JP2003059518A - Carbon dioxide and methane immobilization control system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carbon dioxide and methane immobilization control system with improved immobilization efficiency of carbon dioxide and methane gas which can make an effective use of excess hydrogen after reaction. SOLUTION: Methane gas, carbon dioxide gas, hydrogen gas, and nitrogen gas are guided into a gas blender 1 in a given ratio, are compressed with a pump B4a down to 0.1 to 0.9 MPa through a mixing tank 3, a pump A4, and a check valve 5, and guided into a reaction vessel 6. The guided gas makes catalytic reduction reaction at 400 to 600 deg.C. After that, it is cooled with a condenser 7 to remove vapor, and hydrogen is separated by a hydrogen separator 9, supplied from a hydrogen surge tank 10 to a fuel cell generating device 17 through a pressure regulator 11, and is made reacted with oxygen in the air to generate power.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
Gas as a supply gas source and immobilize the mixed gas in the reaction system.
Related to carbon dioxide / methane fixation control system
To produce carbon by immobilizing carbon dioxide and methane
It relates to a carbon oxide / methane immobilization control system. [0002] 2. Description of the Related Art For reducing greenhouse gas concentrations in the atmosphere,
For this purpose, various methods have been studied. Diacids in the atmosphere
Carbonized (CO₂) And power plants, steelworks, cement plants
CO emissions from large quantities₂Fixed at the emission source and refunded
One of the methods for source conversion is, for example, hydrogen (H₂) Under atmosphere
And CO₂A method for reducing carbon and converting it into finely divided carbon
Have been. The conversion method uses CO2 from air and exhaust gas.₂To
CO to separate₂Separation device and its separated CO₂The dark
CO that shrinks₂Concentrator, CO₂And H₂(Or CH ₄)
CO that reacts in the presence of a catalyst to produce finely divided carbon₂/
H₂(Or CH₄) It consists of a reaction device and the like.
This CO₂/ H₂(Or CH₄) Reactor (hereinafter referred to as diacid
Carbonized / methane fixed control system)
For example, SiO₂And Al₂O₃Ni, Co, etc., using as a carrier
With a catalyst of H₂(Or CH₄Is catalyzed by carbon
Decomposes into hydrogen and hydrogen, and immobilizes CO₂And take
And react in the presence of a catalyst to continuously produce carbon and water
I do. The reaction formula is CO₂+ 2H₂→ C + 2H₂O-
96.0 kJ / mol. Reaction between carbon dioxide and hydrogen
As can be seen from the formula, 96.0k per mol of carbon dioxide
Generates J heat. Also, fixed carbon dioxide / methane
The water vapor (H₂O)
The condensing part is provided, and the condensing part
Drain the drained water. FIG. 4 shows the conventional carbon dioxide fixation.
Carbon dioxide / methane immobilization control system for producing carbon
Is shown. Immobilize carbon dioxide and methane (or water
Element) the gas is adjusted to a predetermined mixing ratio and
It is supplied into the system as a supply gas. compressor
22 increases the pressure of the supply gas and introduces it into the heat exchanger 23
You. The heat exchanger 23 is provided with a high pressure from the exhaust pipe 28 of the reaction tank 25.
Absorbs the preheat of the hot exhaust gas,
Warm supply gas. The supply gas exchanged here is
The gas is introduced into the reaction tank 25 from the gas inlet 24. In FIG.
CO₂And CH₄H₂In the presence of a catalyst
Shown is a reaction tank 25 that reacts to produce fine carbon powder. Anti
The reaction tank 25 is provided with a reactor 25a containing a catalyst 27 therein.
The reactor 25a is supplied with gas supplied from below.
It is possible to pass between the media 27 at the top, and the catalyst 27
500 by the far infrared heater 36 of the external heating furnace 34
It is heated to about 600 ° C. SiO 2 as catalyst 27₂
And Al₂O₃Using a catalyst such as Ni, Co, etc.
Can be The supply gas touches the heated catalyst 27, and methane
The gas is decomposed into carbon and hydrogen by a catalytic reaction. And two
Carbon oxide reacts with the hydrogen to form carbon and water (steam)
Become. The carbon is implanted on the surface of the catalyst and becomes immobilized carbon 35.
You. Excessive high temperature hydrogen and steam generated during the reaction,
Unreacted carbon dioxide and methane are discharged from the reaction tank 25.
You. The gas pressure after the reaction is normal pressure or 0.1 MPa
(1kg / cm²) Driven below. The gas
Heat is exchanged through the heat exchanger 23 and enters the condenser 29 for cooling.
