KR101220120B1 - High efficient Autothermal Reformer with inner preheater - Google Patents

Abstract

Built-in pre-heater that converts heat exchanger and water into water vapor in fuel reformer.The use of Electric Heated Converter (EHC) enables quick start-up of reformer and fluid temperature control of reactant. Possible integrated autothermal reformer (ATR) devices are disclosed. The reformer according to the present invention includes a reactor having an inner cylinder inside the main body, each of which includes an ATR catalyst layer in the main body and the inner cylinder, and a diffusion portion formed at a lower end of the inner cylinder; A head which closes an upper end of the main body and has a power supply part and a first raw material injection part formed thereon; A tube coupled to the upper end of the inner cylinder through the head up and down, a reactant communication in which at least one line is disposed up and down in the tube, a distilled water inlet formed at an upper side of the tube, and a distilled water inlet connected to the lower end of the tube A heat exchanger comprising a zig-zag plate extending in a zigzag form, a water vapor discharge hole formed in one side or both bottom portions of the tube, and a product discharge portion formed on an upper surface of the tube; An electric heater surrounding the tube in the interior of the body; A partial oxidation catalyst layer disposed under the electric heater; And a thermocouple mounted outside the main body to sense an internal temperature.

Description

High efficient autothermal reformer with inner preheater

The present invention relates to a reforming apparatus for producing hydrogen, which is fuel of a fuel cell, in a fuel cell power generation system. More specifically, a heat exchanger and a pre-heater built-in type for converting water into steam are provided. Electric Heated Converter (EHC) relates to an integrated autothermal reformer (ATR) device that enables rapid start-up of the reformer and fluid temperature control of the reactants.

In order to expand the supply of small-sized (several hundred W to several kW scale) polymer electrolyte fuel cell power generation systems, which are expected to be the most commercially available next-generation clean energy environment technology, fuel efficiency It is essential to develop compact integrated systemization technology for high efficiency and miniaturization of reformer.

BACKGROUND ART A fuel reformer is a device for converting a fuel such as natural gas, LPG, gasoline or methanol into a reformed gas containing hydrogen and supplying the reformed gas to a fuel cell. This fuel reformer requires high efficiency and miniaturization applicable to domestic fuel cells It is necessary to stably produce hydrogen at a high concentration.

Fuel reformers are classified into partial oxidation (POX), steam reformer (SR), and autothermal reformer (ATR) depending on the reforming method. Partial oxidation reforming does not require heat supply due to exothermic reaction and has fast response characteristics, but has a disadvantage of low hydrogen conversion efficiency. Steam reforming reactions are usually strong endothermic and require high temperatures to increase the hydrogen conversion of the fuel. In general, the reaction conditions in which the catalyst is used are the reaction temperature of 700 ~ 850 ℃, the pressure is atmospheric pressure ~ 40 atm, the space velocity (GHSV) of about 3,000 ~ 6000hr ^-1 , the catalyst composition is a heat-resistant carrier (α-alumina or calcium aluminate) Since the reduced nickel is supported (about 10 to 12%), the surface area is 10 m ² / g or less. The steam reforming has a high hydrogen conversion efficiency, but it suffers an endothermic reaction and therefore has to supply heat and has a slow response characteristic. The autothermal reformer can take advantage of the partial oxidation reforming and steam reforming methods, and it has the advantages of low energy and fast response characteristics. In the following scheme, steam reforming is endothermic and partial oxidation is exothermic, so if the thermal equilibrium is maintained, the autothermal reforming reaction can proceed without supplying energy.

Steam reforming reaction: CH ₄ + H ₂ O → CO + 3H ₂ △ H = + 205.9kJ / mol

Partial oxidation reforming reaction: CH ₄ + 0.5O ₂ → CO + 2H ₂ △ H = -36kJ / mol

The steam reforming reaction, which is an endothermic reaction during the fuel reforming reaction of a domestic fuel cell, needs to improve the heat supply pattern for the steam reforming reaction because the total thermal efficiency is determined by the supplied thermal energy. Therefore, the new concept of reforming reaction system technology that can improve the heat supply aspect of reaction heat and enable rapid energy supply is the most important technology for maintaining stable hydrogen production performance and high efficiency operation.

