JP2009286666A - Method and apparatus for producing synthesis gas, and fuel cell system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a synthesis gas, in which carbonization is prevented when a raw material is charged, and a high reaction efficiency is obtained in a reaction for obtaining the synthesis gas from the raw material, and to provide an apparatus for producing the synthesis gas. <P>SOLUTION: The apparatus 100 for producing the synthesis gas is equipped with: a combustion device 200 for burning a portion of a synthesis gas by using oxygen; a supply device 300 for supplying a raw material to a reforming device 400; a connection device 350 for connecting the combustion device 200 and the supply device 300; the reforming device for forming the synthesis gas by subjecting a combustion product formed in the combustion device 200 and the raw material to a reforming reaction; and a recycling device for supplying a portion of the formed synthesis gas to the combustion device 200. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a synthesis gas production method for producing synthesis gas from hydrocarbons using oxygen permeation means, a production apparatus therefor, and a fuel cell system.

Conventionally, a steam reforming reaction is well known as a process for producing synthesis gas containing hydrogen (H ₂ ) and carbon monoxide (CO) using hydrocarbon as a raw material. Since this steam reforming reaction is a vigorous endothermic reaction, it requires a lot of energy and requires a large apparatus. Thus, there is a partial oxidation reaction as a technique for solving these drawbacks. The partial oxidation reaction is a method in which a part of hydrocarbon as a raw material is burned with oxygen and the remaining hydrocarbon is reformed by heat at this time. However, this partial oxidation reaction requires pure oxygen, and an apparatus for producing pure oxygen is expensive.
An oxygen permeable membrane has been proposed as a method for producing pure oxygen at a low cost, and oxygen (O ₂ ) permeated through the oxygen permeable membrane and a hydrocarbon as a raw material are partially oxidized (for example, Patent Documents 1 to 5). reference). In order to operate the oxygen permeable membrane, it is necessary to generate an oxygen concentration difference between one side and the other side of the oxygen permeable membrane and to raise the temperature of the oxygen permeable membrane. In order to satisfy these conditions, it has been proposed to coexist an oxygen-permeable membrane and a partial oxidation reaction.

JP 2003-183004 A Japanese Patent Application Laid-Open No. 2004-267884 JP 2005-270895 A JP 2005-281077 A JP 2005-535434 Gazette

However, in patent documents 1-5, the hydrocarbon which is a raw material is directly introduce | transduced into a high temperature oxygen permeable membrane reactor, and the oxygen and hydrocarbon which permeate | transmitted the oxygen permeable membrane are made to carry out a partial oxidation reaction. In this way, when hydrocarbons are directly introduced into the oxygen permeable membrane reactor, the hydrocarbons may be carbonized in the oxygen permeable membrane reactor, reducing the efficiency of the partial oxidation reaction, and further reducing the oxygen permeable membrane reactor. There is a risk of being unable to drive such as being blocked.
In addition, when hydrocarbons are directly introduced into the oxygen permeable membrane reactor, the amount of oxygen permeating through the oxygen permeable membrane cannot be measured, so that the reaction amount of oxygen and hydrocarbons cannot be adjusted. Therefore, there is a possibility that the partial oxidation reaction becomes an unexpected state and the operation becomes impossible.
Furthermore, in order to increase the amount of oxygen that permeates the oxygen permeable membrane, it is necessary to introduce an excessive amount of hydrocarbon as a raw material, which also causes a blockage of the oxygen permeable membrane reactor due to carbonization of the raw material hydrocarbon. there is a possibility.

  Accordingly, an object of the present invention is to provide a method for producing a synthesis gas, a production apparatus thereof, and a fuel cell system that can prevent carbonization at the time of charging the raw material and have high reaction efficiency until the synthesis gas is obtained from the raw material.

  The synthesis gas production method of the present invention is a synthesis gas production method for producing synthesis gas from a compound containing carbon and hydrogen, or a compound containing carbon, hydrogen and oxygen, and supplying an oxygen-containing gas to the oxygen permeation means A separation step of separating oxygen, a combustion step of burning a part of the synthesis gas using the oxygen separated in the separation step, a compound containing carbon and hydrogen, or the carbon, hydrogen and oxygen A supply step of supplying a compound containing the mixture, and a combustion product obtained in the combustion step is discharged out of the system of the combustion step and mixed with the compound containing carbon and hydrogen, or the compound containing carbon, hydrogen and oxygen And a reforming reaction between the combustion product and the compound composed of carbon and hydrogen or the compound composed of carbon, hydrogen and oxygen. A reforming reaction step for generating a synthesis gas, a recycling step for supplying a part of the synthesis gas to the combustion step, a recovery step for recovering the synthesis gas that has not been supplied to the combustion step in the recycling step, It is characterized by implementing.

In this invention, oxygen (O ₂ ) (separation process) separated by the oxygen permeation means reacts with a part of the synthesis gas (CO, H ₂ ) supplied into the combustion process system in the combustion process. For example, a combustion reaction as shown in the following reaction formula (1) occurs. Here, the oxygen permeable means is not limited as long as it can generate oxygen, and for example, an oxygen permeable film can be used.