The water vapor condenses and becomes water and is discharged outside.
You. The remaining unreacted gas is cooled and returned to the original gas supply pipe.
Return, and again carbon dioxide and methane (or hydrogen) from outside
Is mixed with the supply gas of
You. Then, the fixing device is circulated again. After circulating the reaction gas for a predetermined time,
Turn off the power of the stabilizing device and periodically touch the immobilized carbon.
The work of taking out from the reaction tank 25 together with the medium 27 is performed. reaction
Open catalyst / carbon outlet 30 provided in the lower part of tank 25
Then, a catalyst fluidized tank provided at the lower part of the reactor 25a is maintained.
The holding mechanism 26 is released. Fixed inside the reactor 25a
The immobilized carbon 35 adhered on the catalyst 27 is converted into the catalyst 2
7 and descends from the catalyst / carbon outlet 30
Is done. The discharged immobilized carbon 35 and the catalyst 27
It is stored in the element separator 31. The two are mechanically vibrated.
To separate the carbon adhering to the catalyst 27, and use a cyclone
Separate catalyst 27 and carbon and extract only carbon to the outside
You. The catalyst from which the carbon has been separated is introduced into the catalyst regenerator 32.
It is regenerated to a new catalyst by adding an activator. Played
The catalyst 27 is again placed in the upper portion of the reaction tank 25.
Introduced into the reactor 25a inside the reaction tank 25 from the supply port 33
Is done. Repeat this process to fix carbon from carbon dioxide.
And carbon is separated and produced. [0005] SUMMARY OF THE INVENTION Conventional carbon dioxide / medium
The fixed-tanning control system is configured as described above.
From the reaction vessel 25, excess hydrogen, steam,
Unreacted carbon dioxide and methane are emitted, and the reacted gas
The pressure is normal pressure or 0.1 MPa (1 kg / cm²)
The gas is passed through the heat exchanger 23
Heat is exchanged, enters the condenser 29 and is cooled.
Condensed, discharged as water as water and the remaining unreacted gas
The gas cools and returns to the original gas supply line, and again
Circulated by the compressor 22
The cycle efficiency of the immobilization of tongue is higher than before,
5 to increase the carbon generation rate and use excess hydrogen after the reaction
There is a problem of whether or not it can be used. The present invention has been made in view of such circumstances.
Carbon dioxide / meta supplied and circulated
The efficiency of gas immobilization is higher than before,
The production rate is high, and excess hydrogen after the reaction can be used effectively.
To provide a carbon dioxide / methane fixation control system
aimed to. [0007] SUMMARY OF THE INVENTION In order to achieve the above object,
The carbon dioxide / methane immobilization control system of the present invention
Uses carbon dioxide and methane as feed gas
Carbon dioxide / methane immobilization control to immobilize water in the reaction system
In the system, a port for feeding the mixed gas to the reaction system
Pump A and the gas circulating through the mixed gas and reaction system
Pump B which pressurizes and compresses the gas to make it high pressure and sends it to the reaction tank
And the fed gas is continuously subjected to a catalytic reduction reaction for a long time.
The reaction tank and the decompressed gas after the reaction
A condenser that condenses and separates hydrogen from the condensed gas
A hydrogen separator for separating hydrogen and a gas from which hydrogen has been separated.
Pressurized and compressed again with pump B, pump B, reaction tank, condenser,
A circulation type reaction system comprising a hydrogen separator, and the hydrogen
Power generation by taking in hydrogen separated by separator and oxygen in air
And a fuel cell power generator. [0008] The carbon dioxide / methane immobilization control system of the present invention
The stem is configured as described above,
The mixed gas of carbon dioxide / methane to the reaction system
And the mixed gas and the circulating gas of the reaction system by pump B
To a high pressure, for example, about 0.9 MPa.
Send to the tank. Then, a high-pressure gas is continuously fed in the reaction tank for a long time.
It is heated continuously at 400-600 ° C to cause a catalytic reduction reaction.
Carbon can be deposited on the medium surface and fixed. reaction
After that, the gas decompressed to about 0.1 MPa
To condense water vapor and separate water. And
Hydrogen is separated from the condensed gas by a hydrogen separator,
Store in a raw surge tank. The gas from which hydrogen has been separated
Pressurized and compressed again by pump B, pump B, reaction tank, condensation
Circulates through a circulation path composed of a reactor and a hydrogen separator. Circulation
If the gas pressure in the ring path drops, the pump A
A mixed gas of carbon oxide / methane gas is fed into the reaction system.
