JP2002012401A - Film reaction apparatus and gas synthesis system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film reaction apparatus, and a useful gas generation method, a denitration method, and an oxygen manufacturing method using the apparatus. SOLUTION: A gas synthesis system is equipped with a compressing means 13 which compresses an exhaust gas 12 from a boiler 11 for driving a generator 10, a heat exchanger 15 as a heating means which heats the compressed gas 14, a film reaction apparatus 17, in which a high pressure chamber 17H for high partial oxygen pressure and a low pressure chamber 17L for lower partial oxygen pressure are separated from each other with an oxygen ion-electron mixed electric conductive ceramic film 16 as a separating wall, and a heating means 18, which heats the film reaction apparatus 17.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a membrane reaction apparatus, a method for producing a useful gas using the apparatus, a method for denitration, a method for producing high oxygen concentrated air, and a method for producing oxygen.

[0002]

BACKGROUND ART Syngas, which is a mixture of hydrogen (H ₂ ) and carbon monoxide (CO), is produced as various synthetic raw materials such as methanol and ammonia, and as a hydrogen source for petroleum refining. Hydrogen (H ₂ ) and carbon monoxide (C
Conventionally, synthesis gas with O) is mainly produced by the following chemical reaction process.

(1) Steam reforming process [0003] Methane (C) is formed on a catalyst containing nickel (Ni) or the like as a main component.
A hydrocarbon such as H ₄ ) is reacted with steam at a high temperature. As shown in the following equation (1), the methane reforming reaction is an endothermic reaction, in which hydrocarbons are supplied in a gaseous state together with steam to a reaction tube filled with a catalyst, and heat required for the reaction is externally heated. Supply. The gas composition at the outlet of the reaction tube depends on the S / C ratio at the inlet (steam mole number / carbon mole number of raw hydrocarbon), temperature and pressure. Here, the reaction is generally performed in a high temperature range of about 400 to 1000 (to 1200 ° C.). CH ₄ + H ₂ O → CO + 3H ₂ (endothermic)… (1) CO + H ₂ O → CO ₂ + H ₂ (exothermic)… (2)

[0004] In the steam reforming process, in order to maintain the catalyst performance, it is necessary to prevent carbon deposition on the catalyst and to prevent catalyst poisoning by sulfur components contained in the raw material gas. Further, in order to prevent carbon deposition, the amount of water vapor needs to be about three times that consumed in the reaction of the formula (1). Further, in order to prevent sulfur poisoning in the exhaust gas, it is necessary to install a desulfurization device before supplying the reforming catalyst. That is, when this method is performed, a large amount of heat and steam are required to be supplied, and a pretreatment step such as desulfurization is required.

(2) Partial oxidation process For example, a hydrocarbon such as methane and oxygen are reacted on a catalyst containing nickel (Ni) or the like as a main component. CH ₄ + 1 / 2O ₂ → CO + 2H ₂ (exothermic)… (3)

This reaction is an exothermic reaction and reaches a high temperature of 1000 ° C. or more, so that a catalyst having high heat resistance is required. This partial oxidation tends to deposit carbon on the catalyst surface more easily than in the case of the steam reforming process. Not only does this carbon deposition result in a decrease in catalytic activity, but also can cause serious problems such as sometimes clogging of the catalytic reactor. Another problem is that a plant for supplying oxygen is required separately.

[0007] In view of the above problems, an object of the present invention is to provide a membrane reactor, a gas synthesis system using the same, a denitration method, and an oxygen production system.

[0008]

Means for Solving the Problems To solve the above-mentioned problems, the invention of claim 1 increases the partial pressure of oxygen gas on one surface of the oxygen ion-permeable conductive ceramic film,
While lowering the oxygen gas partial pressure on the other surface, supplying the combustion exhaust gas to the one oxygen gas partial pressure high surface, and supplying the hydrocarbon-containing gas to the other oxygen gas partial pressure low surface, Maintaining the temperature at 200 to 1200 ° C., extracting oxygen from oxygen or nitrogen oxides in the combustion exhaust gas,
Oxygen ions and electrons are moved in the oxygen ion-permeable conductive ceramic film, and the transferred oxygen ions partially oxidize hydrocarbons such as CH ₄ in the supplied gas to convert CO and H ₂ . It is characterized by obtaining.

According to the invention of claim 2, the partial pressure of oxygen gas on one surface of the oxygen-ion-permeable conductive ceramic film is increased, and the partial pressure of oxygen gas is reduced on the other surface by evacuation. The combustion exhaust gas is supplied to the surface having a high oxygen gas partial pressure, the temperature is maintained at 200 to 1200 ° C., oxygen in the combustion exhaust gas is extracted, and oxygen ions and electrons are extracted in the oxygen ion-permeable conductive ceramic film. And oxygen is obtained from the moved oxygen ions.

According to the invention of claim 3, the partial pressure of oxygen gas on one surface of the oxygen ion-permeable conductive ceramic film is increased, and the partial pressure of oxygen gas on the other surface is reduced. While supplying combustion exhaust gas to the surface with high partial pressure,
An inert gas is supplied to the other surface having a low oxygen gas partial pressure, the temperature is maintained at 200 to 1200 ° C., oxygen in the combustion exhaust gas is extracted, and oxygen ions and oxygen ions in the oxygen ion-permeable conductive ceramic film are formed. The method is characterized in that electrons are transferred and oxygen is obtained from the transferred oxygen ions.

According to a fourth aspect of the present invention, the partial pressure of oxygen gas on one surface of the oxygen ion-permeable conductive ceramic film is increased while the partial pressure of oxygen gas on the other surface is reduced. While supplying air to the surface having a high partial pressure and supplying gas containing hydrocarbon to the other surface having a low partial pressure of oxygen gas, maintaining the temperature at 200 to 1200 ° C., extracting oxygen from the air, Oxygen ions and electrons are moved in the oxygen ion-permeable conductive ceramic film, and the transferred oxygen ions partially oxidize hydrocarbons such as CH ₄ in the supplied gas to convert CO and H ₂ . It is characterized by obtaining.

According to the invention of claim 5, the partial pressure of oxygen gas on one surface of the oxygen ion-permeable conductive ceramic film is increased, and the other surface is evacuated to reduce the partial pressure of oxygen gas. Air is supplied to one of the surfaces having a high oxygen gas partial pressure, the temperature is maintained at 200 to 1200 ° C., oxygen is extracted from the air, and oxygen ions and electrons are moved in the oxygen ion-permeable conductive ceramic film. And obtaining oxygen from the transferred oxygen ions.

According to a sixth aspect of the present invention, the oxygen gas partial pressure on one surface of the oxygen ion permeable conductive ceramic film is increased, and the oxygen gas partial pressure on the other surface is reduced. Air is supplied to the surface having a high partial pressure, and inert gas is supplied to the other surface having a low partial pressure of oxygen gas.
The temperature is maintained at 00 to 1200 ° C., oxygen in the combustion exhaust gas is extracted, oxygen ions and electrons are moved in the oxygen ion-permeable conductive ceramic film, and oxygen is obtained from the moved oxygen ions. And

According to a seventh aspect of the present invention, there is provided a gas compressing means for compressing a combustion exhaust gas, a heating means for heating the compressed gas to a high temperature, the membrane reactor of the first aspect, and the membrane reactor. Heating means for heating, supplying hydrocarbons to the oxygen ion permeable conductive ceramic film, extracting oxygen from oxygen or nitrogen oxides in the combustion exhaust gas, oxygen ions and oxygen ions in the ceramic film. The electrons are transferred, and the transferred oxygen ions partially oxidize hydrocarbons such as CH ₄ in the supplied gas to convert CO and H
It is characterized by obtaining ₂ .

