WO2022124450A1

WO2022124450A1 - Auto-thermal reforming apparatus

Info

Publication number: WO2022124450A1
Application number: PCT/KR2020/018138
Authority: WO
Inventors: 이현찬
Original assignee: 주식회사 에너지 앤 퓨얼
Priority date: 2020-12-07
Filing date: 2020-12-11
Publication date: 2022-06-16
Also published as: KR20220080315A; KR20230038450A; KR102588374B1; KR102510471B1

Abstract

The present invention relates to an auto-thermal reforming apparatus that can minimize the formation of hot spots inside a reaction tube during hydrogen production using an auto-thermal reforming reaction, and thereby enhance the efficiency of hydrogen production. The apparatus comprises: the reaction tube, which is pipe shaped and extends in one direction; a heat transfer member longitudinally passing through the reaction tube; a catalyst which is charged into the reaction tube and reacts with a raw material injected into the reaction tube, thereby producing hydrogen; a pair of inner caps which are coupled to the inside of both ends of the heat transfer member, respectively, and support the heat transfer member so that the heat transfer member is spaced apart from the inner circumferential surface of the reaction tube; a first outer cap which is coupled to one end of the reaction tube to surround same, and has an injection port for supplying the raw material and air into the reaction tube; and a second outer cap which is coupled to the other end of the reaction tube to surround same, and has a discharge port for discharging the hydrogen produced in the reaction tube.

Description

autothermal reformer

The present invention relates to an autothermal reforming apparatus, and more particularly, to an autothermal reforming apparatus capable of improving hydrogen production efficiency by minimizing hot spots generated in a reaction tube during hydrogen generation using an autothermal reforming reaction.

A fuel cell electric vehicle (FCEV) is a vehicle to which a fuel cell is applied instead of an internal combustion engine, and is a vehicle that uses electric energy generated by an electrochemical reaction of hydrogen and oxygen as a power source.

Hydrogen used as a fuel for fuel cell vehicles exists in a gaseous state at room temperature, so it was not easy to store or store in large quantities. For this reason, the fuel cell vehicle is provided with a fuel reforming device that uses liquid fuel as a raw material to produce hydrogen-rich reformed gas.

The fuel reformer has a structure for generating hydrogen-rich reformed gas using a steam reforming (SR) reaction, a partial oxidation (POX) reaction, and an auto-thermal reforming (ATR) reaction. .

The steam reforming reaction has a relatively high yield and stability of hydrogen, but has the disadvantage of having to supply a large amount of heat from the outside due to the endothermic reaction. has the disadvantage of being

The partial oxidation reforming reaction is a reforming reaction through incomplete combustion of fuel. It is an exothermic reaction, so a separate heating means is not required and the reaction rate is relatively fast, but the hydrogen yield is not high.

An autothermal reformer combines the advantages of a steam reformer with high hydrogen production efficiency and a partial oxidation reformer that maintains a moderate exothermic reaction, and since heat generated in the reaction can be directly consumed, heating means and/or cooling means This is not necessary and has the advantage of fast reaction speed.

The partial oxidation reforming reaction of the above-described autothermal reforming apparatus proceeds rapidly at the front end of the reaction tube into which oxygen is injected, whereas the steam reforming reaction proceeds slowly throughout the reaction tube. That is, the front end of the reaction tube exhibits a high reaction temperature due to the exothermic reaction of partial oxidation reforming, but the reaction temperature decreases toward the rear end of the reaction tube due to the endothermic reaction of steam reforming.

However, in the conventional autothermal reforming apparatus, heat of about 400° C. or more is generated inside the reaction tube, and the generated heat is concentrated on the inner wall of the reaction tube made of a metal material to cause a hot spot phenomenon.

This hot spot phenomenon not only oxidizes the inner wall of the reaction tube, but also forms coke by oxidizing particles inside the reaction tube, so that the movement of reactants including fuel is not smooth, and the reaction efficiency of the catalyst is lowered. And, there was a problem in that the durability and reliability of the entire device is deteriorated.

In addition, the conventional autothermal reforming apparatus has a problem in that it is difficult to uniformly fill each cell with a catalyst because each cell of the honeycomb structure has a separate space.

The present invention is to solve the problems of the prior art, and an object of the present invention is to provide an autothermal reforming apparatus capable of suppressing a hot spot phenomenon occurring in a reaction tube.

Another object of the present invention is to provide an autothermal reforming device capable of minimizing the generation of carbon monoxide by maintaining the reaction temperature of the reaction tube within a range in which the catalyst can stably operate.

