U.S. patent application number 10/511679 was filed with the patent office on 2005-10-20 for nitrogen oxide decomposing element and nitrogen oxide decomposing apparatus including the same.
This patent application is currently assigned to MITSUBISHI DENKI KABUSHIKI KAISHA. Invention is credited to Kimura, Minoru, Machida, Masato, Yamaji, Shigeru, Yamauchi, Shiro.
Application Number | 20050230269 10/511679 |
Document ID | / |
Family ID | 32170976 |
Filed Date | 2005-10-20 |
United States Patent
Application |
20050230269 |
Kind Code |
A1 |
Machida, Masato ; et
al. |
October 20, 2005 |
Nitrogen oxide decomposing element and nitrogen oxide decomposing
apparatus including the same
Abstract
A nitrogen oxide decomposing element and a nitrogen oxide
decomposing apparatus can perform a treatment at a relatively low
temperature without using a material, which is suspected to have
influence on the environment and human body, as an oxidant or a
catalyst. There is proposed a nitrogen oxide decomposing element 1
including a conductive solid electrolyte film 2 for selectively
allowing a hydrogen ion to pass through, a first electrode layer 3
made of an electronic conductivity base material and a catalyst for
accelerating anodic oxidation, a second electrode layer 4 made of
an electronic conductivity basematerialandacatalystforacceleratin-
gcathodicreduction, and a platinum group catalyst 6 supported by a
porous metal oxide 5 disposed to be adjacent to the second
electrode layer 4. A low-power consumption nitrogen oxide
decomposing apparatus which can efficiently use electric energy is
obtained by locating a nitrogen oxide sensor 14 in the vicinity of
the platinum group catalyst 6 supported by the metal oxide 5, and
controlling the magnitude of a current flowing between the first
and the second electrode layers 3 and 4 and the energization time
by a power source/control device 15 in accordance with the
concentration of nitrogen oxide detected by the nitrogen oxide
sensor 14.
Inventors: |
Machida, Masato; (Kumamoto,
JP) ; Yamauchi, Shiro; (Tokyo, JP) ; Kimura,
Minoru; (Tokyo, JP) ; Yamaji, Shigeru; (Tokyo,
JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 PENNSYLVANIA AVENUE, N.W.
SUITE 800
WASHINGTON
DC
20037
US
|
Assignee: |
MITSUBISHI DENKI KABUSHIKI
KAISHA
Tokyo
JP
Masato MACHIDA
Kumamoto-Shi
JP
|
Family ID: |
32170976 |
Appl. No.: |
10/511679 |
Filed: |
October 18, 2004 |
PCT Filed: |
September 26, 2003 |
PCT NO: |
PCT/JP03/12328 |
Current U.S.
Class: |
205/763 ;
204/277; 204/278; 205/765 |
Current CPC
Class: |
B01D 53/56 20130101;
B01D 53/326 20130101 |
Class at
Publication: |
205/763 ;
205/765; 204/277; 204/278 |
International
Class: |
C25C 007/00; C25D
017/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 23, 2002 |
JP |
2002-308447 |
Claims
1-12. (canceled)
13. A nitrogen oxide decomposing element, comprising: a conductive
solid electrolyte film for selectively allowing a hydrogen ion to
pass through; a first electrode made of an electronic conductivity
base material disposed on a part of a surface of the conductive
solid electrolyte film and a catalyst for accelerating anodic
oxidation; a second electrode made of an electronic conductivity
base material disposed on the other part of the surface of the
conductive solid electrolyte film and a catalyst for accelerating
cathodic reduction; and a platinum group catalyst supported by a
porous metal oxide disposed to be adjacent to the second
electrode.
14. The nitrogen oxide decomposing element according to claim 13,
wherein the first and the second electrodes are respectively
provided on opposed plane surfaces of the surface of the conductive
solid electrolyte film.
15. The nitrogen oxide decomposing element according to claim 13,
wherein the first and the second electrodes are provided on a same
plane surface of the surface of the conductive solid electrolyte
film.
16. The nitrogen oxide decomposing element according to claim 13,
wherein a mixed layer including an electronic conductivity base
material, a solid electrolyte film, a platinum group catalyst and a
cathodic catalyst is provided between the conductive solid
electrolyte film and the second electrode.
17. The nitrogen oxide decomposing element according to claim 13,
wherein the metal oxide is an acidic oxide.