12 (CO + H ₂ ) + 6O ₂ → 6 (H ₂ O + CO ₂ ) +6 (H ₂ + CO) (1)

The combustion product generated by this combustion reaction is discharged out of the system of the combustion process, and this combustion product is a compound containing carbon and hydrogen, or carbon, hydrogen and oxygen, which are raw materials supplied in the supply process. It becomes a mixed raw material by being mixed with the compound it contains (mixing step).
In the reforming reaction step, among the mixed raw materials, the raw material compound containing carbon and hydrogen, or the compound containing carbon, hydrogen and oxygen and the combustion product (H ₂ O, CO ₂ ) are, for example, A reforming reaction shown in the reaction formula (2) is caused to generate synthesis gas (CO, H ₂ ). Note that the compound containing carbon and hydrogen or the compound containing carbon, hydrogen and oxygen used in the reaction formula (2) is exemplified by kerosene (C ₁₂ H ₂₄ ).

C ₁₂ H ₂₄ +6 (H ₂ O + CO ₂ ) → 18 (CO + H ₂ ) (2)

  In the recycle process, a part of the synthesis gas generated in the reforming reaction process is supplied into the combustion process system. As a result, the supplied synthesis gas and the oxygen separated by the oxygen permeation means cause a combustion reaction, and the synthesis gas is generated through the same process as described above. Note that the synthesis gas that has not been recycled in the recycling process is recovered (recovery process).

Thus, a combustion process in which a part of the synthesis gas is combusted using oxygen separated by the oxygen permeation means, a combustion product generated by this combustion and a compound containing carbon and hydrogen as raw materials, or carbon, hydrogen A synthesis gas is produced by a two-stage reaction (reaction formulas (1) and (2)) with a reforming reaction step in which a compound containing oxygen and oxygen is reformed.
Therefore, since a raw material compound containing carbon and hydrogen or a compound containing carbon, hydrogen and oxygen is not used in the combustion process, there is no possibility of carbonization in the combustion process system, and there is no possibility of blocking the oxygen permeation means. . As a result, the combustion reaction can proceed efficiently, the efficiency of the reforming reaction can be improved, and the synthesis gas can be produced efficiently.

  In the reforming reaction step, oxygen is not present, and therefore a catalyst having durability against oxygen may not be used. As a catalyst having durability against oxygen, a particularly expensive metal such as rhodium (Rh) is used, so the conventional method is expensive, but an inexpensive catalyst is used in the present invention. can do. That is, cost reduction in the production of synthesis gas can be realized.

  In the synthesis gas production method of the present invention, the supplying step preferably supplies at least one of water and carbon dioxide together with the compound containing carbon and hydrogen or the compound containing carbon, hydrogen and oxygen. .

Water and carbon dioxide are also generated by the combustion reaction in the combustion process. However, by further supplying water (H ₂ O) and carbon dioxide (CO ₂ ) in the supply process, the ratio of H ₂ and CO in the synthesis gas produced by the reforming reaction can be arbitrarily controlled. It becomes. In addition, the supply of water can suppress coking in the reforming reaction step and can improve the reaction efficiency.

  In the method for producing synthesis gas of the present invention, the mixing step may include the step of mixing the combustion product with the compound containing carbon and hydrogen or the compound containing carbon, hydrogen and oxygen before mixing the amount of the combustion product. It is preferable to measure.

According to this invention, by measuring the amount of combustion products generated in the combustion process, the amount of oxygen separated in the separation process can be calculated from the measured value. Specifically, it can be calculated by molar ratio conversion based on the above reaction formula (1).
Therefore, since the amount of oxygen permeating through the oxygen permeation means in the combustion process can be grasped, the amount of synthesis gas recycled corresponding to this amount of oxygen can be adjusted and supplied to the combustion process. Similarly, the amount of the compound containing carbon and hydrogen or the compound containing carbon, hydrogen and oxygen to be supplied in the supply step can be adjusted, and the reforming reaction can proceed efficiently.
As described above, since the progress of the reaction and the production amount of the synthesis gas can be controlled by the present invention, the utility in the production process is high.

  In the synthesis gas production method of the present invention, in the recycling step, an amount of synthesis gas corresponding to the amount of oxygen used in the combustion step converted based on the amount of the combustion product is supplied to the combustion step. It is preferable.

  As described above, since the amount of synthesis gas corresponding to the amount of oxygen permeated through the oxygen permeable means is supplied to the combustion process, the combustion reaction in the combustion process can be efficiently advanced. Further, in order to increase the oxygen permeation amount, the progress of the reaction can be controlled, for example, by increasing the recycle amount of the synthesis gas, which is highly useful in the production process.

In the method for producing synthesis gas of the present invention, the supplying step includes the compound containing carbon and hydrogen in an amount corresponding to the amount of the combustion product generated by the combustion device, or the carbon, hydrogen and oxygen. It is preferred to supply the compound.
As described above, since a compound containing carbon and hydrogen or a compound containing carbon, hydrogen and oxygen corresponding to the amount of the combustion product produced by the combustion device is supplied to the reforming reaction step, The reforming reaction in the quality reaction step can proceed efficiently.

