KR20130054603A - Apparatus and method for treating fuel - Google Patents

Abstract

PURPOSE: An apparatus and method for treating fuel is provided to maintain high hydrogen yield and low carbon monoxide yield and to maintain sufficient temperature difference between an auto-thermal reforming reaction and hydrogenation reaction. CONSTITUTION: An apparatus(100) for treating fuel comprises an auto-thermal reformation reactor(10) which conducts an auto-thermal reforming reaction; a hydrogenation reactor(30) which is located opposite the auto-thermal reformation reactor; and an internal heat exchanger(20) between the auto-thermal reformation reactor and the hydrogenation reactor. The result of the auto-thermal reformer is supplied to the hydrogenation reactor through the internal heat exchanger, as a reactant after heat exchanging. [Reference numerals] (AA) Reactant(Ethanol + Water + Air)

Description

Apparatus and method for treating fuel

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel processing apparatus and a fuel processing method using the same, and more particularly, to a fuel processing apparatus and a method integrated with an autothermal reforming reaction and an aqueous reaction which can be applied to a fuel cell, in particular, a small portable high temperature PEMFC.

A method of supplying hydrogen required for a fuel cell, a method of physically and chemically storing hydrogen (high pressure hydrogen tank, liquefied hydrogen tank, metal hydride, chemical hydride, etc.) or a method of providing hydrogen through reforming of a hydrocarbon. There is this.

Ultimately, it is desirable to provide hydrogen by water decomposition using solar or nuclear energy, but little research is available.

On the other hand, much research is being conducted on a method of reforming a hydrocarbon that can produce hydrogen relatively easily and economically. The method can be used for commercialization of fuel cells in the absence of infrastructure for hydrogen supply.

Hydrocarbon reforming has two major advantages. First, hydrocarbon fuels generally have higher energy storage densities than high pressure gaseous hydrogen, liquefied hydrogen, metal hydrates, and chemical hydrogen storage methods. Second, the existing infrastructure for hydrocarbon fuels can be used.

A continuous reforming reaction is required to feed fuels such as ethanol and gasoline to the high temperature PEMFC. In the first reforming reaction, the fuel consisting of C _x H _y O _z is converted into a hydrogen-rich synthetic gas, depending on whether steam reforming (SR), part, depending on whether water or air is supplied to the reactants. Partial oxidation (POX), autothermal reforming (ATR) method can be divided into.

The steam reforming reaction is a technique that is well known as a process for producing a synthesis gas (hydrogen, carbon monoxide mixed gas) in the chemical industry by producing hydrogen using water together with fuel. When the same fuel is used, the amount of hydrogen generated is higher than that of the partial oxidation reaction or the autothermal reforming reaction method, and shows more stable long-term operation characteristics. However, the steam reforming reaction is an endothermic reaction, and the size of the apparatus is relatively large because an external heat source is required. In addition, fast startup is difficult and the response to dynamic loads on the system is poor. Hence, hydrogen production using steam reforming is not suitable for small reforming reactors.

The partial oxidation reaction is a method of producing hydrogen by partially oxidizing a fuel using oxygen. The rapid exothermic reaction that occurs in the oxidation process not only enables the rapid start-up of the reactor, but also makes the system simple and suitable for small systems. However, the amount of hydrogen produced from the same fuel is relatively low compared to other reforming methods, and due to the high reaction temperature due to severe exothermic reaction, deterioration of the catalyst and the outer wall of the reactor is relatively serious.

The autothermal reforming reaction is a mixture of a steam reforming reaction using only steam and a partial oxidation reaction using only air, and by controlling the amount of water and oxygen, the endothermic amount and calorific value of the entire reaction can be controlled. Self-sustaining condition can be configured. In addition, in the autothermal reforming reaction, the reactor can be started quickly using heat generated by the initial partial oxidation reaction, and since the heat required for the steam reforming reaction can be supplied from the partial oxidation reaction, the system can be configured without an external heat source. It is suitable for small reformers. In addition, the amount of hydrogen generated compared to the same fuel is higher than that of the partial oxidation reaction, and since water is included in the reactants, carbon deposition is less than that of the partial oxidation reaction.