18. The nitrogen oxide decomposing element according to claim 17,
wherein the metal oxide includes at least one component of titanium
dioxide, zirconium dioxide, aluminum oxide, silicon oxide,
magnesium oxide, and tin oxide.
19. The nitrogen oxide decomposing element according to claim 13,
wherein the metal oxide is an amphoteric oxide.
20. The nitrogen oxide decomposing element according to claim 19,
wherein the metal oxide includes at least one component of titanium
dioxide, zirconium dioxide, aluminum oxide, silicon oxide,
magnesium oxide, and tin oxide.
21. The nitrogen oxide decomposing element according to claim 13,
wherein the platinum group catalyst includes at least one component
of platinum, iridium, and palladium.
22. A nitrogen oxide decomposing apparatus, comprising: the
nitrogen oxide decomposing element according to any one of claims
13 to 21 and a frame holding this; a gas supply ports for supplying
an anode gas and a cathode gas into the frame; a gas exhaust port
for exhausting the gases in the frame to outside; and a power
source for applying a DC voltage between the first and the second
electrodes.
23. The nitrogen oxide decomposing apparatus according to claim 22,
wherein a gas containing water vapor is supplied as the anode
gas.
24. The nitrogen oxide decomposing apparatus according to claim 22,
wherein a gas containing nitrogen oxide is supplied as the cathode
gas.
25. The nitrogen oxide decomposing apparatus according to claim 22,
wherein the nitrogen oxide decomposing apparatus further comprises
a sensor for detecting a concentration of nitrogen oxide, and a
control device for controlling a magnitude of a current flowing
between the first and the second electrodes and an energization
time in accordance with the concentration of the nitrogen oxide
detected by the sensor.
26. The nitrogen oxide decomposing apparatus according to claim 25,
wherein the sensor is located in a vicinity of the platinum group
catalyst supported by the metal oxide.
Description
TECHNICAL FIELD
[0001] The present invention relates to a nitrogen oxide
decomposing element for decomposing and removing nitrogen oxide and
a nitrogen oxide decomposing apparatus including the same.
BACKGROUND ART
[0002] A nitrogen oxide purging system for decomposing and removing
nitrogen oxide has various uses, such as an exhaust gas treatment
of an automobile, a distributed cogeneration system, and air
cleaning of an enclosed space such as a long tunnel or a factory,
and increased demand is expected into the future. As a conventional
technique to remove nitrogen oxide, for example, there is
JP-A-2002-153755 as patent document 1. This patent document 1
discloses a method of purging nitrogen oxide NOx by using ammonia
as a reductant. There is disclosed that in this method, an ammonia
molecule (NH.sub.3molecule) donates an electron through an adjacent
noble metal to nitrogen monoxide (NO) adsorbed on the noble metal,
and as a result, the nitrogen monoxide (NO) becomes apt to
dissociate into a (N atoms) become a nitrogen molecule (N.sub.2
molecule). At this time, the temperature of a flowing gas is
400.degree. C.
[0003] As another prior art to remove nitrogen oxide, there is
JP-A-11-342313 as patent document 2. The patent document 2
discloses a method of treating a harmful substance-containing gas
and an apparatus therefor, in which ozone as a highly safe oxidizer
is used to be capable of treating a gas containing harmful
substances such as various organic contaminants, malodorous
components, and bacteria. The patent document 2 proposes that after
ozone is added to and mixed with the gas containing the harmful
substances, the gas is passed through an adsorbent layer filled
with high silica adsorbent for adsorbing the ozone and for
adsorbing the harmful substances, so that the harmful substances in
the gas are made harmless by the action of the ozone.
[0004] However, the method proposed in patent document 1 has
problems that it is not desirable to use ammonia in consideration
for the environment and human body, and further, it is necessary to
perform the treatment at a high temperature of 400.degree. C., it
is difficult to perform the treatment adapted to variations in the
concentration of nitrogen oxide, and the treatment of unreacted
ammonia is required. Also in the method of patent document 2, in
the case where the adsorbed nitrogen oxide is desorbed to reuse the
adsorbent, it is necessary to perform the treatment at a high
temperature of 300 to 400.degree. C.
[0005] The invention has been made to solve the foregoing problems,
and a first object thereof is to propose a nitrogen oxide
decomposing element capable of performing a treatment at a
relatively low temperature without using a material, which is
suspected to have influence on the environment and human body, as
an oxidant or a catalyst.