On the other hand, the hydrogen separated by the hydrogen separator is
To adjust the pressure, and supply it to the fuel cell of the fuel cell power generator.
Is supplied and oxygen in the air is taken in to generate electricity. Generated
DC voltage is converted to AC by a quadrature converter.
Can be. The heat generated by the fuel cell is recovered by exhaust heat recovery.
Energy conversion into hot steam or hot water
Can be. [0009] DETAILED DESCRIPTION OF THE INVENTION Carbon dioxide / methane fixation of the present invention
One embodiment of a computerized control system will be described with reference to FIG.
I do. FIG. 1 shows a control system for immobilizing carbon dioxide / methane according to the present invention.
Schematic structure for stem carbon generation and hydrogen energy conversion
A diagram is shown. This carbon dioxide / methane fixation control system
Means methane gas, carbon dioxide gas, hydrogen gas, nitrogen gas
Pump A4 for feeding the mixed gas of
Pressure of the mixed gas and the gas circulating through the reaction system
And a pump B4a to be fed into the reaction tank 6
Tank 6 for continuous long-term catalytic reduction of gas
And the decompressed gas after the reaction is cooled to condense water vapor
Separating condenser 7 and hydrogen from condensed gas
A hydrogen separator 9 and a pump B4a
Pressurized and compressed again, pump B4a, reaction tank 6, condenser
7, a circulation type reaction system composed of a hydrogen separator 9 and water
Hydrogen surge tank for storing hydrogen separated by element separator 9
10 and its hydrogen pressure can be adjusted and supplied
Pressure regulator 11, pressure-regulated hydrogen and acid in air
Fuel cell, quadrature converter,
And a fuel cell power generation device 17 comprising a heat recovery device.
Have been. [0010] The present carbon dioxide / methane fixing control system
What is different from conventional systems is that carbon dioxide and
Mixed with the reaction tank 6 to fix the carbon
Syngas (newly supplied gas mixture and recirculated
The gas after the reaction) is at normal pressure or
0.1MPa (1kg / cm²) Sent below
However, in this system, to make the reaction efficient, 0.1.
Compressed and sent to a high pressure of about 9MPa, the reaction tank
6 and heated for a long time at 400-600 ° C.
That a method of depositing carbon on the medium surface is used,
Then, after the reaction, the pressure is reduced to about 0.1 MPa and cooled.
Hydrogen from separated gas and convert the hydrogen into a fuel cell power generator
17 to be able to convert energy.
You. The pump A4 is provided with a methane gas and a carbon dioxide gas.
Gas, hydrogen gas, and nitrogen gas at a predetermined ratio
To the mixing tank 3 via the valve 2
The mixed gas that is mixed and sent through the valve 2a is
Lube 2b, feed into reaction system via check valve 5
It is a pump. The pump B4a receives the mixed gas,
And a reaction system (pump B4a, reaction tank 6, condenser 7,
The gas circulating in the circulation system of the hydrogen separator 9 is set to 0.9MP.
A pump that is pressurized and compressed to about a to make it high pressure and sent to the reaction tank 6
It is. Sending the mixed gas at high pressure is a
6 to promote the reduction reaction with the catalyst in 6
This is because it can be fixed. The reaction tank 6 is internal
30wt% Ni / SiO₂Catalyst, etc.
The high-pressure gas mixture is continuously fed for 400 hours.
Heated at 600 ° C, the catalytic reduction reaction causes carbon on the catalyst surface
Is deposited. After the reaction, the condenser 7 is cooled to 0.1%.
Cool high-temperature gas decompressed to about MPa and condense water vapor.
And stored in the drain tank 8 via the valve 2c.
Water. Then, water is drained from the valve 2d if necessary. water
The element separator 9 is a device for separating hydrogen from the condensed gas.
And the reaction gas CH₄The gas is first catalyzed by CH₄
= C + 2H₂Endothermic reaction of +90.1 kj / mol,
Generates hydrogen. And carbon dioxide, methane, hydrogen,
It is converted to a mixed gas of carbon monoxide. From this gas mixture
Hydrogen is separated. The circulation type reaction system is a hydrogen separator 9
Unreacted carbon dioxide and methane emitted from
Hydrogen, carbon monoxide, nitrogen, etc.
The pump B4a is again pressurized and compressed to a high pressure.
a, a reactor 6, a condenser 7, and a hydrogen separator 9
It is a ring reaction pathway. The mixed gas is subjected to a catalytic reduction reaction in the reaction tank 6.