Another object of the present invention is to provide an autothermal reforming device capable of improving reaction efficiency, durability, and reliability of a catalyst.

The present invention for achieving the above object is an autothermal reforming apparatus for generating hydrogen using a partial oxidation reforming reaction and a steam reforming reaction. A heat transfer member, a catalyst filling the inside of the reaction tube and reacting with a raw material injected into the reaction tube to generate hydrogen, are respectively coupled inside both ends of the heat transfer member, and the heat transfer member is spaced apart from the inner circumferential surface of the reaction tube A pair of inner caps for supporting as much as possible, a first outer cap coupled to surround one end of the reaction tube and having an inlet for supplying raw materials and air into the reaction tube, and the other end of the reaction tube and a second outer cap coupled thereto and formed with an outlet through which hydrogen generated in the reaction tube is discharged.

In the above configuration, the heat transfer member includes a first heat transfer member positioned at the center of the reaction tube, and a plurality of second heat transfer members radially arranged with respect to the first heat transfer member. In this case, a baffle for designating positions of the first heat transfer member and the second heat transfer member is installed at one end of the heat transfer member.

The present invention configured as described above transfers heat generated by the partial oxidation reforming reaction from the front end to the rear end of the reaction tube using a heat transfer member, thereby preventing a hot spot phenomenon from occurring at the front end of the reaction tube. , it is possible to improve the reaction efficiency, durability and reliability of the catalyst through this.

In addition, the present invention allows the catalyst to react stably by maintaining a constant reaction temperature of the reaction tube by transferring heat using a heat transfer member, and it is possible to minimize the generation of carbon monoxide, a by-product.

In addition, according to the present invention, since all spaces except the heat transfer member communicate with each other, it is easy to fill the catalyst, and since it is possible to fill the catalyst having a uniform layer, the production efficiency can be increased, as well as the manufacturing cost is reduced, and by the uniform filling It is possible to increase the reaction efficiency and hydrogen production efficiency.

In addition, in the present invention, each component has a prefabricated fastening structure, so not only the man-hours are reduced, but also the assembling method is very easy and the assembling property is excellent, so that the production efficiency can be improved.

In addition, according to the present invention, due to the installation of the baffle, it is possible to add a more efficient function to the removal of hot spots, and to increase the production efficiency by facilitating assembly.

1 is a perspective view of an autothermal reforming apparatus according to an embodiment of the present invention;

2 is an exploded perspective view of an autothermal reforming apparatus according to an embodiment of the present invention;

3 is a cross-sectional perspective view of an autothermal reforming apparatus according to an embodiment of the present invention;

4 is a view of a heat transfer member and an inner cap in the self-heating reforming apparatus according to an embodiment of the present invention;

5 is a cross-sectional perspective view of an autothermal reforming apparatus according to another embodiment of the present invention.

An embodiment according to the present invention will be described in detail with reference to the accompanying drawings. Hereinafter, in describing the embodiment according to the present invention, and in adding reference numerals to the components of each drawing, the same reference numerals are added to the same components even though they are indicated in different drawings as much as possible.

The present invention is an autothermal reforming device for generating hydrogen using a partial oxidation reforming reaction and a steam reforming reaction. By suppressing a hot spot phenomenon that occurs during a partial oxidation reforming reaction at the front end of a reaction tube, the reaction efficiency of the catalyst is increased, and the device It is an autothermal reforming device that can improve the durability and reliability of

An autothermal reforming apparatus according to an embodiment of the present invention will be described in detail with reference to FIGS. 1 to 4 .

The autothermal reforming apparatus 100 according to this embodiment includes a reaction tube 110 , a heat transfer member 120 penetrating the reaction tube 110 in the longitudinal direction, and a catalyst ( 130),

inner caps

140 and 150 respectively coupled to both ends of the heat transfer member 120,

outer caps

160 and 170 coupled to both ends of the reaction tube 110, respectively, and heat transfer surrounding the reaction tube 110 It is configured to include a coil (180).

The reaction tube 110 is a part in which the partial oxidation reforming reaction for hydrogen generation and the steam reforming reaction proceed, and has a hollow pipe shape extending in one direction. The inside of the reaction tube 110 is filled with a catalyst 130 that reacts with the supplied raw material to generate hydrogen.

On the other hand, the partial oxidation reforming reaction for hydrogen generation proceeds in the front end of the reaction tube 110 , and the steam reforming reaction proceeds in the entire portion of the reaction tube 110 . At this time, heat of reaction of 400° C. or more is generated at the front end of the reaction tube 110 in which the partial oxidation reforming reaction proceeds.