[0006] A second object thereof is to propose a nitrogen oxide
decomposing apparatus using the above nitrogen oxide decomposing
element.
DISCLOSURE OF THE INVENTION
[0007] A nitrogen oxide decomposing element of the invention
includes a conductive solid electrolyte film for selectively
allowing a hydrogen ion to pass through, a first electrode made of
an electronic conductivity base material disposed on a part of a
surface of the conductive solid electrolyte film and a catalyst for
accelerating anodic oxidation, a second electrode made of an
electronic conductivity base material disposed on the other part of
the surface of the conductive solid electrolyte film and a catalyst
for accelerating cathodic reduction, and a platinum group catalyst
supported by a porous metal oxide disposed to be adjacent to the
second electrode.
[0008] According to the nitrogen oxide decomposing element of the
invention, the nitrogen oxide decomposing element is obtained in
which a treatment can be performed at a relatively low temperature
(60.degree. C. to 80.degree. C.) without using a material, which is
suspected to have influence on the environment and human body, as
an oxidant or a catalyst.
[0009] Besides, a nitrogen oxide decomposing apparatus of the
invention includes the nitrogen oxide decomposing element, a frame
holding this, a gas supply ports for supplying an anode gas and a
cathode gas into this frame, a gas exhaust port for exhausting the
gases in the frame to outside, and a power source for applying a DC
voltage between the first and the second electrodes.
[0010] According to the nitrogen oxide decomposing apparatus of the
invention, the nitrogen oxide decomposing apparatus is obtained in
which a treatment can be performed at a relatively low temperature
(60.degree. C. to 80.degree. C.) without using a material, which is
suspected to have influence on the environment and human body, as
an oxidant or a catalyst.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a schematic view showing a nitrogen oxide
decomposing apparatus of embodiment 1 of the invention.
[0012] FIG. 2 is a view showing a current effect of the nitrogen
oxide decomposing apparatus of embodiment 1 of the invention with
respect to the removal of nitrogen monoxide at 60.degree. C.
[0013] FIG. 3 is a view showing a current effect of the nitrogen
oxide decomposing apparatus of embodiment 1 of the invention with
respect to the removal of nitrogen monoxide at 70.degree. C.
[0014] FIG. 4 is a view showing a current effect of the nitrogen
oxide decomposing apparatus of embodiment 1 of the invention with
respect to the removal of nitrogen monoxide at 80.degree. C.
[0015] FIG. 5 is aview showing the current effects of the nitrogen
oxide decomposing apparatus of embodiment 1 of the invention with
respect to the removal of nitrogen oxide at 60.degree. C.,
70.degree. C. and 80.degree. C.
[0016] FIG. 6 is a schematic view showing a nitrogen oxide
decomposing apparatus of embodiment 3 of the invention.
[0017] FIG. 7 is a view showing the operation and effect of the
nitrogen oxide decomposing apparatus of embodiment 3 of the
invention.
[0018] FIG. 8 is a schematic view showing a nitrogen oxide
decomposing apparatus of embodiment 4 of the invention.
BEST MODE FOR CARRYING OUT THE INVENTION
[0019] Hereinafter, embodiments of the invention will be described
with reference to the drawings.
EMBODIMENT 1
[0020] FIG. 1 is a schematic view showing a nitrogen oxide
decomposing element of embodiment 1 of the invention and a
structure of a nitrogen oxide decomposing apparatus.
[0021] The nitrogen oxide decomposing apparatus of embodiment 1
includes a nitrogen oxide decomposing element 1 and a frame 7 for
housing it. The nitrogen oxide decomposing element 1 includes a
conductive solid electrolyte film 2 for selectively allowing a
hydrogen ion to pass through, a first electrode layer 3 made of an
electronic conductivity base material disposed to be in contact
with a part of a surface of the solid electrolyte film 2 and a
catalyst (hereinafter referred to as an anodic catalyst) for
accelerating anodic oxidation, a second electrode layer 4 made of
an electronic conductivity base material disposed to be in contact
with the other part of the surface of the solid electrolyte film 2
and a catalyst (hereinafter referred to as a cathodic catalyst) for
accelerating cathodic oxidation, and a platinum group catalyst 6
supported by a porous metal oxide 5 disposed to be adjacent to the
second electrode layer 4.