[0018] The invention of claim 8 provides a gas compression means for compressing combustion exhaust gas, a heating means for heating the compressed gas to a high temperature, the membrane reactor of claim 2 and the membrane reactor. Heating means for heating, the one surface of the oxygen ion-permeable conductive ceramic film is reduced in oxygen partial pressure by vacuum exhaust, and oxygen is extracted from oxygen or nitrogen oxides in the combustion exhaust gas. Oxygen ions and electrons are moved in the ceramic film, and oxygen is obtained by the transferred oxygen ions.

According to a ninth aspect of the present invention, there is provided a gas compression means for compressing a combustion exhaust gas, a heating means for heating the compressed gas to a high temperature, the membrane reactor of the third aspect, and heating the reaction vessel. Heating means for supplying an inert gas to the oxygen-ion-permeable conductive ceramic film, oxygen ions and electrons move through the ceramic, and oxygen is obtained by the transferred oxygen ions. I do.

According to a tenth aspect of the present invention, the partial pressure of oxygen gas on one surface of the oxygen ion-permeable conductive ceramic film is increased while the partial pressure of oxygen gas on the other surface is reduced. Along with supplying the combustion exhaust gas to the surface having a high partial pressure, supplying normal pressure air to the other surface having a low partial pressure of oxygen gas, maintaining the temperature at 200 to 1200 ° C., extracting oxygen from the combustion exhaust gas, Oxygen ions and electrons are moved inside the oxygen ion permeable conductive ceramic film, and the transferred oxygen ions are used to obtain oxygen-enriched air. It comprises gas compression means for compressing the combustion exhaust gas, heating means for heating the compressed gas to a high temperature, and heating means for heating the reaction vessel to obtain oxygen-enriched air. When That.

The invention of claim 11 provides a gas compression means for compressing air, a heating means for heating the compressed gas to a high temperature, the membrane reactor of claim 4, and heating the reaction vessel. A heating means for supplying hydrocarbons to the oxygen-ion-permeable conductive ceramic film, whereby oxygen ions and electrons move through the ceramic, and the transferred oxygen ions cause CH4 in the supplied gas to be increased. And the like, by partially oxidizing hydrocarbons such as CO and H ₂ .

According to a twelfth aspect of the present invention, there is provided a gas compression means for compressing air, a heating means for heating the compressed gas to a high temperature, the membrane reactor of the fifth aspect, and heating the reaction vessel. Heating means, one of the oxygen ion permeable conductive ceramic films is reduced in oxygen partial pressure by evacuation, oxygen ions and electrons move in the ceramics, and oxygen is moved by the transferred oxygen ions. It is characterized by obtaining.

According to a thirteenth aspect of the present invention, there is provided a gas compression means for compressing air, a heating means for heating the compressed gas to a high temperature, the membrane reactor of the sixth aspect, and heating the reaction vessel. Heating means, and supplies an inert gas to one of the oxygen ion-permeable conductive ceramic films,
Oxygen ions and electrons move through the ceramics, and oxygen is obtained by the transferred oxygen ions.

According to a fourteenth aspect of the present invention, the partial pressure of oxygen gas on one surface of the oxygen ion-permeable conductive ceramic film is increased, and the partial pressure of oxygen gas on the other surface is reduced. While supplying air to the surface with high partial pressure, and supplying normal pressure air to the other surface with low partial pressure of oxygen gas,
The temperature was maintained at 200 to 1200 ° C., oxygen was extracted from the air, and oxygen ions and electrons were moved in the oxygen ion-permeable conductive ceramic film. Oxygen was concentrated by the transferred oxygen ions. A membrane reactor for obtaining air, gas compression means for compressing air on one surface having a high partial pressure of oxygen gas, heating means for heating the compressed gas to a high temperature, the membrane reactor described above, And heating means for heating the container to obtain oxygen-enriched air.

According to a fifteenth aspect of the present invention, there is provided the membrane reactor according to the first or fourth aspect, wherein the hydrocarbon of the oxygen ion-permeable conductive ceramic membrane is partially oxidized to obtain CO and H _2. A catalyst active for partial oxidation of hydrocarbons is provided on the pressure side.

According to a sixteenth aspect of the present invention, in the membrane reactor of the first, second and third aspects, the oxygen ion-permeable conductive ceramic membrane is provided with NO It is characterized in that a catalyst active for decomposition of _X is provided.

The invention of claim 17 is the first or fourth aspect of the present invention.
Is characterized in that methanol is synthesized from the synthesis gas obtained from the membrane reactor using a methanol synthesis means.

The invention of claim 18 is a combination of the membrane reactor of claim 2 or claim 3 with the membrane reactor of claim 1, and firstly, the combustion exhaust gas is supplied to the membrane reactor of claim 2 or claim 3. Supply to the reactor, pull out the oxygen in the flue gas,
Subsequently, a synthesis gas of hydrogen and carbon monoxide is produced by the membrane reactor according to claim 1, and nitrogen oxides in the combustion exhaust gas are made harmless by the above-mentioned structure, and the obtained synthesis gas is produced by using a methanol synthesis means. It is characterized by the synthesis of methanol.

The invention of claim 19 is a combination of the system of claim 8 or claim 9 or claim 10 with the system of claim 7. The system is supplied to the system of claim 10 to extract oxygen in the flue gas, and subsequently, the system of claim 7 is used to produce a synthesis gas of hydrogen and carbon monoxide. Along with
It is characterized in that methanol is synthesized from the obtained synthesis gas using a methanol synthesis means.

According to a twentieth aspect of the present invention, the membrane reactor according to the second or third aspect is combined with the membrane reactor according to the first aspect, and the obtained synthesis gas and oxygen are used as fuel for a fuel cell. It is characterized in that it is used as a gas.

According to a twenty-first aspect of the present invention, there is provided the membrane reactor according to the second or third aspect, wherein the obtained oxygen is used as a combustion gas for a coal gas furnace.

[0029] The invention of claim 22 is characterized in that the membrane reactor of claim 4 is heated using waste heat of a high-temperature gas furnace.

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.

[First Embodiment] A first embodiment of the present invention will be described with reference to FIG. FIG. 1 is a schematic diagram of a synthesis gas production system according to the present embodiment. As shown in FIG. 1, the system according to the present embodiment includes, for example, a compression unit 13 that compresses a combustion exhaust gas 12 from a combustion device (boiler) 11 that drives a generator 10 and the like, and the compressed gas 1.
4, a heat exchanger 15 serving as a heating means for heating the compressed combustion exhaust gas, a purifying means 25 for purifying the compressed combustion exhaust gas, and an oxygen ion-permeable conductive ceramic film (hereinafter also referred to as "ceramic film") 16 as a partition wall. Is a high pressure chamber 17H having a high oxygen partial pressure, and the other is a low pressure chamber 17 having a low oxygen partial pressure.
It comprises a membrane reactor 17 serving as L and a heating means 18 for heating the membrane reactor 17.

The compressed / high-temperature gas 19 is supplied to the high-pressure chamber 17H, and natural gas containing hydrocarbons (eg, CH ₄ ) 20 is supplied to the low-pressure chamber 17L from the hydrocarbon supply means 21. Then, the oxygen ion-permeable conductive ceramic film 16 is heated by a heating means 18 to extract oxygen from the nitrogen oxide of the compressed / high-temperature gas 19, thereby moving oxygen ions and electrons through the ceramic film 16, The hydrocarbons 20 such as CH ₄ in the supplied gas are partially oxidized by the
A synthesis gas 22 such as O and H ₂ is obtained.

In the present embodiment, the heating means 18 heats water by means of a heat exchanger 23 for exchanging waste heat of the combustion exhaust gas 12 to produce high-temperature steam 24, and recovers the waste heat to obtain a heat utilization rate. Has been improved.

According to the above device, the ceramic film 1
Oxygen ions and electrons are transferred in 6, and the transferred oxygen ions can partially oxidize hydrocarbons 20 such as CH ₄ in the supplied natural gas to obtain CO and H ₂ .