However, since the reformed gas is not suitable to supply the carbon monoxide concentration to about 10% directly to the high temperature PEMFC, the carbon monoxide concentration should be reduced to about 1 to 2% through water gas shift (WGS).

The aqueous reaction is an exothermic reaction that generates carbon dioxide and hydrogen by reacting water and carbon monoxide in a reaction similar to steam reforming. At lower temperatures thermodynamically, the concentration of carbon monoxide is lower, but higher temperatures are advantageous in terms of reaction rate.

BACKGROUND ART A steam reformer in which a metal monolithic catalyst body is incorporated as a conventional steam reformer is known (Patent Document 1).

In addition, a carbon monoxide removal device for a fuel cell in which a carbon monoxide removal reactor and a heat exchanger are integrated in a device is known (Patent Document 2).

Patent Registration No. 10-0783004 Patent Registration No. 10-0422804

The inventors have intensively studied reactors incorporating autothermal reforming reactions and aqueous reactions that can be applied to fuel cells, in particular small portable high temperature PEMFCs.

As a result, the present inventors can maintain a high hydrogen yield and a low carbon monoxide yield, and maintain a sufficient temperature difference between the autothermal reforming reaction and the aqueous reaction even in a small space without a complicated heat exchanger, thereby miniaturizing and reducing the weight. To provide.

In embodiments of the present invention, an autothermal reforming reactor in which an autothermal reforming reaction occurs; An aqueous hydrolysis reactor positioned opposite the autothermal reforming reactor and undergoing an aqueous reaction; A fuel processing apparatus comprising an internal heat exchanger located between the autothermal reforming reactor and the aqueous reactor, wherein the reactant of the autothermal reforming reactor is supplied to the autothermal reforming reactor via the internal heat exchanger, and the product of the autothermal reforming reactor is Provided is a fuel processing device in which an autothermal reforming reactor and an aqueous reactor are integrated with the reactant of the autothermal reforming reactor via the internal heat exchanger, and then supplied as a reactant to the aqueous reactor.

In an exemplary embodiment of the invention, the autothermal reforming reactor comprises: a reaction zone in which the autothermal reforming reaction occurs; And a passage that exists outside the reaction zone and through which the reactant of the autothermal reforming reaction moves, wherein the reactant of the autothermal reforming reaction moves along the outside of the reaction zone after passing through an internal heat exchanger and is further subjected to an autothermal reforming reaction. After heat exchange with the product is supplied to the reaction zone.

In an exemplary embodiment of the invention, the autothermal reforming reactor is to receive one or more disk-type catalysts having through holes, and the aqueous reactor is to contain one or more disk-type catalysts having through holes.

In an exemplary embodiment of the invention, the reactant of the autothermal reforming reactor is radially spread outward from the center of the disk-shaped catalyst of the autothermal reforming reactor, and the reactant in the aqueous reactor is the disk-type of the aqueous reactor. Radial convergence from the outside of the catalyst to the center of the disk-type catalyst.

In an exemplary embodiment of the present invention, an auxiliary heating device for initial startup of the autothermal reforming reactor is further provided outside the autothermal reforming reactor.

In an exemplary embodiment of the present invention, an external heat exchanger is further provided outside the fuel processing device.

In an exemplary embodiment of the invention, the autothermal reforming reactor comprises: a reaction zone in which the autothermal reforming reaction occurs; And a passage outside the reaction zone and through which the reactant of the autothermal reforming reaction moves, wherein the reaction zone comprises at least one disk-type catalyst having a through hole; A support for supporting the disk catalyst; An igniter which performs ignition in the through hole of the disc catalyst; And an outer housing which receives the catalyst, the support and the igniter and partitions a passage through which the reactants move and a reaction zone.

In an exemplary embodiment of the invention, the aqueous hydrolysis reactor comprises a reaction zone in which an aqueous hydrolysis reaction takes place; And a passage outside the reaction zone and through which the reactant of the aqueous reaction moves, wherein the reaction zone comprises at least one disk-type catalyst having a through hole; A support for supporting the disk catalyst; And an igniter that performs ignition in the through hole of the disc catalyst.