  The synthesis gas production apparatus of the present invention is a synthesis gas production apparatus for producing synthesis gas from a compound containing carbon and hydrogen, or a compound containing carbon, hydrogen and oxygen, comprising oxygen permeation means, and this oxygen permeation means. A combustion apparatus for combusting a part of the synthesis gas using oxygen that has passed through the means, a combustion product generated in the combustion apparatus and the compound containing carbon and hydrogen, or the compound containing carbon, hydrogen and oxygen A reforming apparatus that reacts, a supply unit that supplies the compound containing carbon and hydrogen or a compound containing carbon, hydrogen, and oxygen to the reforming apparatus, and the combustion apparatus and the supply apparatus. Connecting means; and recycling means for connecting the reformer and the combustion device, and supplying a part of the synthesis gas generated by the reformer to the combustion device. Characterized in that was.

By using the manufacturing apparatus of the present invention, the same effects as described above can be obtained. Specifically, a part of the synthesis gas supplied in advance to the combustion apparatus and oxygen that has passed through the oxygen permeation means cause a combustion reaction. Here, an oxygen permeable film or the like can be used as the oxygen permeable means.
And the combustion product produced | generated by this combustion reaction is supplied to a supply means from a combustion apparatus via a connection means.
The supply means supplies a compound containing carbon and hydrogen or a compound containing carbon, hydrogen and oxygen to the reformer, and the combustion product supplied from the connecting means is a compound containing carbon and hydrogen, or carbon , Mixed with a compound containing hydrogen and oxygen to form a mixed raw material, which is supplied to the reformer.
In the reformer, the mixed raw material undergoes a reforming reaction to generate synthesis gas. In the recycling means, a part of the synthesis gas generated by the reformer is supplied to the combustion device, and the synthesis gas not supplied to the combustion device is recovered.

In this way, by separately installing the combustion device and the reformer, the synthesis gas is produced through a two-stage reaction. In particular, in a combustion apparatus provided with an oxygen permeable membrane as an oxygen permeable means, only a combustion reaction using oxygen is performed, so that a compound containing carbon and hydrogen as a raw material or a compound containing carbon, hydrogen and oxygen is contained in the combustion apparatus. Not supplied. Therefore, since carbonization does not occur in the combustion device, there is no possibility that the oxygen permeation means is blocked, and the combustion reaction in the combustion device can be advanced efficiently. As a result, the reforming reaction in the reformer also proceeds efficiently, and the synthesis gas can be produced efficiently.
Further, since oxygen does not exist in the reforming reaction apparatus, it is not necessary to use a catalyst durable to oxygen. As such a catalyst, an expensive noble metal such as rhodium (Rh) is used. Therefore, although the cost is high in the conventional method, an inexpensive catalyst can be used in the present invention. That is, cost reduction in the production of synthesis gas can be realized.

  In the synthesis gas production apparatus of the present invention, it is preferable that the reforming device is provided adjacent to the combustion device.

  The combustion reaction that proceeds in the combustion apparatus is an exothermic reaction. On the other hand, the reforming reaction that proceeds in the reformer is an endothermic reaction. Therefore, by providing the combustion device and the reforming device adjacent to each other, the heat generated in the combustion device is conducted to the reforming device. Therefore, energy can be used effectively and energy saving can be achieved.

  In the synthesis gas production apparatus of the present invention, it is preferable that the supply means supplies at least one of water and carbon dioxide together with the compound containing carbon and hydrogen, or the compound containing carbon, hydrogen and oxygen.

When the supply means supplies at least one of water and carbon dioxide together with the raw material, the ratio of H ₂ and CO of the synthesis gas produced by the reforming reaction can be arbitrarily controlled. Further, the supply of water suppresses coking in the reforming reaction step, and the reforming reaction can proceed efficiently.

  In the synthesis gas production apparatus of the present invention, it is preferable that the connection means includes a product measurement unit that quantifies the combustion product.

In this invention, when a connection means supplies the combustion product produced | generated with the combustion apparatus to a supply means from a combustion apparatus, a fixed quantity of a combustion product is performed by a product measurement part. And based on the above-mentioned reaction formula (1) which is a combustion reaction, the amount of oxygen which permeate | transmitted the oxygen permeation | transmission means with the combustion apparatus can be converted from the quantity of a combustion product.
Therefore, since the amount of oxygen permeating through the oxygen permeable means can be grasped by the combustion apparatus, the amount of synthesis gas recycled corresponding to this amount of oxygen can be adjusted. Similarly, the amount of the compound containing carbon and hydrogen or the compound containing carbon, hydrogen and oxygen supplied by the supply device can be adjusted, and the reforming reaction in the reforming device can be advanced efficiently. . As described above, the progress of the reaction and the production amount of synthesis gas can be controlled.

  In the synthesis gas production apparatus of the present invention, it is preferable that the recycling means includes a recycle control unit that controls the amount of synthesis gas recycled based on the amount of oxygen used in the combustion apparatus.