FIG. 2 shows the principle of oxygen separation in the membrane reactor 17. As shown in FIG. 2, the membrane reactor 17 according to the present embodiment increases the partial pressure of oxygen gas on one surface of the oxygen ion-permeable conductive ceramic film 16 to increase the pressure of the high-pressure chamber 17.
H, and the low-pressure chamber 17L is formed by lowering the oxygen gas partial pressure on the other surface, and the compressed / high-temperature gas 1 which is the combustion exhaust gas is formed on one surface having a high oxygen gas partial pressure.
9 and the gas 20 containing hydrocarbons is supplied from the hydrocarbon supply means 21 to the other surface having a low partial pressure of oxygen gas from the hydrocarbon supply means 21, and the temperature in the membrane reactor 17 is raised to 200 to 1200 ° C. by the heating means 18. And oxygen is extracted from nitrogen oxides (NOx) in the compressed / high-temperature gas 19, which is the combustion exhaust gas, and oxygen ions (O ²⁻ ) and electrons (e ² ) in the oxygen ion-permeable conductive ceramic film 16 are removed. ^- )
The hydrocarbons such as CH ₄ supplied above are partially oxidized by the transferred oxygen ions (O ²⁻ ) to convert C 2 into C 4.
O and H ₂ are obtained.

That is, the oxygen ion-permeable conductive ceramic film 16 is used as a partition wall, one of which is set to a high oxygen partial pressure (high pressure chamber 17H), the other is set to a low oxygen partial pressure (low pressure chamber 17L), and the high oxygen partial pressure is set. Oxygen on the pressure side receives electrons (e ⁻ ) on the film surface and becomes oxygen ions (O ²⁻ ) as shown in the following equation (4). 1/2 O ₂ + 2e ⁻ = O ^2- … (4)

The oxygen ions (O ²⁻ ) diffuse in the oxygen ion-permeable conductive ceramic film 16 toward the low oxygen partial pressure side, and as shown in the following equation (4), the electrons on the surface on the low oxygen partial pressure side Is released to become oxygen gas (O ₂ ). Then, it reacts with the supplied hydrocarbon (for example, CH ₄ etc.) 20 and
As shown in equation (5), CO and H ₂ are synthesized by partial oxidation. O ^2- = 1/2 O ₂ + 2e ⁻ (5) CH ₄ +1/2 O ₂ → CO + 2H ₂ (6)

As shown in FIG. 3, the above reaction proceeds as the difference between the high oxygen partial pressure and the low oxygen partial pressure on both surfaces of the oxygen ion-permeable conductive ceramic film 16 as the partition wall increases.
Here, the relationship between the oxygen permeation amount of the oxygen ion permeable conductive ceramic film 16 and (J) and the oxygen partial pressure (PO ₂ ) is as follows.
It is represented by the formula (I). J · x = D · k · (P _L O ₂ ^-0.5 P _H O ₂ ^-0.5 ) (I) Here, in the formula (I), J is the oxygen transmission rate (cm ³ · min ^-1 · cm). ^-2 ) x is the thickness in the transmission direction (cm) D is the diffusion constant of oxygen ions k is a constant P _H O ₂ is a high oxygen partial pressure (atmospheric pressure) P _L O ₂ is a low oxygen partial pressure (atmospheric pressure) .

[0039] For example, when a low oxygen partial pressure (P _L O ₂₎ is a constant value (A), the oxygen transmission rate is dependent only on the high oxygen partial pressure, will behave as shown in FIG. 3, hyperoxia It is proportional to the -0.5 power of the partial pressure of oxygen.

The reaction rate at the oxygen ion permeable conductive ceramic film 16 depends on the following parameters. (1) Oxygen ion conductivity The oxygen ion conductivity of the oxygen ion-permeable conductive ceramic film 16 is preferably as large as possible, for example, 0.001.
(S / cm) or more, more preferably 0.01 to 100 (S
/ Cm) is preferable.

(2) Electronic Conductivity The electronic conductivity of the oxygen ion-permeable conductive ceramic film 16 is preferably as large as possible, for example, 0.1 (S / c).
m) or more, more preferably 1 to 1000 (S / cm). Note that the oxygen ion conductivity (σ ₀ ) and the electron conductivity (σe) generally indicate that σe> σ ₀
Where oxygen permeation amount is oxygen ion conductivity (σ ₀ )
Is governed by

(3) Film Thickness The thickness of the oxygen ion-permeable conductive ceramic film 16 is preferably as small as possible, for example, preferably in the range of 0.1 to 5000 μm, more preferably 1 to 1000 μm. Is preferred.

(4) Effective Reaction Area of the Membrane The effective reaction area of the oxygen ion permeable conductive ceramic film 16 is preferably as large as possible, but the oxygen permeation amount per unit area of the oxygen ion permeable conductive ceramic film 16 is preferable. The required area is determined from the amount of the processing gas. When the oxygen ion permeable conductive ceramic film 16 is formed in a flat plate or a cylindrical shape, as a means for increasing an effective reaction area per unit volume, the oxygen ion permeable conductive ceramic film 16 is formed into a cylindrical shape or a reciprocal shape. It is effective to make the surface of the conductive ceramic film 16 a surface structure having fine irregularities and undulations.

(5) Operating Temperature of the Membrane The operating temperature of the oxygen ion permeable conductive ceramic film 16 is 200 to 1500 ° C., preferably 200 to 12 ° C.
The temperature is preferably set to 00 ° C. More preferably, the temperature is set to 500 ° C. or higher. In order to maintain the operating temperature, it is performed by using a heating means, but by using waste heat,
System efficiency can also be improved.

(6) Supply gas pressure The oxygen partial pressure on the high pressure chamber 17H side is preferably 0.01 to 40 atm.
Preferably, it is 0.01 to 10 atm. Meanwhile, low pressure chamber
17L oxygen partial pressure, 10^-2-10^-30Barometric pressure , Preferably
Is 10^-2-10^{-twenty five}It is good to be atmospheric pressure.

As the oxygen-ion-permeable conductive ceramic film 16, La _1-x Sr _x Co _1-y Fe _y O ₃ (0 <
A dense ceramic of ABO ₃ perovskite type oxide of x <1,0 <y <1) can be exemplified. In addition, AB
Examples of materials other than the O ₃ perovskite oxide include SrFeCo _0.5 O _x .

The oxygen-ion-permeable conductive ceramic film 16 can perform not only denitration but also oxygen extraction from SOx in the combustion exhaust gas and a desulfurization reaction as shown in FIG. In addition, since the S component remains on the surface,
Although the active site disappears, it is only necessary to periodically remove the S component adhered from the surface.

The obtained useful synthesis gas 22 can be efficiently synthesized with methanol or the like by means of a synthesis means such as methanol.

[Second Embodiment] FIG. 5 is a schematic view of a membrane reactor according to a second embodiment. In FIG. 1, a planar oxygen ion permeable conductive ceramic film 16 is used as the membrane reaction device 17, but the present invention is not limited to this. As shown in FIG. The reaction vessel 33 may be formed by forming an oxygen ion-permeable conductive ceramic film 32 on the surface side of the cylindrical support 31.

The support 31 is made of a ceramic material such as stabilized zirconia or alumina as a raw material. For example, a mixture of raw ceramic particles and an organic binder is formed into a cylindrical shape by extrusion. , 1
It can be obtained by firing at 000 ° C. or higher. The porosity of the porous support after firing is 30 to 35%, and the gas permeability is good. The size of this cylindrical tube is
For example, the diameter may be 20 to 30 mm and the thickness may be 1 to 3 mm. In addition, it is preferable that the thickness is thinner from the viewpoint of gas permeability.

In the case of the embodiment shown in FIG.
The cylindrical support 31 is compressed to a high temperature state by compressing the gas 12.
To the inside and the outside with the low pressure side
(CH _Four) 34, the above ceramics
Reacts with the oxygen separated by the membrane 32 to cause partial oxidation,
Syngas (CO, H_Two) Is synthesized. The fuel
By using air instead of the flue gas 12, air
Oxygen ion permeable conductor ceramic
The membrane film 32 is moved in an ion state, and the hydrocarbons 34 and the like are moved.
Useful synthesis gas can also be synthesized by partial oxidation.
it can.