[0022] The solid electrolyte film 2 has plane surfaces 2a and 2b
opposite to each other, and the first electrode layer 3 and the
second electrode layer 4 are respectively formed to be in close
contact with the plane surfaces 2a and 2b.
[0023] In embodiment 1, as the solid electrolyte film 2, Nafion 117
(trade name) made by Dupont Company is used. As each of the first
electrode layer 3 and the second electrode layer 4, a feeding body
is used in which a porous platinum thin film layer and a porous
titanium are laminated by plating, and a titanium surface of the
porous titanium is further plated with platinum, and the platinum
plating of the surface has functions of the anodic catalyst and the
cathodic catalyst.
[0024] In embodiment 1, although platinum is used as both the
anodic catalyst and the cathodic catalyst, it is not necessary that
these are the same, and as the anodic catalyst, in addition to
platinum, it is possible to use iridium, iridium oxide or the like.
In the case where the first electrode layer 3 and the second
electrode layer 4 respectively do not include the anodic catalyst
and the cathodic catalyst, unless a very high voltage is applied to
the nitrogen oxide decomposing element 1, the reactions of anodic
oxidation and cathodic reduction are not quickly promoted, and
therefore, these catalysts are indispensable.
[0025] Further, the porous metal oxide 5 having the function of
occluding and concentrating nitrogen oxide is disposed to be in
contact with the second electrode layer 4, and platinum as the
platinum group catalyst 6 is supported by the metal oxide 5 at a
weight ratio of 1 wt %. That is, the metal molecules of the
platinum group catalyst 6 are contained in pores of the porous
metal oxide 5. As a method of causing the porous metal oxide 5 to
support the platinum group catalyst 6, a porous body is immersed in
a solution containing a platinum component, for example,
achloroplatinic acid (H.sub.2PtCl.sub.6) solution, and is heated up
to about 400.degree. C., so that platinum is supported by the
porous body. In embodiment 1, hydrogen-terminated zeolite is used
as the porous metal oxide 5. The zeolite includes aluminum oxide
and silicon oxide as components, and is denoted by using a general
formula W.sub.mZ.sub.nO.sub.2n.sH.sub.2O. Where, in this general
formula, W denotes one of sodium (Na), calcium (Ca), potassium (K),
barium (Ba) and strontium (Sr), Z denotes silicon (Si)+aluminum
(Al), the ratio of silicon (Si) to aluminum (Al) is larger than 1
(Si/Al>1), and s is not constant.
[0026] The metal oxide 5 used in embodiment 1 is an acidic oxide or
an amphoteric oxide. The acidic oxide reacts with a base (alkali)
to form salt, and a high oxidation number oxide of transition
metal, for example, titanium oxide (TiO.sub.2) belongs to this. On
the other hand, the amphoteric oxide is one oxide which indicates
an acidity to a base and indicate a basicity to an acid, and for
example, aluminum oxide (Al.sub.2O.sub.3) belongs to this.
[0027] The nitrogen oxide decomposing element 1 constructed of the
solid electrolyte film 2, the first electrode layer 3, the second
electrode layer 4, and the platinum group catalyst 6 supported by
the metal oxide 5 is held by the frame 7. The frame 7 is
constructed of a circular frame body 7a, an upper cover body 7b
airtightly joined to its upper end face through an O-ring 8a, and a
lower cover body 7c airtightly joined to its lower end face through
an O-ring 8b. The space in the frame 7 is divided into one at the
side of the first electrode 3 and one at the side of the second
electrode 4 by the solid electrolyte film 2, and an upper treatment
chamber 7d and a lower treatment chamber 7e are formed. An anode
gas supply port 9 and an anode gas exhaust port 10 are attached to
the upper cover body 7b, and a mixed gas of water vapor (H.sub.2O)
and nitrogen (N.sub.2) is supplied into the upper treatment chamber
7d through the anode gas supply port 9. The nitrogen (N.sub.2) may
be replaced by air. A cathode gas supply port 11 and a cathode gas
exhaust port 12 are attached to the lower cover body 7c, and a
mixed gas of nitrogen monoxide (NO) as nitrogen oxide, oxygen
(O.sub.2) and helium (He) is supplied into the lower treatment
chamber 7e through the cathode gas support port 11.