In an exemplary embodiment of the invention, the autothermal reforming reactor comprises: a reaction zone in which the autothermal reforming reaction occurs; And a passage outside the reaction zone in which the autothermal reforming reaction occurs and in which the reactant of the autothermal reforming reaction moves, wherein the reaction zone in which the autothermal reforming reaction occurs comprises: at least one disk-type catalyst having a through hole; A support for supporting the disk catalyst; An igniter which performs ignition in the through hole of the disc catalyst; And an outer housing accommodating the catalyst, the support and the igniter and defining a passage through which the reactant of the autothermal reforming reaction moves and a reaction zone in which the autothermal reforming reaction takes place, wherein the aqueous reactor is a reaction in which an aqueous reaction occurs. area; And a passage outside the reaction zone in which the aqueous reaction takes place and through which a reactant of the aqueous reaction moves, wherein the reaction zone includes: at least one disk-type catalyst having a through hole; A support for supporting the disk catalyst; And an igniter which performs ignition in the through hole of the disk-type catalyst. The reactant of the autothermal reforming reaction passes through an internal heat exchanger and then moves along the outer housing of the reaction zone where the autothermal reforming reaction occurs, and further autothermal reforming. After heat exchange with the product of the reaction, it is fed to the reaction zone where the autothermal reforming reaction takes place.

Here, the reactant of the autothermal reforming reactor is radially spread outward from the center of the disk-shaped catalyst in the reaction zone of the autothermal reforming reactor, and the reactant of the aqueous reactor is the reaction of the disk-type catalyst in the reaction zone of the aqueous reactor. Radially converging from the outside to the center of the disk catalyst.

In embodiments of the present invention, a fuel treatment method for integrating an autothermal reforming reaction and an aqueous reaction, comprising: allowing a reactant of the autothermal reforming reaction and a product of the autothermal reforming reactant to mutual heat exchange; And supplying a reactant of the heat exchanged autothermal reforming reaction as a reactant to the autothermal reforming reaction and supplying a product of the heat exchanged autothermal reforming reaction as a reactant to the aqueous hydrolysis reaction.

In an exemplary embodiment of the invention, the temperature gradient of the autothermal reforming reaction and the aqueous reaction is 200 to 300 ° C.

According to the fuel processing apparatus and method according to the embodiments of the present invention, it is possible to maintain a high hydrogen yield and a low carbon monoxide yield while maintaining a sufficient temperature difference between an autothermal reforming reaction and an aqueous reaction even in a small space without a complicated heat exchanger. Miniaturization and weight reduction are possible.

1 is a schematic diagram illustrating a fuel processing apparatus in an exemplary embodiment of the present invention.
FIG. 2 is a schematic view showing a disc shaped catalyst (FIG. 2A), a support thereof (FIG. 2B), and a shape in which a disc shaped catalyst is supported on a support (FIG. 2C) in an exemplary embodiment of the present invention.
3 is a schematic diagram illustrating a fuel processing system including a fuel processing apparatus in an embodiment of the present invention.
4 is a graph showing a temperature change at the start of the reactor in the present embodiment.
5 is a graph showing a change in composition during operation of the reactor in the present embodiment.
6 is a graph showing a change in temperature during the operation of the reactor in the present embodiment.

Hereinafter, exemplary embodiments of the present invention will be described in detail.

In constructing an integrated reactor in which the autothermal reforming reactor and the hydrolysis reactor are integrated, the autothermal reforming reactor and the hydrolysis reactor may be, for example, between 200 ° C and 300 ° C in a limited space in the integrated reactor due to the temperature difference between the autothermal reforming reaction and the waterification reaction. It is important to maintain a temperature gradient.

Therefore, in the embodiments of the present invention, an autothermal reforming reactor and an aqueous reactor are integrated, and the reactants and the product of the autothermal reforming reaction are heat-exchanged with each other so that the reactants are preheated, and the product is lowered to supply the aqueous reaction. By doing so, it is possible to maintain a desired temperature gradient.