[Third Embodiment] FIG. 6 is a schematic view of a membrane reactor according to a third embodiment. The configuration of this embodiment is the same as that of the second embodiment, except that an inert gas (containing water vapor) 35 is supplied instead of the hydrocarbon 34 supplied to the external low-pressure side surface. Nitrogen oxides supplied inside are denitrated, and oxygen is produced from oxygen ions separated by the ceramic film 32. Thus, in the present embodiment, nitrogen oxides in exhaust gas from a combustion device (boiler) or the like can be rendered harmless. By using vacuum exhaust and normal-pressure air instead of the inert gas, nitrogen oxides in the combustion exhaust gas supplied inside can be denitrated.

[Fourth Embodiment] FIG. 7 is a schematic view of a membrane reactor according to a third embodiment. In the case of the embodiment shown in FIG. 7, the flue gas 12 is compressed to a high temperature state and supplied to the inside of the cylindrical support 31 and the inert gas 35 is supplied to the outside. The oxygen inside is separated by the ceramic film 32,
This means that oxygen production is being performed. By evacuating instead of the inert gas, the combustion exhaust gas 12
Pure oxygen can be produced by separating oxygen in the ceramic film 32. Furthermore, oxygen-concentrated air can be produced by flowing normal-pressure air instead of the inert gas. Nitrogen can be obtained from the gas having a low oxygen concentration after the oxygen is separated by the ceramic film 32. However, when the inert gas is supplied to the outside, the nitrogen is removed from the low pressure surface outside the ceramic film 32. By supplying the active gas 35, the exhaust gas can be effectively used.

Further, in the case of the second, third and fourth embodiments, the same effect can be obtained even if the kind of gas supplied to the inner and outer surfaces of the cylindrical support 31 is reversed. It is possible to do.

Note that the third embodiment and the fourth embodiment can perform different functions by setting the combustion exhaust gas to be supplied to individual conditions, and can perform the denitration and oxygen production separately. Can be performed simultaneously.

Also, as in the present embodiment, the high pressure chamber side 1
By supplying air instead of supplying combustion exhaust gas 12 to 7H, oxygen in the air can be concentrated.

By using the membrane reactor according to the second to fourth embodiments described above instead of the membrane reactor 17 shown in FIG. 1, a system for producing synthesis gas or oxygen can be obtained. it can.

[Fifth Embodiment] Fifth Embodiment of the Present Invention
The syngas production system according to the embodiment will be described with reference to FIG.
You. FIG. 8 is a synthesis gas production system according to the present embodiment.
FIG. In this embodiment, the waste heat of the high-temperature gas
This is a synthesis gas production system using a membrane reactor
You. As shown in FIG.
1 and the waste heat of the high temperature gas furnace 41 using helium (He).
And an intermediate heat exchanger 42 for recovery
Heating means 43 which recovered heat using helium (He)
And a membrane reaction device 44 having the same. Real truth
In the embodiment, the membrane reactor 44 is a cylindrical reactor.
In addition to the low pressure chamber 44L inside the cylinder,
A high pressure chamber 44H, which is compressed to the high pressure side cylindrical surface side to
Supply the air 45 that is
Gas (CH _Four) 46 and separated by the membrane reactor 44
By reacting with oxygen, useful synthesis gas (CO, H
_Two).

[Sixth Embodiment] A sixth embodiment of the present invention will be described with reference to FIG. FIG. 9 is a schematic diagram of a synthesis gas production system according to the present embodiment. This embodiment applies a membrane reactor to a gas turbine combined cycle,
This is a system for denitrifying nitrogen oxides in exhaust gas discharged from a gas turbine while producing synthesis gas.

As shown in FIG. 9, in the present embodiment, a gas turbine 52 that generates power using natural gas 51 as a fuel is provided.
And an exhaust heat recovery boiler 54 that uses the exhaust gas 53 from the gas turbine 52 as a heat source, and a steam turbine 55 that generates electricity using the steam generated by the exhaust heat recovery boiler 54, in a combined power generation system. An exhaust gas 53 supplied to a heat recovery boiler 54 is supplied to a membrane reactor 56 for denitration and production of a synthesis gas (CO, H ₂ ) 57.

As shown in FIG. 10, the membrane reaction device 56 has a reaction tube 63 in which an oxygen ion-permeable conductive ceramic film 63 is formed on a surface of a cylindrical support body 62 in a cylindrical container body 61. And a high pressure chamber 61
H, and supplies the compressed and heated exhaust gas 53, and supplies the natural gas 51 to the external low-pressure chamber 61 L to the gas turbine 52.
Is supplied to produce the synthesis gas 57.

[Seventh Embodiment] A seventh embodiment of the present invention will be described with reference to FIG. FIG. 11 is a schematic diagram of a synthesis gas production system according to the present embodiment. In this embodiment, a membrane reactor is applied to a gas turbine combined cycle, and only oxygen (O ₂ ) is first separated from exhaust gas 53 discharged from a gas turbine together with production of synthesis gas. This is a composite membrane reaction system for denitrifying nitrogen oxides.

As shown in FIG. 11, in the present embodiment, a gas turbine 52 that generates power using natural gas 51 as a fuel is used.
And an exhaust heat recovery boiler 54 that uses the exhaust gas 53 from the gas turbine 52 as a heat source, and a steam turbine 55 that generates electricity using the steam generated by the exhaust heat recovery boiler 54, in a combined power generation system. The exhaust gas 53 supplied to the heat recovery boiler 54 is sequentially supplied to a first-stage membrane reactor 56A and a second-stage membrane reactor 56B,
In the staged membrane reactor 56A, oxygen in the combustion exhaust gas is separated to produce oxygen, and the second staged membrane reactor 56A is used.
In B, nitrogen oxides in exhaust gas are denitrated, and natural gas 51 is partially oxidized by separated oxygen to synthesize synthesis gas 57.

The structure of the first-stage membrane reactor 56A and the second-stage membrane reactor 56B is the same as that of FIG. FIG. 12 is a drawing showing the outline of the operation. As shown in FIG. 12, in the first-stage membrane reactor 56A, only oxygen (pure O ₂ ) in the exhaust gas 53 is taken out, and the oxygen concentration in the exhaust gas 53 is reduced. Then, the nitrogen oxides in the exhaust gas are denitrified in the second-stage membrane reactor 56B, and the second-stage membrane reactor 56B
In this method, natural gas 51 separately supplied to the low pressure side is partially oxidized by oxygen separated from nitrogen oxides in exhaust gas to synthesize synthesis gas 57. When an inert gas is used for the low-pressure surface of the first-stage membrane reactor 56A through which oxygen permeates, by supplying a part of nitrogen obtained from the high-pressure surface of the second-stage membrane reactor 56B, Exhaust gas can be used effectively.

The above-obtained oxygen and synthesis gas can be used as a raw material for combustion oxygen and synthesis gas for methanol synthesis. As shown by the broken line in FIG.
The oxygen (O ₂ ) separated by the step membrane reactor 56A and the hydrogen (H ₂ ) synthesized by the synthesis gas 57 may be used as a part of the fuel used in the solid oxide fuel cell (SOFC) 71. it can.

In the present embodiment, as shown in FIG.
The resulting synthesis gas 57 is adapted to synthesize methanol 59 by a methanol synthesis system 58.

[Eighth Embodiment] An eighth embodiment of the present invention will be described with reference to FIG. FIG. 13 is a schematic diagram of a synthesis gas production system according to the present embodiment. The present embodiment is a composite membrane reaction system that separates oxygen from exhaust gas generated by using generated gas from a coal gasifier and denitrates nitrogen oxides in the exhaust gas.