  The recycle control unit supplies an amount of synthesis gas corresponding to the amount of oxygen permeated through the oxygen permeation means to the combustion device. That is, the amount of synthesis gas recycled can be adjusted. Therefore, the combustion reaction in the combustion apparatus can be advanced efficiently. Moreover, in order to increase the oxygen permeation amount, the progress of the reaction can be controlled, for example, by increasing the recycle amount of the synthesis gas.

In the syngas production apparatus of the present invention, the supply means is configured to supply the compound containing carbon and hydrogen, or the compound containing carbon, hydrogen and oxygen based on the amount of the combustion product generated by the combustion apparatus. It is preferable to control the supply amount.
According to the present invention, since an optimal amount of a compound containing carbon and hydrogen or a compound containing carbon, hydrogen and oxygen is supplied to the reformer, the reformer in the reformer is improved. The quality reaction can proceed efficiently.

  The fuel cell system of the present invention utilizes the above-described synthesis gas production apparatus, oxygen-containing gas supply means for supplying an oxygen-containing gas, and the oxygen-containing gas supplied by the synthesis gas and the oxygen-containing gas supply means. And a fuel cell for generating electricity.

In this invention, in the fuel cell, the synthesis gas produced by the above-described synthesis gas production apparatus capable of producing synthesis gas using various raw materials and the oxygen-containing gas supplied from the oxygen-containing gas supply means are used. Generate electricity.
As a result, the fuel cell can stably generate power without being limited to raw materials, is suitable for home use, and can stably supply power.

(First embodiment)
Hereinafter, a first embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic diagram illustrating a synthesis gas production apparatus according to an embodiment.
[1. Configuration of manufacturing equipment]
As shown in FIG. 1, a manufacturing apparatus 100 includes a combustion apparatus 200 that burns a part of synthesis gas using oxygen, a supply apparatus 300 as a supply unit that supplies a raw material to a reformer 400 described later, A connecting device 350 as connecting means for connecting the device 200 and the supply device 300, a reforming device 400 for generating a synthesis gas by reforming a combustion product generated in the combustion device 200 and a raw material, and a synthesis And a recycling device 500 as a recycling means for supplying a part of the gas to the combustion device 200.

The combustion apparatus 200 includes an oxygen permeable film 210 as an oxygen permeable means that allows oxygen in the outside air to permeate, and a combustion unit 220 provided adjacent to the oxygen permeable film 210.
The oxygen permeable membrane 210 is formed in a flat plate shape or a cylindrical shape, and one surface thereof is provided in contact with an oxygen-containing gas, for example, air, supplied by an oxygen-containing gas supply means (not shown). In the present embodiment, a flat oxygen permeable membrane 210 is used. When the oxygen permeable membrane 210 is operated, external air is taken into the oxygen permeable membrane 210 and only oxygen is permeated and stored in the combustion unit 220.

The material for forming the oxygen permeable membrane 210 is not particularly limited as long as it can transmit oxygen. For example, an ABO ₃ type perovskite compound reported as a mixed conductor that transmits both oxygen ions and electrons can be used. , ZrO ₂ , CeO ₂ , Bi ₂ O _{3, and the} like as an oxygen ion conductor.
The oxygen permeable membrane 210 has a heating device (not shown), and the temperature of the oxygen permeable membrane 210 is adjusted to about 1000 ° C. when allowing oxygen to permeate. The temperature of the oxygen permeable membrane 210 is preferably 300 ° C. or higher and 1800 ° C. or lower, more preferably 500 ° C. or higher and 1500 ° C. or lower, and further preferably 600 ° C. or higher and 1200 ° C. or lower. If the temperature of the oxygen permeable membrane 210 is less than 300 ° C. or exceeds 1800 ° C., the oxygen permeation amount may be significantly reduced.
As the heating device, in addition to an external combustion type such as a burner or a heater, an internal combustion type in which air and fuel are put into a combustion section and burned can be used.

The combustion unit 220 is disposed at a position adjacent to the oxygen permeable membrane 210 and stores oxygen that has passed through the oxygen permeable membrane 210.
A part of the synthesis gas (H ₂ , CO) generated by the reformer 400 described later is supplied to the combustion unit 220, and the synthesis gas and oxygen that has permeated the oxygen permeable membrane 210 undergo a combustion reaction. Wake up. This combustion reaction is shown in the following reaction formula (1).

12 (CO + H ₂ ) + 6O ₂ → 6 (H ₂ O + CO ₂ ) +6 (H ₂ + CO) (1)

It is preferable that the temperature in the combustion part 220 is 300 degreeC or more and 1800 degrees C or less, More preferably, it is 500 degreeC or more and 1500 degrees C or less, More preferably, they are 600 degreeC or more and 1200 degrees C or less. When the temperature of the combustion part 220 is less than 300 ° C. or exceeds 1800 ° C., the combustion reaction does not proceed efficiently.
The combustion unit 220 is charged with a combustion catalyst for advancing this combustion reaction. The combustion catalyst is not particularly limited. For example, in addition to base metal catalysts such as aluminum, gallium, indium, tin, thallium, lead, and bismuth, noble metals such as gold, silver, platinum, palladium, rhodium, iridium, ruthenium, and osmium. Examples thereof include a catalyst and a transition metal oxide catalyst. Note that the combustion catalyst may not be input.