During the fuel reforming reaction, the autothermal reformer must generate an ignition spark by heating the temperature above the ignition point of the fuel for initial start-up or by adjusting the ratio of oxygen to fuel. Starting the reformer requires a separate device such as a heating wire, an igniter, a start control device, which complicates the structure of the reformer and consumes a lot of energy. In addition, the initial startup of the heating method has a disadvantage that it takes a long time to preheat up to the temperature of the reformer.

The present invention has been made to solve the above problems, a pre-heater built-in type for converting the heat exchange (heat exchange) and water to water vapor in the fuel reformer (Electric Heated Converter, EHC) The aim is to provide an integrated autothermal reformer (ATR) device that enables rapid start-up of the reformer and fluid temperature control of the reactants.

The present invention to achieve the above object,

A reactor having an inner cylinder in the main body, each having an ATR catalyst layer in the main body and the inner cylinder, and a diffusion portion formed at a lower end of the inner cylinder;

A head which closes an upper end of the main body and has a power supply part and a first raw material injection part formed thereon;

A tube coupled to the upper end of the inner cylinder through the head up and down, a reactant communication in which at least one line is disposed up and down in the tube, a distilled water inlet formed at an upper side of the tube, and a distilled water inlet connected to the lower end of the tube A heat exchanger comprising a zig-zag plate extending in a zigzag form, a water vapor discharge hole formed in one side or both bottom portions of the tube, and a product discharge portion formed on an upper surface of the tube;

An electric heater surrounding the tube in the interior of the body;

A partial oxidation catalyst layer disposed under the electric heater; And

It is mounted to the outside of the main body to provide a reforming device comprising a; a thermocouple for sensing the internal temperature.

In addition, a second raw material introduction portion may be further formed on the outside of the main body located under the partial oxidation catalyst layer.

According to the present invention, a pre-heater built-in type for converting heat exchange and distilled water into steam, and an integrated autothermal reformer composed of an electric heater (ECH), enables quick start-up and hydrogen conversion efficiency of fuel. To maximize.

1 is a front sectional view of a self-heating reformer with a preheating function according to the present invention.

Hereinafter, a reforming apparatus according to a preferred embodiment of the present invention will be described with reference to the accompanying drawings.

Referring to FIG. 1, the reforming apparatus 100 according to the present invention includes a reactor 110 having a large tubular body 111, a head 120 finishing an upper portion of the reactor 110, and a head from outside. The heat exchanger 130 is connected to the inside of the reactor 110 through the 120, and the electric heater 140 surrounding the outside of the heat exchanger 130 in the reactor 110 is configured.

The reactor 110 is provided with a main body 111 made of a cylinder and an inner cylinder 112 partitioned into a cylindrical shape spaced apart from the inner surface and the bottom surface of the main body 111, and inside and outside the inner cylinder 112. The catalyst layer 113 is embedded. The catalyst layer 113 is an ATR (Autothermal Reformer) catalyst layer. And the lower end of the inner cylinder 112, the reactant diffusion portion 115 is formed through a plurality of through holes 116 are formed.

The head 120 is coupled to the upper end of the main body 111 of the reactor 110, the power supply 121 is coupled to both sides of the head 120, the first raw material introduction portion 122 is formed on any one side of the upper surface do.

The heat exchanger 130 is integrally coupled to the upper surface of the inner cylinder 112 installed inside the reactor 110 while the tubular tube 131 penetrates the center portion of the head 120 up and down. On the upper surface is formed a product discharge portion 136 through which the reformed gas containing hydrogen is discharged. At least one reactant communication 132 extending up and down is disposed inside the tube 131, and a distilled water inlet 133 is formed at an upper end of one side of the tube 131. A plurality of zigzag plates 134 are integrally formed so that the distilled water introduced from the distilled water introduction unit 133 passes zigzag downwardly. At this time, the flow path formed by the zigzag plate 134 is formed in a state in which the reactant communication 132 is exposed inside the flow path. In addition, a steam discharge hole 135 is formed at one side or both bottom ends of the tube 131 to discharge steam toward the reactor 110.