As shown in FIG. 13, this embodiment comprises a furnace 83 having a combustor 81 for performing combustion therein and a reducer 82 formed above the combustor 81 for performing a gasification reaction. Pulverized coal supply means 85 for supplying pulverized coal 84 in which coal is pulverized, air supply means 87 for supplying air (oxygen) 86 for combustion, and pulverized coal for supplying pulverized coal 84 to a reducer 82 Supply means 8
And a purifying means 91 for purifying generated gas 90 generated in the gas furnace 89.
And a gas turbine 92 for generating power using the purified product gas as fuel, and a membrane reactor 94 for purifying the exhaust gas 93 of the gas turbine 92 and condensing oxygen in the exhaust gas. In the present embodiment, the membrane reactor 9
Reference numeral 4 denotes a cylindrical reactor, which has a high-pressure side inside the cylinder, a low-pressure side outside the cylinder, and supplies a high-temperature compressed exhaust gas 93 to the inside of the high-pressure side cylinder and a low-pressure outside. An inert gas 95 is supplied and separated by a membrane reactor 94 to obtain oxygen (O ₂ ).
The obtained oxygen is sent to the air supply means 87 and can be used as a part of the combustion air. Further, nitrogen obtained after separating oxygen in exhaust gas and oxygen of nitrogen oxides in the membrane reactor 94 is supplied to a gasification furnace and its peripheral equipment (B
OP) etc., for example, as a part of a carrier gas for transportation of a pulverized coal supply means or as a part of a carrier gas at the time of back washing of a purification means (filter), and It can be used as an inert gas source for the membrane reactor 94.

[Ninth Embodiment] FIG. 14 is a schematic view of a membrane reactor according to a ninth embodiment. The embodiment shown in FIG. 14 shows a case where hydrocarbon is supplied inside the support 31 and combustion exhaust gas is supplied outside the support 31. Ceramic film 32 and support 31 on the side supplying hydrocarbons
A partial oxidation catalyst 96 for hydrocarbons is installed between the catalysts to further enhance the reactivity between oxygen permeating from the high oxygen partial pressure side and hydrocarbons on the low oxygen partial pressure side, and to increase the useful synthesis gas (C
O, H ₂ ). Conventionally used Ni, Rh, etc. can be applied to the partial oxidation catalyst.

[Tenth Embodiment] FIG. 15 is a schematic view of a membrane reactor according to a tenth embodiment. The embodiment shown in FIG. 15 supplies a hydrocarbon inside the support body 31,
The case where the combustion exhaust gas is supplied to the outside of the support 31 is shown. A hydrocarbon partial oxidation catalyst 96 is installed inside the support 31 in contact with the ceramic film 32 on the hydrocarbon supply side, and the reactivity between oxygen transmitted from the high oxygen partial pressure side and the low oxygen partial pressure hydrocarbon is reduced. While further improving, a useful synthesis gas (CO, H ₂ ) is obtained. Conventionally used Ni, Rh, etc. can be applied to the partial oxidation catalyst.

[Eleventh Embodiment] FIG. 16 is a schematic view of a membrane reactor according to an eleventh embodiment. The embodiment shown in FIG. 16 supplies hydrocarbon to the outside of the support 31,
The case where the combustion exhaust gas is supplied to the inside of the support 31 is shown. A hydrocarbon partial oxidation catalyst 96 is provided on a part or the whole of the outer surface of the ceramic film 32 on the side to supply hydrocarbons, and the oxygen permeating from the high oxygen partial pressure side inside the support 31 and the low oxygen partial pressure side While further improving the reactivity of hydrocarbons, useful synthesis gas (CO, H ₂ ) is obtained. Conventionally used Ni, Rh, etc. can be applied to the partial oxidation catalyst.

[Twelfth Embodiment] FIG. 17 is a schematic view of a membrane reactor according to a twelfth embodiment. The embodiment shown in FIG. 17 supplies a hydrocarbon inside the support 31,
The case where the combustion exhaust gas is supplied to the outside of the support 31 is shown. By disposing the nitrogen oxide decomposition catalyst 97 on a part or the entire outer surface of the ceramic film 32 on the side to which the combustion exhaust gas is supplied, the decomposition characteristics of the nitrogen oxide in the combustion exhaust gas are further improved. A noble metal such as Pt or a perovskite oxide such as La ₀₈ Sr _0.2 CoO ₃ can be used as a catalyst for decomposing nitrogen oxides.

[Thirteenth Embodiment] FIG. 18 is a schematic view of a membrane reactor according to a thirteenth embodiment. The embodiment shown in FIG. 18 supplies hydrocarbon to the outside of the support 31,
The case where the combustion exhaust gas is supplied to the inside of the support 31 is shown. It established the NO _X decomposition catalyst 97 between the ceramic film 32 on the side of supplying the combustion exhaust gas support 31, by placing a catalyst for decomposing nitrogen oxides, further decomposition characteristics of the nitrogen oxides in the combustion exhaust gas Have improved. Noble metals such as Pt or La ₀₈ Sr _0.2 C
A perovskite oxide such as oO ₃ can be used.

[Fourteenth Embodiment] FIG. 19 is a schematic view of a membrane reactor according to a fourteenth embodiment. The embodiment shown in FIG. 19 supplies hydrocarbon to the outside of the support 31,
The case where the combustion exhaust gas is supplied to the inside of the support 31 is shown. By disposing the nitrogen oxide decomposition catalyst 97 inside the support 31 in contact with the ceramic film 32 on the side of supplying the combustion exhaust gas, the decomposition characteristics of the nitrogen oxide in the combustion exhaust gas are further improved. A noble metal such as Pt or a perovskite oxide such as La ₀₈ Sr _0.2 CoO ₃ can be used as a catalyst for decomposing nitrogen oxides.

When the hydrocarbon is supplied to the inside of the support 31, the ninth, tenth, and twelfth embodiments can be used in combination.
In the case where the hydrocarbon is supplied to the outside of
Embodiment 13 and Embodiment 14 can be used in combination.

[0076]

As described above, according to the first aspect of the present invention, the oxygen gas partial pressure on one surface of the oxygen ion-permeable conductive ceramic film is increased, and the oxygen gas on the other surface is increased. The partial pressure is lowered, and the combustion exhaust gas is supplied to one surface having a high partial pressure of oxygen gas, and the gas containing hydrocarbon is supplied to the other surface having a low partial pressure of oxygen gas. And oxygen is extracted from oxygen or nitrogen oxides in the combustion exhaust gas, and oxygen ions and electrons are moved in the oxygen ion-permeable conductive ceramic film.
CO and H ₂ can be obtained by partially oxidizing hydrocarbons such as CH ₄ in the supplied gas. Therefore, according to the present invention, it is possible to synthesize a synthesis gas from a combustion exhaust gas and a natural gas (such as CH ₄ ), and it is possible to greatly reduce the production cost of the synthesis gas.

According to the invention of claim 2, the oxygen gas partial pressure on one surface of the oxygen ion-permeable conductive ceramic film is increased, and the oxygen gas partial pressure on the other surface is decreased.
The combustion exhaust gas is supplied to one surface having a high partial pressure of oxygen gas, and the other surface having a low partial pressure of oxygen gas is discarded in a vacuum. The temperature is maintained at 200 to 1200 ° C. From the oxygen ions and electrons in the oxygen ion permeable conductive ceramics film, oxygen can be obtained from the transferred oxygen ions. As a result, nitrogen oxides contained in the fuel exhaust gas are separated into nitrogen and oxygen to render them harmless, and pure oxygen can be produced on a surface having a low oxygen partial pressure.

According to the invention of claim 3, the oxygen gas partial pressure on one surface of the oxygen ion-permeable conductive ceramic film is increased, and the oxygen gas partial pressure on the other surface is reduced.
While supplying the combustion exhaust gas to one surface having a high partial pressure of oxygen gas and supplying the inert gas to the other surface having a low partial pressure of oxygen gas, the temperature is maintained at 200 to 1200 ° C. Is extracted and oxygen ions and electrons are moved in the oxygen ion-permeable conductive ceramic film, so that oxygen can be obtained from the moved oxygen ions. Therefore, it is possible to selectively extract oxygen contained in the fuel exhaust gas into the inert gas and produce a nitrogen-oxygen mixed gas having an adjusted oxygen concentration.