Specifically, in the embodiments of the present invention, the autothermal reforming reactor in which the autothermal reforming reaction takes place, the hydrolysis reactor located opposite to the autothermal reforming reactor and in which the hydrolysis reaction occurs, located between the autothermal reforming reactor and the aqueous hydrolysis reactor. A fuel processing apparatus incorporating an autothermal reforming reactor and an aqueous reactor including an internal heat exchanger is provided.

1 is a schematic diagram illustrating a fuel processing apparatus in an exemplary embodiment of the present invention.

As shown in FIG. 1, a fuel processing apparatus 100 according to an exemplary embodiment of the present invention includes an autothermal reforming reactor 10 and an aqueous hydrolysis reactor 30 positioned opposite thereto, wherein the autothermal reforming An internal heat exchanger 20 may be provided between the reactor 10 and the aqueous reactor 30.

The autothermal reforming reactor 10 may include a reaction zone in which the autothermal reforming reaction occurs and a passage outside the reaction zone and through which the reactants of the autothermal reforming reaction move (the passage in which the reactants move in the vertical upward direction in FIG. 1). Can be.

The reaction zone in which the autothermal reforming reaction occurs comprises at least one disk-type catalyst having a through hole, a support for supporting the disk-type catalyst, an igniter for igniting at the hole of the disk-type catalyst and the catalyst, the support and the igniter It may include an outer housing that receives and defines a passageway and a reaction zone through which the reactants of the autothermal reforming reaction travel.

Here, the reactant of the autothermal reforming reaction passes through an internal heat exchanger as shown in FIG. 1, and then further heat exchanges with the product of the autothermal reforming reaction while moving along the outside of the reaction zone (ie, the outer housing described above). May be fed to the reaction zone.

The autothermal reforming reactor 10 may be an auxiliary heating device 15 for the initial start-up, the auxiliary heating device 15 may be formed to surround the autothermal reforming reactor 10, for example. The fuel processing apparatus may be provided with passages 6 and 7 through which reactants or products may be introduced or discharged, and an igniter charging passage 5 for charging an igniter may also be provided.

Reactants of the autothermal reforming reactor (which may include, but are not particularly limited to, for example, ethanol, water and air) are fed into the internal heat exchanger 20 along the reactant feed passage 6 and the internal heat exchanger 20 Is supplied to the autothermal reforming reactor (10), and the product of the autothermal reforming reactor (10) is heat exchanged with the reactants of the autothermal reforming reactor via the internal heat exchanger (20), and then the aqueous reactor (30). Can be supplied as a reactant.

The aqueous reactor may comprise a reaction zone in which the aqueous reaction takes place and a passage that exists outside of the reaction zone where the aqueous reaction takes place and through which the reactants of the aqueous reaction move. The reaction zone in which the aqueous reaction takes place may include an igniter which performs ignition in one or more disk-type catalysts having through holes therethrough, a support for supporting the disk-type catalysts and in the holes of the disk-type catalysts. It may include.

According to the integrated configuration of the autothermal reforming reactor and the hydrolysis reactor as described above, the temperature gradient between the reaction zones of the two reactions can be maintained well, so that the space between the autothermal reforming reactor and the hydrolysis reactor in a small space without using a complicated heat exchanger is required. It is possible to maintain a sufficient temperature difference.

For example, it is easy to drop the outlet gas temperature of the autothermal reforming reactor of 700 ° C. or higher in a small space to, for example, 500 ° C. or lower suitable for an aqueous reaction (ie, a temperature gradient of, for example, 200 ° C. to 300 ° C .; The measurement of the temperature gradient is, for example, by measuring the temperature gradient between T1, which is the center of the autothermal reforming reactor and T3, which is the center of the hydrolysis reactor, or T2, which is the outlet side of the autothermal reforming reactor, and T3, which is the center of the hydrolysis reactor, in FIG. Can be checked). In addition, the reactants of the autothermal reforming reactor can also be easily preheated and fed to the autothermal reforming reaction. The combined reactor of the autothermal reforming reaction and the aqueous reaction which has such a characteristic can be made small and light, and thus is particularly suitable as a fuel processor for a portable system. For reference, FIG. 1 shows the route of reaction of reactants and products in a compact, lightweight integrated reactor.