The electric heater 140 is installed to be wrapped outside the tube 131 of the heat exchanger 130 located in the main body 111 of the reactor 110, the electric heater 140 is a power source 121 formed in the head 120 Power on. A partial oxidation catalyst (POXC) layer 150 is disposed below the electric heater 140.

On the other hand, the second raw material introduction portion 160 may be further formed in the main body 111 positioned below the partial oxidation catalyst layer 150. The raw material introduction part is sufficient to use only the first raw material introduction part 122, but it is good to install two for convenience of use because it must flow not only the raw material but also air into the raw material introduction part.

The thermocouple (TC, Thermocouple) 170 is formed in the main body 111 of the reactor 110 according to the present invention so as to measure the internal temperature at a position as shown in the drawing. That is, the thermocouple 170 detects the temperature in the catalyst layer 113 embedded in the inner cylinder 112 and between the inner cylinder 112 and the main body 111, the bottom temperature sensing of the main body 111, and the partial oxidation catalyst layer 150. Is formed at each position for sensing the lower temperature of the), the upper temperature of the electric heater 140, and the like.

The following briefly describes the process of modifying the raw material using the reforming apparatus 100 according to the present invention.

The reforming apparatus 100 according to the present invention starts with injecting air into the first raw material introduction portion 122. When air is injected, the electric power is applied to the power supply unit 121 and the electric heater 140 is operated accordingly.

When it reaches about 350 ~ 400 ℃ due to the operation of the electric heater 140, the raw material is injected through the first raw material introduction portion 122 or the second raw material introduction portion 160.

Then, when the temperature of the heat exchanger 130 reaches 600 ~ 700 ℃, distilled water is introduced through the distilled water introduction unit 133. The distilled water injected into the distilled water introduction unit 133 descends along the flow path formed by the zigzag plate 134 in the shell & tube heat exchange 130 and vaporizes the pre-heated distilled water. It is injected into the reactor 110.

Meanwhile, the raw material introduced into the reactor 110 reacts through the outer catalyst layer 113 of the inner cylinder 112, and then is diffused by the reactant diffuser 115 formed at the lower end of the inner cylinder 112 and thus the inner cylinder 112. The inner catalyst layer 113 and water vapor react with each other to maximize the hydrogen conversion rate, and the reactants thus generated are discharged to the product outlet 136 through the reactant communication 132 of the heat exchanger 130.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined by the appended claims. .

100: reformer
110 reactor 111 body
112: inner cylinder 113: catalyst layer
115: reactant diffusion 116: through hole
120: head 121: power supply
122: first raw material introduction portion 130: heat exchanger
131 tube 132 reactant communication
133: distilled water introduction portion 134: zigzag plate
135: water vapor discharge hole 136: product discharge
140: electric heater 150: partial oxidation catalyst layer
160: second raw material introduction portion 170: thermocouple

Claims (2)

The reactor 110 includes an inner cylinder 112 inside the main body 111, and an ATR catalyst layer 113 is built in the main body 111 and the inner cylinder speed, respectively, and a diffusion part 115 is formed at a lower end of the inner cylinder 112. ;
A head 120 finishing an upper end of the main body 111 and having a power supply 121 and a first raw material injection part 122 formed therein;
A tube 131 coupled to an upper end of the inner cylinder 112 by penetrating the head 120 upward and downward, and reactant communication 132 having at least one or more lines disposed up and down in the tube 131, and The distilled water introduction unit 133 formed on an upper portion of one side of the tube 131, the zigzag plate 134 communicating with the distilled water introduction unit 133 and extending in a zigzag form to the lower end of the tube 131, and the tube 131. A heat exchanger (130) composed of steam discharge holes (135) formed at either one side or both sides of the bottom), and a product discharge part (136) formed on the upper surface of the tube (131);
An electric heater 140 surrounding the tube 131 in the main body 111 and receiving power from the power supply 121;
A partial oxidation catalyst layer 150 disposed below the electric heater 140; And
And a thermocouple (170) mounted outside the main body (111) to sense an internal temperature. The reforming apparatus according to claim 1, wherein a second raw material introduction portion (160) is formed outside the main body (111) located below the partial oxidation catalyst layer (150).

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