According to the invention of claim 4, the partial pressure of oxygen gas on one surface of the oxygen ion-permeable conductive ceramic film is increased, and the partial pressure of oxygen gas on the other surface is reduced.
While supplying air to the surface with high oxygen gas partial pressure,
A hydrocarbon-containing gas is supplied to the other surface having a low oxygen gas partial pressure, the temperature is maintained at 200 to 1200 ° C., oxygen is extracted from the air, and oxygen is introduced into the oxygen ion-permeable conductive ceramic film. Since ions and electrons are transferred, hydrocarbons such as CH ₄ in the supplied gas are partially oxidized by the transferred oxygen ions to produce CO 2.
And H ₂ can be obtained. Therefore, by supplying air other than the combustion exhaust gas, production of synthesis gas and production of oxygen become possible.

According to the invention of claim 5, the partial pressure of oxygen gas on one surface of the oxygen ion-permeable conductive ceramic film is increased, and the other surface is evacuated to reduce the partial pressure of oxygen gas. Then, air is supplied to one surface having a high partial pressure of oxygen gas, the temperature is maintained at 200 to 1200 ° C., oxygen is extracted from the air, and oxygen ions and electrons are extracted in the oxygen ion-permeable conductive ceramic film. The oxygen ions can be obtained from the transferred oxygen ions. Therefore, pure oxygen can be produced by selectively extracting oxygen from the air.

According to the invention of claim 6, the oxygen gas partial pressure on one surface of the oxygen ion-permeable conductive ceramic film is increased, and the oxygen gas partial pressure on the other surface is decreased.
While supplying air to the surface with high oxygen gas partial pressure,
An inert gas is supplied to the other surface having a low oxygen gas partial pressure, the temperature is maintained at 200 to 1200 ° C., oxygen in the combustion exhaust gas is extracted, and oxygen ions and oxygen ions in the oxygen ion-permeable conductive ceramic film are formed. By transferring electrons, oxygen can be obtained from the transferred oxygen ions. Therefore, a nitrogen-oxygen mixed gas in which oxygen in the air is selectively taken out and the oxygen concentration is adjusted can be produced.

According to the invention of claim 7, gas compression means for compressing the combustion exhaust gas, heating means for heating the compressed gas to a high temperature, the membrane reactor of claim 1, and the membrane reaction apparatus Heating means for heating the container, supplying hydrocarbons to the oxygen ion permeable conductive ceramic film, extracting oxygen from oxygen or nitrogen oxide in the combustion exhaust gas, and removing oxygen from the ceramic film. Since ions and electrons are moved, hydrocarbons such as CH ₄ in the supplied gas are partially oxidized by the moved oxygen ions to obtain CO and H ₂ .

According to the invention of claim 8, gas compression means for compressing combustion exhaust gas, heating means for heating the compressed gas to a high temperature, the membrane reactor of claim 2, and the reaction vessel Heating means for heating the oxygen-permeable conductive ceramics film, and evacuating one surface of the oxygen-ion-permeable conductive ceramics film to low oxygen partial pressure, extracting oxygen from nitrogen oxides in the combustion exhaust gas, and removing the ceramics. Since oxygen ions and electrons are moved in the film, pure oxygen can be obtained on the evacuated side by the moved oxygen ions.

According to the invention of claim 9, gas compression means for compressing the combustion exhaust gas, heating means for heating the compressed gas to a high temperature, the membrane reactor of claim 3, and the reaction vessel And heating means for heating the oxygen ion-permeable conductive ceramics film to supply an inert gas to move the oxygen ions and electrons through the ceramic. Obtainable.

According to the tenth aspect of the present invention, the oxygen gas partial pressure on one surface of the oxygen ion-permeable conductive ceramic film is increased, and the oxygen gas partial pressure on the other surface is decreased. While supplying the combustion exhaust gas to the surface having a high oxygen gas partial pressure and supplying normal pressure air to the other surface having a low oxygen gas partial pressure, the temperature is maintained at 200 to 1200 ° C., and oxygen is extracted from the combustion exhaust gas. Wherein oxygen ions and electrons are moved in the oxygen ion-permeable conductive ceramics membrane, and oxygen-enriched air is obtained by the transferred oxygen ions. Gas compression means for compressing the combustion exhaust gas on the surface having a high gas partial pressure, heating means for heating the compressed gas to a high temperature, the membrane reactor, and heating means for heating the reaction vessel From becoming Te, it can be oxygen obtain enriched air.

According to the eleventh aspect of the present invention, a gas compressing means for compressing air, a heating means for heating the compressed gas to a high temperature, the membrane reactor of the fourth aspect, and the reactor A heating means for heating, supplying hydrocarbons to the oxygen-ion-permeable conductive ceramic film, oxygen ions and electrons move through the ceramic, and the transferred oxygen ions cause CO and H ₂ can be obtained by partially oxidizing a hydrocarbon such as CH ₄ .

According to the invention of claim 12, gas compression means for compressing air, heating means for heating the compressed gas to a high temperature, the membrane reactor of claim 5, and the reaction vessel Heating means for heating, one of the oxygen ion permeable conductive ceramics film is reduced in oxygen partial pressure by evacuation, oxygen ions and electrons move the ceramics, by the moved oxygen ions, Oxygen can be obtained.

According to a thirteenth aspect of the present invention, a gas compressing means for compressing air, a heating means for heating the compressed gas to a high temperature, the membrane reactor of claim 6, and the reactor Heating means for heating, supplying an inert gas to one of the oxygen ion-permeable conductive ceramic films, oxygen ions and electrons move through the ceramics, and oxygen is moved by the transferred oxygen ions. Obtainable.

According to the fourteenth aspect, the oxygen gas partial pressure on one surface of the oxygen ion-permeable conductive ceramic film is increased while the oxygen gas partial pressure on the other surface is reduced. While supplying air to the surface having a high oxygen gas partial pressure and supplying normal pressure air to the other surface having a low oxygen gas partial pressure, maintaining the temperature at 200 to 1200 ° C. and extracting oxygen from the air, By moving oxygen ions and electrons within the oxygen ion permeable conductive ceramic film,
A membrane reactor for obtaining oxygen-enriched air by the transferred oxygen ions, a gas compression means for compressing air on one surface having a high oxygen gas partial pressure, and a heating for heating the compressed gas to a high temperature Means, the above-mentioned membrane reactor, and a heating means for heating the above-mentioned reaction vessel, so that oxygen-enriched air can be obtained.

According to a fifteenth aspect of the present invention, in the membrane reactor according to the first or fourth aspect, low oxygen is obtained by partially oxidizing hydrocarbons of the oxygen-ion-permeable conductive ceramic film to obtain CO and _2. By installing a catalyst active in partial oxidation of hydrocarbons on a part of the partial pressure side, the partial oxidation performance of hydrocarbons can be improved, and a useful synthesis gas can be obtained.

According to a sixteenth aspect of the present invention, in the membrane reactor according to the first, second, or third aspect, the oxygen ion-permeable conductive ceramic membrane on the high oxygen partial pressure side for supplying the combustion exhaust gas. By disposing a catalyst active in the decomposition of NOx on a part of the surface, the NOx decomposition characteristics in the combustion exhaust gas can be further improved.

According to the invention of claim 17, claim 1
Alternatively, methanol can be synthesized by synthesizing the synthesis gas obtained from the membrane reactor according to claim 4 with methanol synthesizing means, thereby improving system efficiency.

According to the invention set forth in claim 18, claim 2 is provided.
Alternatively, the membrane reactor according to claim 3 and the membrane reactor according to claim 1 are combined. First, the combustion exhaust gas is supplied to the membrane reactor according to claim 2 or 3, and oxygen in the combustion exhaust gas is extracted. And producing a synthesis gas of hydrogen and carbon monoxide in the membrane reactor of claim 1, detoxifying nitrogen oxides in the combustion exhaust gas by the above-mentioned structure, and converting the obtained synthesis gas into methanol using methanol synthesis means. Can be synthesized, and the system efficiency is improved.