The reaction tube 110 of this embodiment is made of a thermally conductive material such as copper or aluminum so that the reaction heat generated at the front end can be transferred to the rear end. In particular, the inner wall of the reaction tube 110 is surface-treated or film-treated to prevent oxidation of the reaction tube 110 made of metal by reaction heat.

The heat transfer member 120 is a heat transfer means for transferring reaction heat generated at the front end of the reaction tube 110 to the rear end. The heat transfer member 120 has a shaft shape extending in one direction, and is installed to penetrate the reaction tube 110 in the longitudinal direction. In this case, the heat transfer member 120 is made of a copper material having excellent thermal conductivity so as to effectively transfer the reaction heat.

In the present embodiment, the heat transfer member 120 is illustrated in the shape of a shaft having a circular cross section, but is not necessarily limited thereto. As shown in FIG. 4 , the cross section of the heat transfer member 120 may be formed in a polygonal shape including a star shape. In this case, the surface area of the heat transfer member 120 may increase to improve heat transfer efficiency.

Fastening

rods

122 and 124 for coupling with the

inner caps

140 and 150 protrude from both ends of the above-described heat transfer member 120 . The

fastening rods

122 and 124 include a first fastening rod 122 inserted and coupled to the first inner cap 140 and a second fastening bar 124 screwed to the second inner cap 150 .

The first fastening rod 122 and the second fastening rod 124 have a shaft shape having a smaller diameter than that of the heat transfer member 120 . At this time, the first fastening rod 122 is formed in a tapered shape with a diameter decreasing toward the tip so that it can be easily inserted into the first inner cap 140 . In addition, the second fastening rod 122 has a screw thread formed on its outer circumferential surface so that it can be screwed to the second inner cap 150 .

On the other hand, the heat transfer member 120 is composed of a plurality of radially disposed inside the reaction tube (110). As shown in FIG. 2 , the heat transfer member 120 includes a first heat transfer member 120a passing through the center of the reaction tube 110 and a plurality of first heat transfer members radially arranged based on the first heat transfer member 120a. It is composed of two heat transfer members (120b). In this case, the first heat transfer member 120a is formed to have a larger diameter than the second heat transfer member 120b.

In this way, when the heat transfer member 120 is disposed radially, the reaction heat generated throughout the interior of the reaction tube 110 can be absorbed and transmitted effectively. In particular, it is possible to prevent a hot spot phenomenon by absorbing and transferring the reaction heat concentrated on the inner wall of the reaction tube.

The catalyst 130 serves to generate hydrogen by reacting with the raw material supplied to the reaction tube 110 . In this embodiment, a copper/zinc (Cu/ZnO)-containing catalyst is used to generate hydrogen by reacting with methanol as a raw material. The copper/zinc containing catalyst is obtained by reducing a copper oxide/zinc oxide catalyst or the like. In this case, the catalyst 130 may be in the form of pellets in which fine alumina is formed as a dispersant so as to increase the surface area and improve the contact efficiency.

The

inner caps

140 and 150 serve to support the heat transfer member 120 so that it can be installed spaced apart from the inner circumferential surface of the reaction tube 110 . The

inner caps

140 and 150 include a first inner cap 140 coupled to one end of the heat transfer member 120 and a second inner cap 150 coupled to the other end of the heat transfer member 120 .

The first inner cap 140 is a disk having a predetermined thickness. A first fastening hole 142 into which the first fastening rod 122 of the heat transfer member 120 is inserted is formed in the first inner cap 140 . In addition, a first through hole 144 through which raw materials and air supplied through an inlet 162 of a first outer cap 160 to be described later are transferred are formed in the first inner cap 140 .

The first fastening hole 142 and the first through hole 144 are formed in a plurality of radially arranged with respect to the center of the first inner cap 140 . In particular, the first through hole 144 is formed in a tapered shape with a diameter extending from the front side to the rear side of the first inner cap 140. In this way, when the first through hole 144 is formed in a tapered shape, the reaction tube 110 ) can improve the reaction efficiency with the catalyst 130 by reducing the speed of the raw material and air transferred to the inside.

The second inner cap 150 has the same disk shape as the first inner cap 140 . The second inner cap 150 has a second fastening hole 152 to which the second fastening rod 124 of the heat transfer member 120 is screwed, and a second through hole through which the hydrogen generated in the reaction tube 110 is transferred. (154) is formed.

The second fastening hole 152 and the second through hole 154 are composed of a plurality of radially arranged with respect to the center of the second inner cap 150 . In particular, a thread is formed in the second through hole 154 for screw coupling with the second fastening rod 124 .