The supply apparatus 300 supplies a raw material compound containing carbon and hydrogen or a compound containing carbon, hydrogen and oxygen to a reformer described later, and has a raw material supply section 310.
Here, the compound containing carbon and hydrogen is a hydrocarbon, and specific examples include methane, city gas, liquefied petroleum gas (LPG), naphtha, gasoline, kerosene, light oil, and heavy oil. In addition, examples of the compound containing carbon, hydrogen, and oxygen include ether-based compounds having a hydrocarbon skeleton and alcohol-based compounds having a hydrocarbon skeleton. Examples of the ether type having a hydrocarbon skeleton include dimethyl ether (DME: Dimethyl ether). Examples of alcohols having a hydrocarbon skeleton include methanol and ethanol. In the present embodiment, kerosene (C ₁₂ H ₂₄ ) is used as a raw material.
The raw material supply unit 310 adjusts the supply amount of the compound containing carbon and hydrogen or the compound containing carbon, hydrogen and oxygen according to the amount of combustion products generated by the combustion apparatus 200.

The connection device 350 includes a tubular first connection portion 351 that connects the combustion device 200 and the supply device 300, and a product measurement portion 352 provided in the middle of the first connection portion 351.
The first connection unit 351 supplies the combustion product generated by the combustion device 200 to the supply device 300.
The product measurement unit 352 is disposed on the first connection unit 351 on the combustion device 200 side relative to the raw material supply unit 310 to which kerosene or water is supplied, and measures the amount of combustion products generated by the combustion device 200. . Specifically, the combustion products generated by the combustion apparatus 200 are water (H ₂ O) and carbon dioxide (CO ₂ ). The amount of these combustion products can be measured, and the oxygen permeation amount in the combustion apparatus 200 can be converted from the molar ratio of the reaction formula (1).

  Then, the combustion product supplied from the first connection part 351 and the kerosene supplied from the raw material supply part 310 are mixed and supplied to the reformer 400. At this time, water or carbon dioxide may be supplied simultaneously with the supply of kerosene.

The reformer 400 is provided adjacent to the combustion device 200 and includes a reforming reaction unit 410 adjacent to the combustion unit 220. A partition plate 420 that partitions between the combustion unit 220 and the reforming reaction unit 410 has heat resistance against the temperature of the combustion unit 220 and is formed of a material having high thermal conductivity. Examples of such a material include metals such as stainless steel.
In the reforming reaction unit 410, the following reaction formula is obtained by using combustion products (H ₂ O, CO ₂ ) generated by the combustion apparatus 200 and kerosene (C ₁₂ H ₂₄ ) as a raw material supplied by the supply apparatus 300. The reforming reaction shown in (2) occurs, and synthesis gas (CO, H ₂ ) is generated.

C ₁₂ H ₂₄ +6 (H ₂ O + CO ₂ ) → 18 (CO + H ₂ ) (2)

The reforming reaction unit 410 has a heating device (not shown), and the temperature in the reforming reaction unit 410 can be adjusted when the reforming reaction represented by the reaction formula (2) proceeds. . The temperature in the reforming reaction section 410 may be lower than the temperature in the combustion section 220, but it is preferable to heat to 500 ° C. or higher in order to advance the reforming reaction. A more preferable range is 600 ° C. or higher and 900 ° C. or lower. If the temperature in the reforming reaction section 410 is less than 500 ° C. or exceeds 900 ° C., the reforming reaction does not proceed efficiently.
As the heating device, in addition to an external combustion type such as a burner or a heater, an internal combustion type in which air and fuel are put into a combustion section and burned can be used.
The reforming reaction unit 410 is charged with a reforming catalyst for causing the reforming reaction to proceed. Although it does not specifically limit as a reforming catalyst, The same thing as what was illustrated with the above-mentioned combustion catalyst can be used.

The recycling apparatus 500 recycles the tubular second connection portion 510 that connects the reforming apparatus 400 and the combustion apparatus 200, and the synthesis gas (CO, H ₂ ) generated by the reforming apparatus 400 to the combustion apparatus 200. A recycle control unit 520 that controls the amount of synthesis gas.
The second connection unit 510 includes a recycle unit 511 that supplies the synthesis gas generated by the reformer 400 to the combustion device 200 and a recovery unit 512 that recovers the generated synthesis gas.
The recycle control unit 520 adjusts the recycle amount of the synthesis gas generated by the reformer 400. The amount of recycling is adjusted according to the amount of combustion products measured by the product measuring unit 352.
Then, the recycle control unit 520 distributes the synthesis gas to be recycled to the recycle unit 511 so that a part of the synthesis gas is supplied to the combustion device 200 and the remaining synthesis gas is supplied to the recovery unit 512 and recovered.

[2. Method for producing synthesis gas]
Next, a method for producing synthesis gas using the production apparatus 100 will be described below.
First, the oxygen permeable membrane 210 is heated to 1000 ° C. by a heating device (not shown). Thereby, oxygen in the air permeates the oxygen permeable membrane 210 and is stored in the combustion unit 220 (separation process).