Then, the pressure is reduced to about 0.1 MPa, and
When the gas in the cyclic reaction system becomes low, the check valve
5 is released and the valve 2 is externally supplied by the pump A4.
Reaction gas is supplied into the system via b and check valve 5
Is done. Then, the mixed gas is pumped by the pump B4a.
It is compressed to a high pressure of about 9MPa and sent to the reaction tank 6.
Circulate through the reaction system. The hydrogen surge tank 10 stores hydrogen
The pressure regulator 1 stores hydrogen separated by the separator 9.
1 is to adjust the pressure of the hydrogen, and
It supplies hydrogen to the device. FIG. 2A shows the structure of the fuel cell power generator 17.
(B) shows the structure of the fuel cell. Fuel cell power generation equipment
The device 17 includes a fuel cell 17a, an orthogonal transformer 40,
And a collection device 41. The fuel cell 17a has a pressure
Hydrogen whose pressure has been adjusted by the force regulator 11 and oxygen in the air
This is a fuel cell that captures and generates power.
Is used. This battery has a separate
Electrode 17d composed of a platinum-based catalyst via a radiator 17C
However, on the side that takes in oxygen in the air,
The air electrode 17f is connected between the fuel electrode 17d and the air electrode 17f.
Electrolyte 17e containing acid cools the heat during the reaction at the bottom
A cooling plate 17g for cooling
To generate a DC voltage. Orthogonal transformer 40
Converts the DC voltage generated by the fuel cell 17a into AC
To take out electric power as AC output
Can be. The exhaust heat recovery device 41 uses oxygen in the fuel cell 17a.
Heat and water generated when hydrogen reacts with hydrogen
With high temperature water as steam, and as hot water
Can be used. This fuel cell power generator 17
Energy conversion efficiency is AC output when hydrogen gas is used as a reference.
About 40%, high temperature water (steam) about 20%, warm water about 20%
This is a very efficient device. Next, the carbon dioxide / methane immobilization control system
The reaction of carbon fixation of the tem will be described. First,
In the blender 1, carbon dioxide gas, methane gas, nitrogen gas
Mixed with carbon dioxide gas and methane gas at 70: 3
0 is mixed. Nitrogen gas is the internal standard gas.
Check the component ratio of the reaction system gas as necessary.
Gas from the reaction system and use a gas chromatograph
Used for analysis by mixing with the reaction gas
Flow through the reaction channel,
And flowed at a mixing ratio of 10%. By pump B4a
The mixed gas is pressurized and compressed to a high pressure of 0.9 MPa,
6, continuously heated at 400-600 ° C for a long time,
Medium 30wt% Ni / SiO₂High pressure gas mixture touches
By a medium reduction reaction, carbon is deposited on the catalyst surface. This anti
The reaction is that the methane gas in the mixed gas is
₄= C + 2H₂+ 90.1kj / mol Endothermic reaction
And generate hydrogen. And carbon dioxide, methane, water
It is converted to a mixed gas of carbon and carbon monoxide. And dioxide
The carbon undergoes a catalytic reduction reaction with hydrogen to produce CO2₂+ 2H₂= C +
2H₂O-96 kj / mol is performed, and the reaction proceeds
When running, the overall reaction is CH₄+ CO₂= 2C +
2H ₂O-5.9 kj / mol, and a small amount of heat
The carbon precipitates on the surface of the catalyst just by adding it. the first
If hydrogen is difficult to generate during the reaction,
Gas into the gas blender 1 and mix it with the mixed gas.
The reaction can be promoted by supplying it to the reaction tank 6.
You. Next, the carbon dioxide / methane immobilization control system
The control method of the stem will be described with reference to FIG. Figure
3 is to feed the mixed gas to the reaction tank 6 and heat it to reduce the
Control program that responds and repeats the reaction.
You. First, the supplied mixed gas is added by the pump B4a.
Compression to about 0.9 MPa
Send to 6. Continuously in the reaction tank 6 for a long time,
Heat at 600 ° C and reduce high pressure mixed gas with catalyst
To deposit carbon on the surface of the catalyst. Predetermined time response
After that, the reaction gas is exhausted, and the pressure is reduced, and the pressure is increased.
Atmospheric pressure to about 0.1 MPa. Again, to pump B4a
Therefore, pressurize and compress to a high pressure of about 0.9 MPa
Then, it is sent to the reaction tank 6. Continuous long time in the reaction tank 6
While heating at 400-600 ° C and mixing at high pressure by catalyst
The gas is reduced. Repeat this process,
If the gas in the reaction system decreases, add a mixed gas from outside
Supply. By the above process, carbon is produced by high pressure reaction
It can be immobilized efficiently and separates hydrogen
To perform effective energy conversion with a fuel cell power generator.