[0028] Reactions at the respective places of the nitrogen oxide
decomposing element 1 in embodiment 1 are as follows.
[0029] Reaction (anodic reaction) on the first electrode layer
H.sub.2O.fwdarw.2H.sup.++1/2O.sub.2+2e.sup.- (chemical formula
1)
[0030] Reaction (cathodic reaction) on the second electrode
layer
2H.sup.++1/2O.sub.2+2e.sup.-.fwdarw.H.sub.2O (chemical formula
2)
2H.sup.++2e.sup.-.fwdarw.H.sub.2 (chemical formula 3)
2H.sup.++2NO+2e.sup.-.fwdarw.N.sub.2+H.sub.2O+1/2O.sub.2 (chemical
formula 4)
2H.sup.++2e.sup.-+1/2NO+1/4O.sub.2.fwdarw.1/4N.sub.2+H.sub.2O
(chemical formula 5)
2H.sup.++2e.sup.-+2/3NO+1/3O.sub.2.fwdarw.1/3N.sub.2O+H.sub.2O
(chemical formula 6)
N.sub.2O+2H.sup.++2e.sup.-.fwdarw.N.sub.2+H.sub.2O (chemical
formula 7)
[0031] Reaction on the platinum group catalyst (cathode side)
H.sub.2+2NO.fwdarw.N.sub.2+H.sub.2O+1/2O.sub.2 (chemical formula
8)
2H.sub.2+NO+1/2O.sub.2.fwdarw.2/1N.sub.2+2H.sub.2O (chemical
formula 9)
3/2H.sub.2+NO+1/2O.sub.2.fwdarw.1/2N.sub.2O+3/2H.sub.2O (chemical
formula 10)
N.sub.2O+H.sub.2.fwdarw.N.sub.2+H.sub.2O (chemical formula 11)
[0032] The function of the nitrogen oxide decomposing element 1 of
embodiment 1 will be described with reference to the chemical
formula 1 to the chemical formula 11. A nitrogen gas containing
water vapor is supplied through the anode gas supply port 9 into
the upper treatment chamber 7d at the side of the first electrode
layer 3, and is made to come in contact with the first electrode
layer 3. At the same time, a gas containing nitrogen oxide is
supplied through the cathode supply port 11 into the lower
processing chamber 7e at the side of the second electrode layer 4,
and is made to come in contact with the second electrode layer 4.
In this state, the energization of a DC power source 13 is started,
and when a DC voltage is applied between the first and the second
electrode layers 3 and 4, the first electrode layer 3 becomes an
anode, the second electrode layer 4 becomes a cathode, and the
anodic oxidation and cathodic reduction occur by the actions of the
catalysts provided in the respective layers.
[0033] First, in the first electrode layer 3 as the anode, as
indicated by the formula (chemical formula 1), the water molecule
(H.sub.2O) is electrolyzed and the hydrogen ion (H.sup.+) is
produced. The hydrogen ion is moved to the side of the second
electrode 4 through the solid electrolyte film 2, reacts with the
nitrogen oxide (NO) on the second electrode layer 4, and as
indicated by (chemical formula 4) and (chemical formula 5), the
nitrogen oxide is electrochemically reduced and decomposed into the
nitrogen molecule (N.sub.2) and water molecule. Besides, as
indicated by the formula (chemical formula 6), in the case where
nitrous oxide (N.sub.2O) is produced, it is further reduced and
decomposed as indicated by the formula (chemical formula 7), and is
decomposed into the nitrogen molecule and water molecule. On the
platinum group catalyst 6 at the cathode side, the hydrogen
molecule (chemical formula 3) produced on the second electrode 4
and the nitrogen oxide react with each other by the action of the
platinum group catalyst 6, and the nitrogen oxide is chemically
reduced and decomposed as indicated by the formulas (chemical
formula 8) to (chemical formula 11).
[0034] As stated above, in the nitrogen oxide decomposing element 1
of embodiment 1, the nitrogen oxide is decomposed by two kinds of
reactions, that is, the chemical reductive reaction (formulas
(chemical formula 8) to (chemical formula 11)) in which only
molecules are involved, and the electrochemical reductive reaction
(formulas (chemical formula 1) to (chemical formula 7)) in which
ions are involved. There is a case where these two kinds of
reactions occur at the same time, and there is a case where only
one of them occurs.