Further, synthesis gas (CO, H ₂ ) is supplied to the combustion unit 220. As a result, the combustion reaction shown in the above reaction formula (1) occurs by the oxygen and the synthesis gas that have passed through the oxygen permeable membrane 210, and water (H ₂ O) and carbon dioxide (CO ₂ ) as combustion products are generated. (Combustion process)

The combustion products are supplied to the reformer 400 by the connecting device 350 and the supply device 300 (mixing process and supply process).
In the mixing step, the product measurement unit 352 measures water (H ₂ O) and carbon dioxide (CO ₂ ) as combustion products, and converts the molar ratio of the above reaction formula (1) to the combustion device 200. The amount of oxygen transmitted through the oxygen permeable membrane 210 can be converted. And a combustion product is supplied to a supply process.
In the supply step, the raw material and water are supplied from the raw material supply unit 310, mixed with the combustion product supplied from the connection device 350, and supplied to the reformer 400. At this time, carbon dioxide may be supplied as necessary.
The raw material used here is a compound containing carbon and hydrogen, or a compound containing carbon, hydrogen and oxygen. In the present embodiment, kerosene (C ₁₂ H ₂₄ ) is used as a compound containing carbon and hydrogen, or a compound containing carbon, hydrogen and oxygen.
Moreover, the supply amount of the compound containing carbon and hydrogen or the compound containing carbon, hydrogen and oxygen is supplied according to the production amount of the combustion product produced | generated at the combustion process. Specifically, the supply amount can be calculated by converting the molar ratio of the above reaction formula (2).

In the reformer 400, the reforming reaction represented by the above reaction formula (2) occurs by the kerosene, water, and combustion products (CO, H ₂ O) supplied from the supply device 300 (reaction process). At this time, the temperature in the reforming reaction unit 410 can be adjusted with a heating device (not shown) so as to be 500 ° C. or higher. Further, heat generated by the combustion reaction in the combustion unit 220 is conducted to the reforming reaction unit 410 through the partition plate 420.

The synthesis gas (CO, H ₂ ) generated by the reformer 400 circulates through the second connection unit 510 of the recycle device 500, and the recycle control unit 520 and the synthesis gas recycled to the combustion device 200 (recycle process) ) And the recovered synthesis gas and (recovery step).

The amount of synthesis gas recycled to the combustion apparatus 200 is supplied in an amount corresponding to the amount of oxygen permeated through the oxygen permeable membrane 210 and stored in the combustion section 220. Since the amount of oxygen permeated through the oxygen permeable membrane 210 is converted from the measured value in the product measuring unit 352, the amount of synthesis gas recycled can be converted by converting the converted value and the molar ratio of the above reaction formula (1). it can.
After the synthesis gas is recycled, the synthesis gas is manufactured through the separation process, the combustion process, the mixing process, the supply process, and the reaction process in the same manner as described above, and a part of the synthesis gas is recycled (recycle process) and remains. The synthesis gas is recovered (recovery step).
The synthesis gas that has not been recycled flows through the collection unit 512 and is collected.

  As described above, when the reaction formula (1) indicating the combustion reaction in the combustion apparatus 200 and the reaction formula (2) indicating the reforming reaction in the reformer 400 are put together, the following reaction is performed in the manufacturing apparatus 100 of the present invention. Equation (3) is obtained.

C ₁₂ H ₂₄ + 6O ₂ → 12 (CO + H ₂ ) (3)

Next, a method for stopping the manufacturing apparatus 100 will be described below.
First, the supply of the raw material to the supply apparatus 300 is stopped. As a result, the reforming reaction in the reforming reaction section 410 stops and the generation of synthesis gas stops. Furthermore, the synthesis gas that has been supplied to the combustion device 200 through the recycle unit 511 stops. When the supply of the synthesis gas that is the fuel of the combustion unit 220 is stopped, the combustion reaction is stopped and the temperature of the manufacturing apparatus 100 is lowered. At this time, the temperature may be forcibly lowered by a cooling device or the like. Finally, an inert gas such as nitrogen (N ₂ ) or helium (He) or hydrogen (H ₂ ) is supplied into the combustion unit 220 and the reforming reaction unit 410 to supply the raw material and the synthesis gas into the manufacturing apparatus 100. Completely expelled from. After the apparatus is stopped, in order to protect the catalyst in the combustion section 220 and the reforming reaction section 410, the inside of the manufacturing apparatus 100 is more than the external pressure with the aforementioned inert gas or hydrogen so that air does not enter from the outside. Hold with pressure.

  A fuel cell system can be configured using the manufacturing apparatus 100 as described above. The fuel cell system is a household system in which a synthesis gas is generated by the manufacturing apparatus 100 and electric power is generated by the fuel cell using the synthesis gas. The fuel cell system is installed adjacent to a house.