Can be. [0015] According to the present invention, the carbon dioxide / methane immobilization control of the present invention is performed.
The system is configured as above and supplied
The mixed gas is compressed and compressed to a high pressure of about 0.9 MPa.
Sent to the tank and continuously at 400-600 ° C for a long time
Heating causes a catalytic reduction reaction to deposit and fix carbon. Anti
Response pressure is normal pressure or 0.1MPa or less as before
Is performed at high pressure instead of at
Rate can be improved. In addition, after the reaction, the atmosphere is reduced to 0 to 0.1.
The pressure is reduced to about 1 MPa, and the water is
After separation, hydrogen is separated by a hydrogen separator and
It is supplied to the battery and reacts with oxygen in the air to generate electricity.
You. Then, the power is exchanged from DC by an orthogonal transformer.
It can be converted to a stream and supplied to the outside. Also, the exhaust heat
The heat generated by the fuel cell by the collecting device is
Energy can be converted to hot water. Therefore,
Unreacted gas is used by circulating through the circulation path
As well as effectively use the generated hydrogen gas as energy
Is converted and carbon dioxide /
The efficiency of methane immobilization can be improved.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing one embodiment of a carbon dioxide / methane immobilization control system of the present invention. FIG. 2 is a diagram showing a fuel cell power generator of the carbon dioxide / methane immobilization control system of the present invention. FIG. 3 is a diagram showing a control method of the carbon dioxide / methane immobilization control system of the present invention. FIG. 4 is a diagram showing a conventional carbon dioxide / methane immobilization control system. FIG. 5 is a diagram showing the structure of a reaction tank of a conventional carbon dioxide / methane immobilization control system. [Description of Signs] 1 ... Gas blender 2, 2a, 2c, 2d ... Valve 3 ... Mixing tank 4 ... Pump A 4a ... Pump B 5 ... Check valve 6 ... Reaction tank 7 ... Condenser 8 ... Drain tank 9 ... Hydrogen separation Unit 10 Hydrogen surge tank 11 Pressure regulator 17 Fuel cell generator 17a Fuel cell 17b Single cell 17c Separator 17d Fuel electrode (platinum catalyst) 17e Electrolyte (phosphoric acid) 17f Air electrode (platinum) 17g Cooling plate 21 Gas supply port 22 Compressor 23 Heat exchanger 24 Gas inlet 25 Reaction tank 25a Reactor 26 Catalyst fluid tank holding mechanism 27 Catalyst 28 Exhaust pipe 29 Condensation Device 30: Catalyst / carbon outlet 31 ... Catalytic carbon separator 32 ... Catalyst regenerator 33 ... Catalyst supply port 34 ... Heating furnace 35 ... Immobilized carbon 36 ... Far-infrared heater

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C01B 31/02 ZAB C01B 31/02 ZAB (72) Inventor Toshihiro Kobayashi 1 Nishinokyo Kuwaharacho, Nakagyo-ku, Kyoto Stock Exchange F-term in Shimadzu Corporation (reference) 4G040 EA03 EA05 EB33 EB41 FA02 FB02 FC08 FE06 4G046 BA03 BA04 4G075 AA04 AA05 AA42 AA43 AA62 BA01 BA05 BD14 CA54 CA65 CA66 DA03 DA04 5H027 AA02 BA16 DD05 DD09

Claims (1)

Claims: 1. A carbon dioxide / methane immobilization control system in which a mixed gas is immobilized in a reaction system using carbon dioxide and methane as supply gas sources, and a pump A for feeding the mixed gas into the reaction system. A pump B that pressurizes and compresses the supplied gas mixture and the gas circulating in the reaction system and sends it to the reaction tank at a high pressure; a reaction tank for continuously and prolonged catalytic reduction of the supplied gas; A condenser that cools down the decompressed gas to condense and separate water vapor and separates hydrogen, a hydrogen separator that separates hydrogen from the condensed gas, and pressurizes and compresses the gas from which hydrogen has been separated again using the pump B. A circulation-type reaction system including a pump B, a reaction tank, a condenser, and a hydrogen separator; and a fuel cell power generator that generates electricity by taking in the hydrogen separated by the hydrogen separator and oxygen in the air. Characterized by Carbon dioxide / methane immobilization control system.