[0035] FIGS. 2, 3 and 4 show current effects with respect to the
removal of nitrogen oxide in the case where in the nitrogen oxide
decomposing apparatus constructed as described above, the area of
each of the reaction surfaces, that is, the first and the second
electrode layers 3 and 4 is 0.8 cm.sup.2, nitrogen monoxide, as the
nitrogen oxide, having a concentration of 1000 ppm and contained in
helium (He) gas is supplied at a flow rate 10 ml/min, and a DC
constant current is supplied between the first and the second
electrode layers 3 and 4. Here,the nitrogen oxide (NOx) is the sum
of NO and NO.sub.2. In FIGS. 2, 3 and 4, the ratios of NOx
decomposed at 60.degree. C., 70.degree. C. and 802 C. are obtained
by analyzing gases exhausted from the cathode gas exhaust port 12
by an analyzer.
[0036] That is, they are obtained by (ratio % of decomposed
NOx)={(NOx concentration (0.1%) at the supply port)-(NOx
concentration % at the exhaust port)}.div.(NOx concentration (0.1%)
at the supply port).times.100. Here, the NOx concentration is the
sum of the concentrations of NO and NO.sub.2.
[0037] In FIG. 5, the vertical axis indicates the nitrogen monoxide
concentration at the exhaust port and the horizontal axis indicates
the current, and FIGS. 2, 3 and 4 are shown as a graph. A curved
line A indicates the case of 60.degree. C. of FIG. 2, a curved line
B indicates the case of 70.degree. C. of FIG. 3, and a curved line
C indicates the case of 80.degree. C. of FIG. 4. As shown in FIG.
5, at any temperatures, as the current density increases, the
decomposition removal effect of the nitrogen oxide increases, and
in the range of the current density of 15 mA/cm.sup.2 or higher,
about 80% of the nitrogen oxide was removed. Since the nitrogen
oxide removal effect at 80.degree. C., which is highest among
these, is inferior to the results at 60.degree. C. and 70.degree.
C., it is indicated that even in the case where the temperature is
raised up to 80.degree. C. or higher, a higher effect is not
obtained. That is, the nitrogen oxide decomposing apparatus in this
embodiment can sufficiently exhibit the effect at a relatively low
temperature of 60.degree. C. to 80.degree. C.
[0038] As stated above, according to embodiment 1, there is
proposed the nitrogen oxide decomposing element 1 including the
first electrode layer 3 and the second electrode layer 4
respectively disposed on the opposed plane surfaces 2a and 2b of
the surface of the solid electrolyte film 2, and the platinum group
catalyst 6 supported by the porous metal oxide 5 disposed to be
adjacent to the second electrode layer 4. This nitrogen oxide
decomposing element 1 is held by the frame 7, the gas containing
water vapor as the anode gas is supplied through the anode gas
supply port 9 into the frame 7 and the gas containing nitrogen
oxide as the cathode gas is supplied through the cathode gas supply
port 11, and the DC voltage is applied between the first and the
second electrode layers 3 and 4 by the DC power source 13. As a
result, the nitrogen oxide decomposing apparatus is obtained which
can perform the treatment at a relatively low temperature
(60.degree. C. to 80.degree. C.) without using a material, which is
suspected to have influence on the environment or human body, as
the oxidant or the catalyst.
[0039] In embodiment 1, although the example has been described in
which the hydrogen-terminated zeolite is used as the porous metal
oxide 5 for supporting the platinum group catalyst 6, the same
effect is obtained even in the case where a metal oxide containing
at least one component of titaniumdioxide, zirconium dioxide,
aluminum oxide, silicon oxide, magnesium oxide and tin oxide is
used. Besides, in embodiment 1, although the example has been
described in which platinum is used as the platinum group catalyst
6 supported by the metal oxide 5, the same effect is also obtained
by iridium or palladium.
EMBODIMENT 2
[0040] A nitrogen oxide decomposing element of embodiment 2 (not
shown) is such that a mixed layer including an electronic
conductivity base material, a solid electrolyte film, a platinum
group catalyst and a cathodic catalyst is disposed between the
solid electrolyte film 2 of the nitrogen oxide decomposing element
1 (see FIG. 1) of embodiment 1 and the second electrode 4 and is
brought into close contact therewith. This mixed layer can be
formed by dispersing aplatinum group catalyst, a cathodic catalyst,
a fine-grained electronic conductivity base material, and a
fine-grained solid electrolyte film into a solution, heating them
to evaporate volatile components, and combining the fine grain
components with each other.