According to the invention of claim 19, claim 8
Alternatively, the system according to claim 9 or claim 10 is combined with the system according to claim 7, and first, the flue gas is supplied to the system according to claim 8 or claim 9 and the oxygen in the flue gas is supplied. , Followed by production of hydrogen, carbon monoxide syngas by the system of claim 7,
With the above configuration, nitrogen oxides in the combustion exhaust gas can be rendered harmless, and the obtained synthesis gas can be used to synthesize methanol using a methanol synthesis means, further improving system efficiency.

According to the invention set forth in claim 20, claim 2 is provided.
Alternatively, the membrane reactor according to claim 3 and the membrane reactor according to claim 1 are combined, and the obtained synthesis gas and oxygen can be used as fuel gas for a fuel cell, thereby improving system efficiency.

According to the twenty-first aspect of the present invention, the second aspect is provided.
Or, using the membrane reactor of claim 3, the obtained oxygen can be used as a combustion gas in a coal gas furnace,
System efficiency is improved.

According to the invention of [Claim 22], Claim 4 is applicable.
Since the waste heat of the high-temperature gas furnace is used for heating the membrane reactor, the system efficiency is improved.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a gas synthesis system according to a first embodiment.

FIG. 2 is a principle diagram of oxygen separation and denitration.

FIG. 3 is a diagram showing a relationship between an oxygen ion permeation amount and an oxygen partial pressure.

FIG. 4 is a principle view of desulfurization.

FIG. 5 is a schematic view of a membrane reaction device according to a second embodiment.

FIG. 6 is a schematic diagram of a membrane reactor according to a third embodiment.

FIG. 7 is a schematic view of a membrane reactor according to a fourth embodiment.

FIG. 8 is a synthesis gas production system according to a fifth embodiment.

FIG. 9 is a synthesis gas production system according to a sixth embodiment.

FIG. 10 is a schematic view of a membrane reactor according to a sixth embodiment.

FIG. 11 shows a synthesis gas production system according to a seventh embodiment.

FIG. 12 is a schematic view of a membrane reaction device according to a seventh embodiment.

FIG. 13 is a synthesis gas production system according to an eighth embodiment.

FIG. 14 is a schematic view of a membrane reaction device according to a ninth embodiment.

FIG. 15 is a schematic view of a membrane reaction device according to a tenth embodiment.

FIG. 16 is a schematic view of a membrane reaction device according to an eleventh embodiment.

FIG. 17 is a schematic view of a membrane reaction device according to a twelfth embodiment.

FIG. 18 is a schematic view of a membrane reaction device according to a thirteenth embodiment.

FIG. 19 is a schematic view of a membrane reaction device according to a fourteenth embodiment.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 10 Generator 11 Combustion device (boiler) 12 Combustion flue gas 13 Compression means 14 Compressed gas 15 Heat exchanger 16 Oxygen ion / electron mixed conductive ceramic film (ceramic film) 17H High pressure chamber 17L Low pressure chamber 17 Membrane reactor 18 Heating means 19 Compressed / high-temperature gas 20 Hydrocarbon (for example, CH ₄ ) 21 Hydrocarbon supply means 22 Syngas 23 Heat exchanger 24 High-temperature steam 31 Cylindrical support body 32 Oxygen ion-permeable conductive ceramic film 33 Reaction vessel 34 Hydrocarbon 35 Inert gas 41 High-temperature gas furnace 42 Intermediate heat exchanger 43 Heating means 44 Membrane reactor 45 Air 46 Natural gas 51 Natural gas 52 Gas turbine 53 Exhaust gas 54 Exhaust heat recovery boiler 55 Steam turbine 56 Membrane reactor 57 Synthetic gas (CO, H ₂₎ 58 methanol synthesis system 59 meta Tool 61 Cylindrical container main body 62 Support 63 Oxygen ion-permeable conductive ceramic film 71 Solid oxide fuel cell (SOFC) 81 Combustor 82 Reductor 83 Fire furnace 86 Air 89 Two-stage spouted bed gasifier 92 Gas turbine 93 Exhaust gas 94 membrane reactor 95 inert gas 96 methane partial oxidation catalyst 97 NO _X decomposition catalyst

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C01B 13/02 ZAB H01M 8/06 R H01M 8/06 K B01J 23/74 321M (71) Applicant 598037570 Yamazoe ▲ Shooting ▼ 4-32 Matsugaoka, Kasuga-shi, Fukuoka (71) Applicant 000006208 Mitsubishi Heavy Industries, Ltd. 2-5-1 Marunouchi, Chiyoda-ku, Tokyo (72) Inventor Norio Miura 1-11 Hirao, Chuo-ku, Fukuoka, Fukuoka −18−1402 (72) Inventor Yasugo Teraoka 227-1-909, Oozonocho, Nagasaki City, Nagasaki Prefecture (72) Inventor Tatsumi Ishihara 959-22 Oshino, Oita City, Oita Prefecture (72) Inventor Yamazoe ▲ Nobu ▼ Fukuoka Prefecture 4-32 Matsugaoka, Kasuga-shi (72) Inventor Akihiro Yamashita 5-717-1 Fukabori-cho, Nagasaki-shi, Nagasaki F term in Sanyo Heavy Industries, Ltd. Nagasaki Research Laboratory 4D006 GA41 HA21 KA33 KA 64 KD30 KE07P KE08P KE16P KE16Q KE16R MA02 MB04 MB15 MC03 MC03X PA04 PB19 PB62 PC69 PC80 4G040 EA03 EA06 EA07 EB01 EB14 EB16 EB44 4G042 BA08 BA29 BA30 BA39 BB01 BB02 BC06 4G0B BCBC BC3 BC03 BC03 4G0B BC06 DD02

Claims (22)