Hereinafter, the case where the autothermal reforming reactor 10 and the aqueous reactor 30 accommodate the disk-type catalyst will be described in more detail.

As described above, the autothermal reforming reactor 10 may be to accommodate one or more disk-type catalyst having a through hole. In addition, the aqueous reactor 30 may also be to accommodate one or more disk-type catalyst having a through hole.

At least two or more disk-type catalysts may be stacked to form a stack. In the case of forming the stack in this way, the disk-type catalysts should be sufficiently in contact with each other so that there is no gap.

The disk-type catalyst is a metal having a high redox stability such as platinum (Pt), rhodium (Rh), ruthenium (Ru), palladium (Pd) and high redox stability is cerium oxide (CeO ₂ ), aluminum oxide (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), doped cerium oxide (eg Sm, Gd, Zr, Y, Ca—CeO ₂ ) The supported supported catalyst may be, for example, a catalyst having a structure coated on a metal structure such as iron-chromium-aluminum alloy (FeCrAl) or Inconnel. Catalysts having such a structure are excellent in reforming activity, redox stability, thermal conductivity and heat resistance.

As described above, when the autothermal reforming reactor 10 and the aqueous reactor 30 contain a disk-type catalyst, the reactants of the autothermal reforming reactor 10 are disk-shaped at the center of the disk-type catalyst of the autothermal reforming reactor 10. It is possible to carry out the autothermal reforming reaction, spreading outward, ie radially outward of the disc-shaped catalyst.

In addition, the reactants (ie, the product of the autothermal reforming reaction) in the aqueous reactor 30 converge to the center of the disk catalyst on the outside of the disk catalyst in the aqueous reactor 30, i.e., radially. The aqueous reaction can be carried out while moving to converge to the center of the disc type catalyst (see reactants and product migration path in FIG. 1). The product which has passed through the aqueous reactor may be discharged through the outlet 7.

As described above, when the autothermal reforming reactor 10 and the aqueous reactor 30 have a disk-type catalyst, the reactants naturally spread out along each disk-type catalyst in the autothermal reforming reaction, It is collected from the outside along the disk-type catalyst.

As a result, the autothermal reforming product is naturally structured to exchange heat more smoothly with the reactants entering the autothermal reforming reactor in a large area (see the reactants and the product migration path of FIG. 1).

That is, in the autothermal reforming reaction, the spreading of the reactants from the center outward along the disk-type catalyst means that the reactants of the autothermal reforming reaction are more likely to reach outwards from the autothermal reforming reaction zone and thus along the outside of the reaction zone of the autothermal reforming reaction. It means more advantageous to further heat exchange with the reactants of the moving autothermal reforming reaction. This feature can further contribute to miniaturization and weight reduction of the fuel processing device.

On the other hand, in the aqueous reactor, the product of the aqueous reaction is collected at the center of the disk-type catalyst and exits to the reactor.

In an exemplary embodiment of an integrated reactor, the autothermal reforming reactor 10 may comprise a reaction zone in which the autothermal reforming reaction takes place and a passage outside the reaction zone in which the autothermal reforming reaction occurs and in which the reactants of the autothermal reforming reaction travel. The reaction zone in which the autothermal reforming reaction occurs may include at least one disk-type catalyst having a through hole, a support for supporting the disk-type catalyst, an igniter for igniting at the hole of the disk-type catalyst and the catalyst, the support and It may include an outer housing that receives an igniter and defines a passage through which the reactants of the autothermal reforming reaction travel and a reaction zone in which the autothermal reforming reaction occurs. Wherein the reactant of the autothermal reforming reaction passes through an internal heat exchanger and moves along the outer housing of the reaction zone where the autothermal reforming reaction takes place and further heat exchanges with the product of the autothermal reforming reaction to be supplied to the reaction zone where the autothermal reforming reaction occurs. Can be.