(Second embodiment)
In the second embodiment, synthesis gas is manufactured using the manufacturing apparatus 100 described in the first embodiment. Since the manufacturing process is the same as the first embodiment except that the method for starting the manufacturing apparatus 100 is different, only the method for starting the manufacturing apparatus 100 will be described.
[1. Method for producing synthesis gas]
First, the inside of the reforming reaction section 410 is heated to 500 ° C. or higher by a heating device (not shown). As a result, kerosene (C ₁₂ H ₂₄ ) and water (H ₂ O) supplied from the supply device 300 cause a reforming reaction in the reforming reaction section 410, and synthesis gas (CO, H ₂ ) is generated. . When a part of the synthesis gas is supplied to the combustion device 200 via the recycle device 500, the oxygen in the combustion unit 220 and the synthesis gas cause a combustion reaction, so that the oxygen concentration in the combustion unit 220 decreases. . In this way, the difference in oxygen concentration between the inside of the combustion section 220 and the outside through the oxygen permeable membrane 210 is increased, so that oxygen permeation of the oxygen permeable membrane 210 is promoted. Therefore, a large amount of oxygen is supplied into the combustion section 220, and the combustion reaction represented by the above reaction formula (1) between the synthesis gas and oxygen is promoted.
Thereafter, the process proceeds in the same manner as in the first embodiment, and the synthesis gas is produced while recycling a part of the synthesis gas.

(Operational effects in this embodiment)
In the above-described embodiment, the supply of kerosene as a raw material is started from the supply device 300, and the reforming reaction between the combustion product obtained by the oxygen combustion reaction and the kerosene as the raw material is advanced by the reformer 400. I did it.
That is, since kerosene which is a raw material does not exist in the combustion apparatus 200, there is no possibility that the raw material is carbonized in the combustion apparatus 200. Therefore, the combustion reaction in the combustion apparatus 200 and the reforming reaction in the reformer 400 can be efficiently advanced.

Further, the amount of combustion product is measured by the product measuring unit 352 to convert the amount of oxygen that permeates the oxygen permeable membrane 210, and the recycle control unit 520 converts the amount of synthesis gas corresponding to the amount of oxygen. It was decided to recycle to the combustion device 200.
Thus, the reaction amount of oxygen and synthesis gas that react in the combustion section 220 can be adjusted. That is, since the combustion reaction in the combustion unit 220 can be controlled, the reaction can be efficiently advanced. Furthermore, in order to advance the combustion reaction more quickly, it is necessary to increase the amount of oxygen that permeates the oxygen permeable membrane 210. For this purpose, the amount of synthesis gas to be recycled needs to be increased. Can be adjusted.

Further, the kerosene supplied by the supply device 300 is supplied in an amount corresponding to the amount of combustion products measured by the product measuring unit 352.
In this way, by controlling the supply amount of kerosene, the reforming reaction represented by the aforementioned reaction formula (2) occurring in the reformer 400 can be efficiently advanced.

In this embodiment, the synthesis gas is produced by a two-stage reaction in which a combustion reaction is caused in the combustion device 200 and a reforming reaction is caused in the reformer 400.
Usually, a part of hydrocarbon as a raw material is combusted with oxygen in one reactor and the remaining hydrocarbon is reformed by heat at this time. Therefore, as a partial reforming catalyst placed in the reactor, Among precious metals such as rhodium (Rh) that is durable against oxygen, particularly expensive metals are used.
However, in the present embodiment, as described above, since the combustion reaction and the reforming reaction are performed in separate apparatuses, it is not necessary to use a catalyst having durability against oxygen as the reforming reaction catalyst. That is, it is not necessary to use a particularly expensive metal among the noble metals, so that an inexpensive manufacturing apparatus can be provided.

Further, in the present embodiment, at least one of water and carbon dioxide is supplied simultaneously with supplying the raw material to the reformer 400. Water and carbon dioxide are also generated in the combustion reaction of the combustion apparatus 200, but by further supplying water and carbon dioxide to the supply apparatus 300, the synthesis gas H ₂ and CO produced by the reformer 400 The ratio can be arbitrarily controlled. Further, the supply of water suppresses coking in the reformer 400, and the reforming reaction can proceed efficiently.

In this embodiment, the combustion unit 220 of the combustion device 200 and the reforming reaction unit 410 of the reformer 400 are disposed adjacent to each other. Since the reforming reaction in the reforming reaction unit 410 is an endothermic reaction, a large amount of energy is required, but the heat generated by the combustion reaction of the adjacent combustion device 200 is transferred to the reforming reaction unit 410 via the partition plate 420. Conducted and this heat is used for the reforming reaction. Therefore, energy efficiency can be improved.
In addition, since stainless steel is used as the material of the partition plate 420 that partitions the combustion device 200 and the reformer 400, it is excellent in heat resistance and thermal conductivity, and further energy efficiency can be achieved.

  As shown in the first embodiment and the second embodiment described above, the manufacturing apparatus 100 of the present invention can be started by raising the temperature of either the combustion apparatus 200 or the reforming apparatus 400. The usage method of 100 can be effectively used without limitation.

  By using the fuel cell using the manufacturing apparatus 100, the synthesis gas can be obtained stably, so that stable power supply can be performed and energy saving can be achieved.

(Modification)
It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
For example, in the above embodiment, the flat oxygen permeable membrane 210 is used, but a cylindrical oxygen permeable membrane may be used. Since the oxygen-permeable membrane having such a shape has a large surface in contact with external air, it can transmit more oxygen. Therefore, it is suitable for producing a large amount of synthesis gas.