[0041] Since the electrochemical reactions described in embodiment
1 occur at an interface between each electrode and the solid
electrolyte film, the amount of reaction and the reaction speed are
increased in proportion to the area of the interface. In embodiment
2, the interface between the electrode and the solid electrolyte
film, that is, the reaction site of the electrochemical reaction is
increased at the side of the second electrode layer 4, so that the
efficiency of the electrochemical reductive reaction of the
nitrogen oxide is improved.
EMBODIMENT 3
[0042] FIG. 6 is a schematic view showing a nitrogen oxide
decomposing apparatus of embodiment 3. In the drawings, same or
equivalent parts are denoted by the same reference numerals and
their description will be omitted. The nitrogen oxide decomposing
apparatus in this embodiment includes a nitrogen oxide sensor 14
for detecting the concentration of nitrogen oxide, and a power
source/control device 15 for controlling the magnitude of a current
flowing between a first and a second current layers 3 and 4 and an
energization time in accordance with the concentration of the
nitrogen oxide detected by the nitrogen oxide sensor 14. By this,
it is possible to control the magnitude of the current flowing
through the nitrogen oxide decomposing element 1 and the
energization time in accordance with the concentration of the
nitrogen oxide. Incidentally, it is desirable that the nitrogen
oxide sensor 14 is disposed in the vicinity of a platinum group
catalyst 6 supported by a metal oxide 5 at a cathode side. For
example, the nitrogen oxide sensor 14 including a sensitive part
having a size of about {fraction (1/10)} of the nitrogen oxide
decomposing element 1 is fixed in the vicinity of the metal oxide 5
and information is extracted to the outside through a signal
line.
[0043] The operation and effect of the nitrogen oxide decomposing
apparatus of this embodiment will be described with reference to
FIG. 7. In the drawing, y1 and y2 denote previously set nitrogen
oxide concentration values, y1 denotes an energization stop
concentration, and y2 denotes an energization start concentration.
That is, at time points t1 and t3 when the nitrogen oxide
concentration detected by the nitrogen oxide sensor 14 exceeds y2,
the energization by the power source/control device 15 is started,
and the decomposition and removal of the nitrogen oxide is
performed. At time points t2 and t4 when the nitrogen oxide
concentration is lowered to y1 or less, the energization is
stopped. Thus, only in the case where the nitrogen oxide
concentration in the atmosphere becomes high, or the amount of the
nitrogen oxide occluded and stored in the platinum group catalyst 6
supported by the metal oxide 5 becomes high and the nitrogen oxide
concentration of a vapor phase in equilibrium with the amount
(occlusion concentration) becomes high, a current flows through the
nitrogen oxide decomposing element 1, and the nitrogen oxide is
decomposed and removed. Further, although not shown, the power
source/control device 15 can also operate to increase or decrease
the amount of the flowing current in accordance with the increase
or decrease amount of the nitrogen oxide concentration.
[0044] As described above, according to this embodiment, the
low-power consumption nitrogen oxide decomposing apparatus is
obtained which can deal with the concentration change of the
nitrogen oxide, and can efficiently use electric energy.
EMBODIMENT 4
[0045] FIG. 8 is a schematic view showing a nitrogen oxide
decomposing apparatus of embodiment 4 of the invention. This
embodiment 4 includes a case 1 shown in FIG. 8(a) and a case 2
shown in FIG. 8(b). Each of these cases 1 and 2 includes one gas
supply port 16 and one gas exhaust port 17. Besides, in each of
both the cases 1 and 2, a first electrode layer 3 and a second
electrode layer 4 are disposed to be separate from each other on
one surface 2a of a solid electrolyte film 2, and a metal oxide 5
and a platinum group catalyst 6 are disposed on the second
electrode layer 4.