In addition, the aqueous reactor 30 may include a reaction zone in which the aqueous reaction takes place and a passage outside the reaction zone where the aqueous reaction takes place and through which the reactants of the aqueous reaction move, wherein the aqueous solution is obtained. The reaction zone in which the reaction takes place may comprise one or more disk-type catalysts having a through hole, a support for supporting the disk-type catalyst, and an igniter for igniting in the hole of the disk-type catalyst.

Here, the reactant of the autothermal reforming reactor is radially spread outward from the center of the disk-shaped catalyst in the reaction zone of the autothermal reforming reactor, and the reactant of the aqueous reactor is the reaction of the disk-type catalyst in the reaction zone of the aqueous reactor. It may be a radial convergence from the outside to the center.

2 is a schematic view showing a disk-shaped catalyst, a support thereof, and a shape in which a disk-type catalyst is supported on a support in an exemplary embodiment of the present invention.

FIG. 2A is an illustration showing the disk-shaped catalyst 1, FIG. 2B is an illustration showing the support 2, and FIG. 2C is an illustration showing that the disk-type catalyst 1 is supported on the support 2. For reference, FIG. 1 simulates that the support 2 on which the disk-shaped catalyst 1 was supported is mounted on the fuel processing apparatus 100.

On the other hand, in the embodiments of the present invention, the fuel treatment method is performed by integrating an autothermal reforming reaction and an aqueous reaction, the step of allowing the reactant of the autothermal reforming reaction and the product of the autothermal reforming reaction to mutual heat exchange, the heat exchange Provided is a fuel treatment method for supplying a reactant of the prepared autothermal reforming reaction as a reactant to the autothermal reforming reaction, and supplying a product of the heat exchanged autothermal reforming reaction as a reactant to the aqueous reaction.

Here, the heat exchange, for example, referring to Figure 1, after the reactant of the autothermal reforming reaction and the product of the autothermal reforming reaction is primarily heat exchanged on the internal heat exchanger side, that is, the final outlet side of the product of the autothermal reforming reaction, The reactants of the first heat exchanged autothermal reforming reaction may include both secondary heat exchange while moving along the reaction zone of the autothermal reforming reactor.

As described above, according to this heat exchange, during the autothermal reforming reaction, the temperature gradient between the autothermal reforming reaction and the aqueous reaction can be maintained at a low temperature of 200 to 300 ° C.

According to the fuel processing apparatus and method according to the embodiments of the present invention as described above, it is possible to maintain a high hydrogen yield and a low carbon monoxide yield and at the same time maintain a temperature gradient between the autothermal reforming reaction and the aqueous reaction in a small space without a complicated heat exchanger. It is possible to achieve miniaturization and weight reduction.

Hereinafter, exemplary embodiments of the present invention will be described in more detail with reference to specific examples.

3 is a schematic diagram illustrating a fuel processing system including a fuel processing apparatus in an embodiment of the present invention.

As shown in FIG. 3, in the present embodiment, the carbon monoxide concentration is dropped to about 2% or less through an integrated reactor including an autothermal reforming reactor 10, an internal heat exchanger 20, and an aqueous reactor 30. In order to improve the performance of the high-temperature PEMFC, an external aqueous hydrolysis reactor 50 was further installed at the rear of the integrated integrated reactor so as to lower the carbon monoxide concentration to an additional 0.1% level.

The liquid reactant (water, ethanol) was supplied using a pump (P) (Isocratic Pump: Lab Alliance), and a fluid flow controller (MFC: Mass Flow Controller) was used for air supply.

The air was sequentially preheated by the aqueous gasification reactor 30 and the autothermal reforming reactor 10 outlet gas by the external heat exchanger 40 and the internal heat exchanger 20 for air, and then supplied to the inlet to the autothermal reforming reactor.

For example, the liquid fuel and water, which are ethanol, are directly supplied to the internal heat exchanger 20 by a pump P, and are sufficiently vaporized at the outer wall of the internal heat exchanger 20 and the autothermal reforming reactor 10, and then the autothermal reforming reactor 10 ) Can be supplied.