The above-described first inner cap 140 and second inner cap 150 are inserted into the reaction tube 110 when the heat transfer member 120 is installed. That is, it is closely coupled to the inner wall of the reaction tube 110 so that the heat transfer member 120 is spaced apart from the inner circumferential surface of the reaction tube 110 .

The

outer caps

160 and 170 include a first outer cap 160 coupled to the front end of the reaction tube 110 and a second outer cap 170 coupled to the rear end of the reaction tube 110 .

The first outer cap 160 is formed in a cup shape to surround the front end of the reaction tube 110 into which the first inner cap 140 is inserted. An inlet 162 for supplying raw materials and air into the reaction tube 110 is formed in the first outer cap 160 .

In addition, the second outer cap 170 is formed in a cup shape to surround the rear end of the reaction tube 110 into which the second inner cap 150 is inserted. An outlet 172 for discharging hydrogen generated in the reaction tube 110 is formed in the second outer cap 170 .

The heat transfer coil 180 is a heat transfer means for transferring reaction heat generated at the front end of the reaction tube 110 to the rear end, and absorbs heat emitted from the front end of the reaction tube 110 to the outside of the reaction tube 110 . It serves as a transmission to the rear end. To this end, the heat transfer coil 180 may be in the form of a spiral extending in the longitudinal direction while surrounding the outer circumferential surface of the reaction tube 110 .

In the autothermal reforming apparatus 100 configured as described above, when raw material and air are injected through the inlet 162 of the first outer cap 160 , it reacts with the catalyst 130 filled in the reaction tube 110 to generate hydrogen to create

When raw materials and air are injected, a partial oxidation reforming reaction and a steam reforming reaction proceed in the reaction tube 110 . As described above, the partial oxidation reforming reaction proceeds rapidly at the front end of the reaction tube 110 , while the steam reforming reaction proceeds slowly throughout the reaction tube 110 . At this time, at the front end of the reaction tube 110, reaction heat of high temperature (400° C. or more) is generated according to the partial oxidation reforming reaction.

The autothermal reforming apparatus 100 of this embodiment is configured to include a reaction tube 110 , a heat transfer member 120 , and a heat transfer coil 180 as heat transfer means, and reacts the reaction heat generated at the front end of the reaction tube 110 . It may be transmitted to the rear end through the tube 110 , the heat transfer member 120 , and the heat transfer coil 180 .

Accordingly, it is possible to prevent a hot spot phenomenon due to heat concentration occurring at the front end of the reaction tube 110 . In addition, since the heat of reaction can be transferred through the heat transfer means and used as heat required for the steam reforming reaction, there is no need to add a separate heat supply means. In particular, since the reaction temperature of the reaction tube 110 can be kept constant, the reaction efficiency, durability and reliability of the catalyst can be improved, and the catalyst can react stably to minimize the generation of carbon monoxide, a by-product.

5 is a cross-sectional view of an autothermal reforming apparatus according to another embodiment of the present invention.

5 , the autothermal reforming apparatus 200 according to the present embodiment includes a reaction tube 210 , a heat transfer member 220 penetrating the reaction tube 210 in the longitudinal direction, and a reaction tube 210 . ), the

inner caps

240 and 250 respectively coupled to both ends of the heat transfer member 220, and the

outer caps

260 and 270 respectively coupled to both ends of the reaction tube 110, and the reaction tube. It is configured to include a heat transfer coil 180 surrounding the circumference of 210 , and a baffle 290 installed inside the reaction tube 210 .

Among the above-described components, other components except for the

outer caps

260 and 270 and the baffle 190 are the same as those of the above-described exemplary embodiment, and thus a detailed description thereof will be omitted.

The

outer caps

260 and 270 of the present embodiment include a first outer cap 260 coupled to the front end of the reaction tube 210 and a second outer cap 270 coupled to the rear end of the reaction tube 110 .

The first outer cap 260 and the second outer cap 270 are formed in a cup shape surrounding the front and rear ends of the reaction tube 210 , and the first outer cap 260 has the raw material inside the reaction tube 210 . and

inlets

262 and 264 for supplying air are formed, and an outlet 272 for discharging hydrogen generated in the reaction tube 210 is formed in the second outer cap 270 . At this time, the

injection ports

262 and 264 of the first outer cap 260 are composed of a first injection port 262 for supplying raw materials and a second injection port 264 for supplying air.

In this way, if the inlet 262 for injecting the raw material and the inlet 264 for injecting air are separately formed, the amount of raw material and/or air supplied to the reaction tube 110 can be adjusted according to the user's needs. have. That is, since the amount of raw material and/or air can be adjusted according to the amount of the catalyst 230 filled in the reaction tube 110 , the reaction efficiency with the catalyst 230 can be improved.