[0046] The case 1 of FIG. 8(a) is the case in which similarly to
the gases from the gas supply ports 9 and 11 of embodiment 1, water
vapor (H.sub.2O), nitrogen gas (N.sub.2), nitrogen monoxide gas
(NO), oxygen gas (O.sub.2), and helium gas (He) are supplied from
the gas supply port 16, and a reaction with the water vapor
(H.sub.2O) occurs at the side of the first electrode 3 as the
anode. The case 2 of FIG. 8(b) is the case in which water vapor
(H.sub.2O), nitrogen gas (N.sub.2), nitrogen monoxide gas (NO),
oxygen gas (O.sub.2), helium gas (He) and hydrocarbon gas
(CH.sub.4) are supplied from the gas supply port 16, and a reaction
of the hydrocarbon (CH.sub.4) with the water vapor occurs at the
side of the first electrode layer 3 as the anode. In the drawings,
same or equivalent portions are denoted by the same reference
numerals and their description will be omitted.
[0047] In the nitrogen oxide decomposing apparatus of embodiment 4,
the first electrode layer 3 and the second electrode layer 4 are
respectively provided on the same plane surface of the surface of
the solid electrolyte film 2. The materials constituting the solid
electrolyte film 2 and the first and the second electrode layers 3
and 4 are the same as those of embodiment 1. As the platinum group
catalyst 6 supported by hydrogen-terminated zeolite as the porous
metal oxide 5, for example, iridium is provided on the second
electrode layer 4. A mixed gas of a gas containing water vapor and
a gas containing nitrogen oxide is made to come into contact with
the first and the second electrode layers 3 and 4, so that
similarly to the embodiment 1, the nitrogen oxide is decomposed and
removed. The reactions at the respective places of the nitrogen
oxide decomposing element of embodiment 4 will be set forth below
with respect to the case 1 and the case 2.
[0048] Case 1
(anode) 2H.sub.2O.fwdarw.4H.sup.++O.sub.2+4e.sup.- (chemical
formula 12)
(cathode) 2NO+4H.sup.++4e.sup.-.fwdarw.N.sub.2+2H.sub.2O (chemical
formula 13)
(total) 2NO.fwdarw.N.sub.2+O.sub.2 (chemical formula 14)
[0049] Case 2
(anode) CH.sub.4+2H.sub.2O.fwdarw.8H.sup.++CO.sub.2+8e.sup.-
(chemical formula 15)
(cathode) 4NO+8H.sup.++8e.sup.-.fwdarw.2N.sub.2+4H.sub.2O (chemical
formula 16)
(total) 4NO+CH.sub.4.fwdarw.2N.sub.2+CO.sub.2+2H.sub.2O (chemical
formula 17)
[0050] In the case 1, at the first electrode layer 3 as the anode,
as indicated by the formula (chemical formula 12), the water
molecule (H.sub.2O) is electrolyzed, and hydrogen ions (H.sup.+)
are produced. In the case 2, as indicated by the formula (chemical
formula 15), the water molecule and the hydrocarbon (CH.sub.4) are
electrolyzed, and hydrogen ions and carbon dioxide (CO.sub.2) are
produced. These hydrogen ions pass through the solid electrolyte
film 2 and are moved to the side of the second electrode layer 4,
and as indicated by the formulas (chemical formula 13) and
(chemical formula 16), the nitrogen oxide (NO) is reduced and
decomposed into the nitrogen (N.sub.2) and the water molecule
(H.sub.2O).
[0051] In embodiment 4, in contrast to embodiment 1 (see FIG. 1) in
which the space in the frame 7 is divided into the upper treatment
chamber 7d and the lower treatment chamber 7e by the solid
electrolyte film 2, the reactions at the anode side and the cathode
side occur in the same processing chamber 7f. Thus, the one gas
supply port 16 used both as the anode gas supply port 9 and the
cathode gas supply port 11 can be adopted, and as a result,the
anode gas and the cathode gas are mixed. However, since the
objective reactions occur by the actions of the anodic catalyst and
the cathodic catalyst provided in the respective electrodes, the
same effect as the embodiment 1 can be obtained. Further, since the
structural parts of the apparatus are decreased, and the
integration of the element on the plane surface becomes possible,
the nitrogen oxide decomposing apparatus can be simplified and
miniaturized. By this, the installation in the vicinity of the
source of nitrogen oxide becomes possible, and the decomposition
and removal can be efficiently performed in a high concentration
area of the nitrogen oxide.
INDUSTRIAL APPLICABILITY
[0052] The nitrogen oxide decomposing element of the invention and
the nitrogen oxide decomposing apparatus including the same have
various uses such as exhaust gas treatment of an automobile, a
distributed cogeneration system, and air cleaning of an enclosed
space such as a long tunnel or a factory.
* * * * *