The autothermal reforming reactor 10 is initially started by an auxiliary heating device, such as a heating wire, wound around the reactor wall. For example, using a 70W auxiliary battery, the temperature of the outer wall of the reactor is increased to 300 ° C in the first 10 minutes, and then ethanol and air are supplied at full combustion conditions at a gradually increasing flow rate and reformed conditions (ethanol 0.711 min / min , OCR = 0.7, SCR = 2.5).

The OCR was kept slightly high at 0.7 to maintain the autothermal reforming reactor 10 temperature above 700 ° C. by internal exotherm.

Long-term performance evaluation of the fuel treatment system was conducted.

Figure 4 is a graph showing the temperature change at the start-up of the reactor in this example, shows that it can be started in 35 minutes. 5 is a graph showing a change in composition during operation of the reactor in the present embodiment, Figure 6 is a graph showing a change in temperature during operation of the reactor in the present embodiment. For reference, in FIGS. 4 and 6, the ATR outlet represents the autothermal reforming reactor outlet, the WGS outlet represents the aqueous hydrolysis reactor outlet, and the Surface of the reactor represents the integrated reactor surface.

Hydrogen production was 700 sccm or less (130W, LHV) for 700 hours, fuel conversion rate 100%, reforming efficiency 40-50% (LHV), carbon monoxide concentration was less than 1% (dry basis) was confirmed . For reference, the fuel conversion rate is expressed as (carbon monoxide and carbon dioxide production rate) / (carbon feed rate), and the reforming efficiency is expressed as (LHV flow of hydrogen produced) / (LHV flow of fed ethanol).

For reference, the product composition (dry basis) is 24.9 mol% hydrogen, 55 mol% nitrogen, 1.2 mol% methane, 2.5 mol% carbon monoxide, 16.3 mol% carbon dioxide for an integrated reactor, and 27 mol% hydrogen for an external aqueous reactor. , 51.4 mol% of nitrogen, 1.3 mol% of methane, 0.7 mol% of carbon monoxide, and 19.4 mol% of carbon dioxide.

TC denotes the temperature measurement site, TC2 is the inlet of the autothermal reforming reactor 10, TC3 is the outlet of the autothermal reforming reactor 10, TC4 is the outlet of the hydrolysis reactor 30, TC5 is the outer wall of the integrated reactor, TC6 is the outside The inlet of the aqueous hydrolysis reactor 50, TC7 is the outlet of the external aqueous hydrolysis reactor 50.

For reference, the temperature of the autothermal reactor 10 outlet (TC3) was maintained at 700 ~ 800 ℃, the aqueous reactor (30) outlet (TC4) could be maintained at 250 ℃. The external aqueous reactor inlet (TC6) and outlet (TC7) are relatively well maintained at 200 ° C, which makes them suitable for, for example, PBI electrolyte based high temperature polymer electrolyte fuel cells operating below 200 ° C, considering some external heat loss. Could.

1: disco type catalyst, 2: support
5: ignition device charging passage 6, 7: reactant or product passage
10: autothermal reforming reactor 15: auxiliary heating device
20: internal heat exchanger 30: aqueous reactor
40: external heat exchanger 50: external aqueous hydration reactor
P: Pump

Claims (12)