[Claims] 1. An oxygen ion-permeable conductive ceramic film having a high partial pressure of oxygen gas on one surface, a low partial pressure of oxygen gas on the other surface, and burning on one surface having a high partial pressure of oxygen gas. Along with supplying the exhaust gas, a hydrocarbon-containing gas is supplied to the other surface having a low oxygen gas partial pressure, the temperature is maintained at 200 to 1200 ° C., and oxygen is removed from oxygen or nitrogen oxides in the combustion exhaust gas. The oxygen ions and the electrons are moved in the oxygen ion permeable conductive ceramics film, and the transferred oxygen ions cause C in the supplied gas.
A membrane reactor for partially oxidizing a hydrocarbon such as H ₄ to obtain CO and H ₂ . 2. The partial pressure of oxygen gas on one surface of an oxygen ion-permeable conductive ceramic film is increased, and the partial pressure of oxygen gas is reduced on the other surface by evacuation, and the partial pressure of oxygen gas on one surface is increased. Supplying the combustion exhaust gas to the surface, maintaining the temperature at 200 to 1200 ° C., extracting oxygen from the combustion exhaust gas, and moving oxygen ions and electrons within the oxygen ion-permeable conductive ceramic film. A membrane reactor characterized in that oxygen is obtained from oxygen ions. 3. An oxygen ion-permeable conductive ceramic film having a high partial pressure of oxygen gas on one surface, a low partial pressure of oxygen gas on the other surface, and burning on one surface having a high partial pressure of oxygen gas. In addition to supplying the exhaust gas, an inert gas is supplied to the other surface having a low oxygen gas partial pressure, the temperature is maintained at 200 to 1200 ° C., oxygen in the combustion exhaust gas is extracted, and the oxygen ion-permeable conductive ceramics is provided. A membrane reactor wherein oxygen ions and electrons are moved in a membrane, and oxygen is obtained from the moved oxygen ions. 4. An oxygen ion-permeable conductive ceramic film having a high partial pressure of oxygen gas on one surface, a low partial pressure of oxygen gas on the other surface, and air having a high partial pressure of oxygen on one surface. Along with
A gas containing hydrocarbon is supplied to the other surface having a low partial pressure of oxygen gas, the temperature is maintained at 200 to 1200 ° C., oxygen is extracted from the air, and oxygen is extracted from the oxygen ion-permeable conductive ceramic film. Ions and electrons are transferred, and the transferred oxygen ions cause C in the supplied gas.
A membrane reactor for partially oxidizing a hydrocarbon such as H ₄ to obtain CO and H ₂ . 5. An oxygen gas permeable conductive ceramic film having one surface having a high partial pressure of oxygen gas, and having the other surface evacuated to reduce the partial pressure of oxygen gas. Air is supplied to the high surface, the temperature is maintained at 200 to 1200 ° C., oxygen is extracted from the air, and oxygen ions and electrons are moved in the oxygen ion-permeable conductive ceramic film. A membrane reactor characterized by obtaining oxygen from ions. 6. An oxygen ion-permeable conductive ceramic film, wherein the partial pressure of oxygen gas on one surface is increased, the partial pressure of oxygen gas on the other surface is reduced, and air having a high partial pressure of oxygen is Along with
An inert gas is supplied to the other surface having a low oxygen gas partial pressure, the temperature is maintained at 200 to 1200 ° C., oxygen in the combustion exhaust gas is extracted, and oxygen ions and oxygen ions in the oxygen ion-permeable conductive ceramic film are formed. A membrane reaction apparatus comprising: moving electrons; and obtaining oxygen from the transferred oxygen ions. 7. A gas compression means for compressing the combustion exhaust gas, a heating means for heating the compressed gas to a high temperature, the membrane reactor of claim 1, and a heating means for heating the membrane reaction vessel. Supplying hydrocarbon to the oxygen ion permeable conductive ceramic film, extracting oxygen from oxygen or nitrogen oxide in the combustion exhaust gas, and moving oxygen ions and electrons in the ceramic film; C in the supplied gas by the oxygen ions
Gas synthesis system, characterized in that to obtain a CO and H ₂ to hydrocarbon H ₄ or the like by partial oxidation. 8. A gas compression means for compressing the combustion exhaust gas, a heating means for heating the compressed gas to a high temperature, a membrane reactor according to claim 2, and a heating means for heating the membrane reaction vessel. One surface of the oxygen-ion-permeable conductive ceramic film is reduced in oxygen partial pressure by vacuum evacuation, oxygen is extracted from oxygen or nitrogen oxide in the combustion exhaust gas, and oxygen ions and A gas synthesis system wherein electrons are transferred, and oxygen is obtained by the transferred oxygen ions. 9. A gas compression means for compressing combustion exhaust gas, a heating means for heating the compressed gas to a high temperature, a membrane reactor according to claim 3, and a heating means for heating the reaction vessel. An oxygen production system, characterized in that an inert gas is supplied to the oxygen ion-permeable conductive ceramic film, oxygen ions and electrons move through the ceramic, and oxygen is obtained by the transferred oxygen ions. 10. A partial pressure of oxygen gas on one surface of an oxygen ion permeable conductive ceramic film is increased, a partial pressure of oxygen gas on the other surface is decreased, and combustion is performed on a surface having a high partial pressure of oxygen gas. At the same time as supplying exhaust gas, supplying normal-pressure air to the other surface having a low partial pressure of oxygen gas, and controlling the temperature to 200 to 1
Maintaining at 200 ° C., oxygen is extracted from the combustion exhaust gas, and oxygen ions and electrons are moved in the oxygen ion-permeable conductive ceramic film, whereby oxygen-enriched air is obtained by the transferred oxygen ions. A membrane reactor, gas compression means for compressing the combustion exhaust gas on one surface having a high oxygen gas partial pressure, heating means for heating the compressed gas to a high temperature, and heating means for heating the reaction vessel. A high oxygen concentration air production system characterized by obtaining oxygen-enriched air. 11. A gas compression means for compressing air, a heating means for heating the compressed gas to a high temperature, a membrane reactor according to claim 4, and a heating means for heating said reaction vessel. A hydrocarbon is supplied to the oxygen-ion-permeable conductive ceramic film, oxygen ions and electrons move through the ceramic, and the transferred oxygen ions cause CH4 in the supplied gas.
A gas synthesis system characterized in that CO and H ₂ are obtained by partially oxidizing hydrocarbons such as 12. A gas compression means for compressing air, a heating means for heating the compressed gas to a high temperature, a membrane reactor according to claim 5, and a heating means for heating said reaction vessel. Then, one of the oxygen ion-permeable conductive ceramic films is reduced to a low oxygen partial pressure by evacuation, and oxygen ions and electrons move through the ceramics.
A gas synthesis system characterized by obtaining oxygen. 13. A gas compressor for compressing air, a heater for heating the compressed gas to a high temperature, a membrane reactor according to claim 6, and a heater for heating the reactor. A gas synthesis system characterized in that an inert gas is supplied to one of the oxygen ion permeable conductive ceramic films, oxygen ions and electrons move through the ceramics, and oxygen is obtained by the transferred oxygen ions. . 14. An oxygen ion-permeable conductive ceramic film having a high partial pressure of oxygen gas on one surface, a low partial pressure of oxygen gas on the other surface, and air having a high partial pressure of oxygen on one surface. While supplying normal-pressure air to the other surface having a low oxygen gas partial pressure, and adjusting the temperature to 200 to 120.
Maintained at 0 ° C., oxygen was extracted from the air, and oxygen ions and electrons were moved in the oxygen ion-permeable conductive ceramic film.
A membrane reactor for obtaining oxygen-enriched air; a gas compressor for compressing air on one surface having a high partial pressure of oxygen gas; a heating unit for heating the compressed gas to a high temperature; A high-oxygen-concentration air production system, comprising: an apparatus; and heating means for heating the reaction vessel, wherein oxygen-enriched air is obtained. 15. The membrane reactor according to claim 1, wherein
And the hydrocarbons in the oxygen ion permeable conductive ceramic film
CO and H after oxidation _TwoOn the low oxygen partial pressure side
Characterized by installing an active catalyst for partial oxidation of sulfur
Gas synthesis equipment. 16. The membrane reactor according to claim 1, wherein a catalyst active in the decomposition of NOx is provided on a high oxygen partial pressure side of the oxygen ion permeable conductive ceramic membrane, which supplies combustion exhaust gas. A gas synthesis device characterized by being installed. 17. A gas synthesis system, wherein methanol is synthesized from the synthesis gas obtained from the membrane reactor according to claim 1 using methanol synthesis means. 18. The membrane reactor according to claim 2 or 3 and the membrane reactor according to claim 1 are combined. First, the combustion exhaust gas is supplied to the membrane reactor according to claim 2 or 3. , The oxygen in the flue gas is extracted,
The synthesis gas of hydrogen and carbon monoxide is produced by the membrane reactor according to claim 1, the nitrogen oxides in the combustion exhaust gas are made harmless by the above configuration, and the obtained synthesis gas is converted into methanol using a methanol synthesis means. A gas synthesis system characterized by synthesis. 19. The method of claim 8, claim 9, or claim 10.
And the system of claim 7 are combined, and first, the combustion exhaust gas is supplied to claim 8 or claim 9 or claim 1
0, and the oxygen in the flue gas is extracted therefrom. Then, the synthesis gas of hydrogen and carbon monoxide is produced by the system of claim 7, and the nitrogen oxides in the flue gas are made harmless by the above configuration. And synthesizing the obtained synthesis gas using methanol synthesis means. 20. The membrane reactor according to claim 2 or 3, and the membrane reactor according to claim 1, wherein the obtained synthesis gas and oxygen are used as fuel gas for a fuel cell. Gas synthesis system. 21. A gas synthesis system using the membrane reactor according to claim 2 or 3, wherein the obtained oxygen is used as combustion gas for a coal gas furnace. 22. A gas synthesis system, wherein heating of the membrane reactor according to claim 4 is performed using waste heat of a high-temperature gas furnace.