in the gas at the inlet was 170 ppm in place of the 150 ppm in
test 6 in example 2.
[0070] Test 18 . . . An activity evaluation test was conducted by
the same method as that of test 6 except that the concentration of
O.sub.2 in the gas at the inlet was 2% in place of the 1.3% in test
6 in example 2.
[0071] Test 19 . . . An activity evaluation test was conducted by
the same method as that of test 6 except that the concentration of
SOx in the gas at the inlet was 4000 ppm (including 80 ppm of
concentration of SO.sub.3) in place of the 2900 ppm (including 80
ppm of concentration of SO.sub.3) in test 6 in example 2.
[0072] Table 3 gives the exhaust gas treatment test results in the
above-described tests 15 to 19.
3TABLE 3 Exhaust gas treatment performance of combined catalysts
under each test condition Preceding-stage Following-stage NOx Leak
of Changed item of catalyst (SO.sub.3 catalys removal SO.sub.3
reduction NE Test test conditions reducing catalyst) (denitrifying
catalyst) efficiency (%) amount (ppm) (ppm) 15 NH.sub.3 Catalyst 6
Catalyst 11 90 4 1 Concentration 153 ppm 16 SO.sub.3 Catalyst 6
Catalyst 11 96 6 8 concentration 50 ppm 17 Nox Catalyst 6 Catalyst
11 91 5 1 concentration 170 ppm 18 O.sub.2 Catalyst 6 Catalyst 11
93 4 3 concentration 2% 19 SOx Catalyst 6 Catalyst 11 95 6 8
concentration 4000 ppm
[0073] From the test results given in Table 3, it was confirmed
that the catalyst systems in tests 15 to 19, in which the SO.sub.3
reducing catalyst is provided at the preceding stage and the
denitrifying catalyst is provided at the following stage, are
effective for denitrification, SO.sub.3 reduction, and decrease in
leak of NH.sub.3 under any of the test conditions.
Comparative Example 1 (Exhaust Gas Treatment Test)
[0074] Exhaust gas treatment tests were conducted under the
following conditions using the aforementioned SO.sub.3 reducing
catalyst 6 singly.
[0075] [Test Conditions]
[0076] The gas composition was 150 ppm NOx, 2900 ppm SOx (including
80 ppm SO.sub.3), 180 ppm NH.sub.3, 1.3% O.sub.2, 10% H.sub.2O, 10%
CO.sub.2, the balance being N.sub.2.
[0077] The test conditions were as follows: temperature:
380.degree. C., superficial velocity: 3.3 mN/s, gas quantity: 30
m.sup.3N/s, catalyst formation: 50 mm square.times.800 mm (three
SO.sub.3 reducing catalysts), and GHSV: 15000 h.sup.-1 at outlet of
the first SO.sub.3 reducing catalyst, 7500 h.sup.-1 at outlet of
the second one, and 5000 h.sup.-1 at outlet of the third one (AV:
34 m.sup.3/m.sup.2.multidot.h at outlet of the first SO.sub.3
reducing catalyst, 17 m.sup.3/m.sup.2 h at outlet of the second
one, and 11 m.sup.3/m.sup.2.multidot.h at outlet of the third
one).
[0078] Table 4 gives the exhaust gas treatment performance results
at the catalyst outlet at each GHSV (comparative tests 1, 2 and
3).
[0079] Further, an exhaust gas treatment test was conducted by
arranging two denitrifying catalysts at the preceding stage and one
SO.sub.3 reducing catalyst at the following stage in series under
the same test conditions as described above. Table 4 concurrently
gives the exhaust gas treatment performance result at the catalyst
outlet (total GHSV 5000 h.sup.-1: comparative test 4).
4TABLE 4 Exhaust gas treatment performance of comparative catalyst
NOx removal Comparative Preceding-stage Following-stage efficiency
SO.sub.3 reduction Leak of NH.sub.3 test catalyst catalyst (%)
amount (ppm) (ppm) 1 Catalyst 6 -- 52 10 70 (one SO.sub.3 reducing
catalyst, GHSV 15000 h.sup.-1) 2 Catalyst 6 -- 74 13 15 (two
SO.sub.3 reducing catalysts, GHSV 7500 h.sup.-1 ) 3 Catalyst 6 --
80 5 0 (three SO.sub.3 reducing catalysts, GHSV 5000 h.sup.-1 ) 4
Catalyst 11 Catalyst 6 85 -5 3 (two denitrifying catalysts) (one
SO.sub.3 reducing catalyst) (Increase)
[0080] From the above-described test results, the following facts
were found: In comparative test 1 in which one SO.sub.3 reducing
catalyst is used, although a decrease in SO.sub.3 is recognized,
NOx removal efficiency and leak of NH.sub.3 do not satisfy the
target performance. Also, in comparative test 2 in which two
SO.sub.3 reducing catalysts are used, although a decrease in
SO.sub.3 is recognized as in comparative example 2 and leak of
NH.sub.3 is little, NOx removal efficiency does not satisfy the
target performance. Further, in comparative test 3 in which three
SO.sub.3 reducing catalysts are used, SO.sub.3 reduction amount is
small and NOx removal efficiency is still low.
[0081] Also, in comparative test 4 in which two denitrifying
catalysts are arranged at the preceding stage and one SO.sub.3
reducing catalyst is arranged at the following stage, the SO.sub.3
reducing function is not recognized, and inversely SO.sub.3 tends
to increase.
[0082] The above-described results revealed the following fact: In
the case where a large quantity of NH.sub.3 is contained, (1)
SO.sub.3 reducing reaction, (2) denitrifying reaction, and (3)
NH.sub.3 decomposing reaction take place concurrently, and the
SO.sub.3 reducing catalyst can carry out denitrification and
SO.sub.3 reduction at the same time.
[0083] On the other hand, in the case where a small quantity of
NH.sub.3 is contained, only (3) NH.sub.3 decomposing reaction
proceeds, and (1) SO.sub.3 reducing reaction and (2) denitrifying
reaction scarcely proceed.
[0084] For the above reason, it was clarified that in order to
remove exhaust gas efficiently using the SO.sub.3 reducing
catalyst, it is preferable that the SO.sub.3 reducing catalyst be
arranged at the preceding stage and the denitrifying catalyst be
arranged at the following stage, by which NOx, SO.sub.3 and
NH.sub.3 are reduced efficiently.
* * * * *