An autothermal reforming reactor in which an autothermal reforming reaction occurs;
An aqueous hydrolysis reactor positioned opposite the autothermal reforming reactor and undergoing an aqueous reaction; And
A fuel processing apparatus comprising an internal heat exchanger located between the autothermal reforming reactor and the aqueous reactor,
The reactant of the autothermal reforming reactor is supplied to the autothermal reforming reactor via the internal heat exchanger, and the product of the autothermal reforming reactor is heat exchanged with the reactant of the autothermal reforming reactor via the internal heat exchanger and then supplied as a reactant to the aqueous reactor. A fuel processing device, characterized in that. The method of claim 1,
The autothermal reforming reactor includes a reaction zone in which the autothermal reforming reaction occurs; And a passage outside the reaction zone and through which the reactant of the autothermal reforming reaction moves, wherein the reactant of the autothermal reforming reaction moves along the outside of the reaction zone after passing through an internal heat exchanger, And further heat-exchange and then feed to said reaction zone. 3. The method according to claim 1 or 2,
Wherein said autothermal reforming reactor contains one or more disk-type catalysts having through holes therein, and said aqueous hydrolysis reactor contains one or more disk-type catalysts having through holes therethrough. The method of claim 3, wherein
The reactant of the autothermal reforming reactor is radially spread outward from the center of the disk type catalyst in the autothermal reforming reactor, and the reactant of the aqueous hydrolysis reactor radially converges from the outer side of the disk type catalyst in the aqueous reactor. A fuel processing device, characterized in that. The method of claim 1,
A fuel processing device further comprises an auxiliary heating device for initial startup of the autothermal reforming reactor outside the autothermal reforming reactor. The method of claim 1,
An external heat exchanger is further provided outside the fuel processing device. The method of claim 1,
The autothermal reforming reactor includes a reaction zone in which the autothermal reforming reaction occurs; And a passage outside the reaction zone and through which the reactant of the autothermal reforming reaction moves, wherein the reaction zone comprises at least one disk-type catalyst having a through hole; A support for supporting the disk catalyst; An igniter which performs ignition in the through hole of the disc catalyst; And an outer housing which receives the catalyst, the support and the igniter and partitions a passage through which the reactant moves and a reaction zone. The method of claim 1,
The aqueous reactor comprises a reaction zone in which the aqueous reaction takes place; And a passage outside the reaction zone and through which the reactant of the aqueous reaction moves, wherein the reaction zone comprises at least one disk-type catalyst having a through hole; A support for supporting the disk catalyst; And an igniter which performs ignition in the through hole of the disc catalyst. The method of claim 1,
The autothermal reforming reactor includes a reaction zone in which the autothermal reforming reaction occurs; And a passage outside the reaction zone in which the autothermal reforming reaction occurs and in which the reactant of the autothermal reforming reaction moves, wherein the reaction zone in which the autothermal reforming reaction occurs comprises: at least one disk-type catalyst having a through hole; A support for supporting the disk catalyst; An igniter which performs ignition in the through hole of the disc catalyst; And an outer housing accommodating the catalyst, the support and the igniter and defining a passage through which the reactants of the autothermal reforming reaction move and a reaction zone in which the autothermal reforming reaction occurs,
The aqueous reactor comprises a reaction zone in which the aqueous reaction takes place; And a passage outside the reaction zone in which the aqueous reaction takes place and through which a reactant of the aqueous reaction moves, wherein the reaction zone includes: at least one disk-type catalyst having a through hole; A support for supporting the disk catalyst; And an igniter which performs ignition in the through hole of the disc catalyst.
The reactant of the autothermal reforming reaction passes along the outer housing of the reaction zone where the autothermal reforming reaction occurs after passing through an internal heat exchanger and is further fed to the reaction zone where the autothermal reforming reaction occurs after further heat exchange with the product of the autothermal reforming reaction. A fuel processing device characterized by the above-mentioned. The method of claim 9,
The reactant of the autothermal reforming reactor is radially spread outward from the center of the disk-shaped catalyst in the reaction zone of the autothermal reforming reactor, and the reactant of the aqueous reactor is outside of the disk-type catalyst in the reaction zone of the aqueous reactor. A fuel processing apparatus, characterized by radially converging to the center. A fuel processing method performed by integrating an autothermal reforming reaction and an aqueous reaction,
Allowing the reactant of the autothermal reforming reaction and the product of the autothermal reforming reactant to heat exchange with each other; And
And supplying a reactant of the heat exchanged autothermal reforming reaction as a reactant to the autothermal reforming reaction and supplying a product of the heat exchanged autothermal reforming reaction as a reactant to the aqueous hydrolysis reaction. The method of claim 11,
And a temperature gradient of the autothermal reforming reaction and the aqueous reaction is 200 to 300 ° C.

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