  Moreover, in the said embodiment, although the fuel cell system using the manufacturing apparatus 100 was illustrated, it is not restricted to this, Hydrogen production methods, such as a hydrogen station, a refinery, a factory, etc. from which the production | generation of synthesis gas is required, methanol It can also be used for synthesis reactions and FT (Fischer-Tropsch) reactions.

  INDUSTRIAL APPLICABILITY The present invention can be used as a hydrogen production method for fuel cells, hydrogen stations, refineries, factories, and the like, and a synthesis gas production method such as methanol synthesis reaction and FT (Fischer-Tropsch) reaction.

Schematic which shows the synthesis gas manufacturing apparatus concerning one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 ... Manufacturing apparatus 200 ... Combustion apparatus 210 ... Oxygen permeable film 220 ... Combustion part 300 ... Supply apparatus 350 ... Connection apparatus 352 ... Product measurement part 400 ... Reformer 410 ... Reformer reaction part 420 ... Partition plate 500 ... Recycler 510 ... Second connection unit 511 ... Recycling unit 512 ... Recovery unit 520 ... Recycling control unit

Claims (12)

A method for producing a synthesis gas comprising producing a synthesis gas from a compound containing carbon and hydrogen, or a compound containing carbon, hydrogen and oxygen,
A separation step of separating oxygen by supplying an oxygen-containing gas to the oxygen permeation means;
A combustion step of burning a part of the synthesis gas using oxygen separated in the separation step;
Supplying a compound containing carbon and hydrogen or a compound containing carbon, hydrogen and oxygen;
A mixing step in which the combustion product obtained in the combustion step is discharged out of the combustion step and mixed with the compound containing carbon and hydrogen or the compound containing carbon, hydrogen and oxygen to produce a mixed raw material. When,
A reforming reaction step of generating synthesis gas by a reforming reaction between the combustion product and the compound composed of carbon and hydrogen or the compound composed of carbon, hydrogen and oxygen;
A recycling step of supplying a portion of the synthesis gas to the combustion step;
And a recovery step of recovering the synthesis gas that has not been supplied to the combustion step in the recycling step. A method for producing a synthesis gas, comprising: The method for producing a synthesis gas according to claim 1,
The supply step supplies at least one of water and carbon dioxide together with the compound containing carbon and hydrogen, or the compound containing carbon, hydrogen and oxygen. The method for producing a synthesis gas according to claim 1 or 2,
The mixing step measures the amount of the combustion product before mixing the combustion product with the compound containing carbon and hydrogen, or the compound containing carbon, hydrogen and oxygen. Production method. In the manufacturing method of the synthesis gas as described in any one of Claims 1-3,
The recycle process supplies a synthesis gas in an amount corresponding to the amount of oxygen used in the combustion process converted based on the amount of the combustion product to the combustion process. . The method for producing a synthesis gas according to any one of claims 1 to 4,
The supplying step supplies the compound containing carbon and hydrogen, or the compound containing carbon, hydrogen and oxygen, in an amount corresponding to the amount of the combustion product generated by the combustion device. Gas production method. An apparatus for producing synthesis gas for producing synthesis gas from a compound containing carbon and hydrogen or a compound containing carbon, hydrogen and oxygen,
A combustion apparatus comprising oxygen permeation means, and combusting a part of the synthesis gas using oxygen permeated through the oxygen permeation means;
A reformer for reacting the combustion product generated in the combustion device with the compound containing carbon and hydrogen, or the compound containing carbon, hydrogen and oxygen;
Supply means for supplying the reformer with the compound containing carbon and hydrogen or the compound containing carbon, hydrogen and oxygen;
Connection means for connecting the combustion device and the supply device;
A synthesis gas production apparatus, comprising: a recycle unit that connects the reformer and the combustion device and supplies a part of the synthesis gas generated by the reformer to the combustion device. . In the synthesis gas production apparatus according to claim 6,
The reforming apparatus is provided adjacent to the combustion apparatus. A synthesis gas production apparatus, wherein: In the synthesis gas production apparatus according to claim 6 or 7,
The supply means supplies at least one of water and carbon dioxide together with the compound containing carbon and hydrogen, or the compound containing carbon, hydrogen and oxygen. In the synthesis gas production apparatus according to any one of claims 6 to 8,
The said connection means is provided with the product measurement part which quantifies the said combustion product. The synthesis gas manufacturing apparatus characterized by the above-mentioned. The syngas production apparatus according to any one of claims 6 to 9,
The recycle means includes a recycle control unit that controls a recycle amount of the synthesis gas based on an oxygen amount used in the combustion device. In the synthesis gas production apparatus according to any one of claims 6 to 10,
The supply means controls the supply amount of the compound containing carbon and hydrogen or the compound containing carbon, hydrogen and oxygen based on the amount of the combustion product generated by the combustion device. Syngas production equipment. The syngas production apparatus according to any one of claims 6 to 11,
An oxygen-containing gas supply means for supplying an oxygen-containing gas;
A fuel cell that generates electric power using the oxygen-containing gas supplied by the synthesis gas and the oxygen-containing gas supply means;
A fuel cell system comprising:

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