Meanwhile, although not shown in the drawing, a plurality of outlets 272 of the second outer cap 270 may also be configured. can

The baffle 290 is installed on the front end of the heat transfer member 220 to fix the front end of the heat transfer member 220 to prevent the front end of the heat transfer member 220 from sagging or flowing.

The baffle 290 includes an annular rim 292 and a plurality of spokes 294 radially arranged with respect to the center of the rim 292 . At this time, a seating ring 296 through which the first heat transfer member 220a passes is formed in the center of the rim 292 , and a seating ring 298 into which the second heat transfer member 220b is fitted is formed on the spokes 294 . do.

In addition to the role of preventing the front end of the heat transfer member 220 from sagging or flowing, the above-described baffle 290 forms a catalyst unreacted space 212 at the front end of the reaction tube 210 to improve heat transfer efficiency. do

That is, since the baffle 290 is made of a plurality of spokes 294 arranged in a radial direction, the thermal contact area is increased, so that heat generated in the catalyst unreacted space 212 can be easily transferred to the reaction tube 210 , so that heat transfer efficiency can improve

The present invention has been described above through preferred embodiments, but the above-described embodiments are merely illustrative of the technical spirit of the present invention, and various changes are possible without departing from the technical spirit of the present invention in this field. Those of ordinary skill in the art will be able to understand. Therefore, the protection scope of the present invention should be interpreted by the matters described in the claims, not specific embodiments, and all technical ideas within the equivalent range should be interpreted as being included in the scope of the present invention.

Claims

In the autothermal reforming apparatus for generating hydrogen using partial oxidation reforming reaction and steam reforming reaction,

a pipe-shaped reaction tube extending in one direction;

a heat transfer member passing through the reaction tube in the longitudinal direction;

a catalyst filled in the reaction tube and reacting with the raw material injected into the reaction tube to generate hydrogen;

a pair of inner caps respectively coupled to both ends of the heat transfer member and supporting the heat transfer member to be spaced apart from the inner circumferential surface of the reaction tube;

a first outer cap coupled to surround one end of the reaction tube and having an inlet for supplying raw materials and air into the reaction tube; and

and a second outer cap coupled to surround the other end of the reaction tube and formed with an outlet through which hydrogen generated in the reaction tube is discharged,

The autothermal reforming device, characterized in that the heat transfer member prevents a hot spot phenomenon by transferring heat generated by the partial oxidation reforming reaction at the front end of the reaction tube to the rear end of the reaction tube.
The method according to claim 1,

The self-heating reforming device, characterized in that the heat transfer member is a shaft extending in one direction.
3. The method according to claim 2,

The self-heating reforming device, characterized in that the heat transfer member is made of copper.
4. The method according to claim 3,

The self-heating reforming device, characterized in that the cross section of the heat transfer member is a polygon including a star shape.
3. The method according to claim 2,

A first fastening rod and a second fastening rod having a diameter smaller than that of the heat transfer member protrude from both ends of the heat transfer member, respectively.
6. The method of claim 5,

The first fastening rod has a tapered shape that decreases in diameter toward the tip, and the second fastening rod has a thread formed on an outer circumferential surface of the self-thermal reforming device.
7. The method according to any one of claims 2 to 6,

and the heat transfer member includes a first heat transfer member positioned at the center of the reaction tube and a plurality of second heat transfer members radially arranged with respect to the first heat transfer member.
8. The method of claim 7,

and the first heat transfer member has a larger cross-sectional area than the second heat transfer member.
8. The method of claim 7,

A baffle for designating positions of the first heat transfer member and the second heat transfer member is installed at one end of the heat transfer member.
10. The method of claim 9,

The baffle consists of an annular rim and a plurality of spokes arranged radially with respect to the center of the rim,

A seat ring through which the first heat transfer member passes is formed in the center of the rim, and a seat ring through which the second heat transfer member is fitted is formed on the spokes.
11. The method of claim 10,

The baffle is an autothermal reforming device, characterized in that when the heat transfer member is installed, a catalyst unreacted space is formed at the front end of the reaction tube.
The method according to claim 1,

and the inner cap includes a first inner cap coupled to one end of the heat transfer member and a second inner cap coupled to the other end of the heat transfer member.
13. The method of claim 12,

The self-thermal reforming apparatus of claim 1, wherein a first fastening hole to which one end of the heat transfer member is fastened and a first through hole through which the raw material and air supplied through the inlet are transferred are formed in the first inner cap.
14. The method of claim 13,

The self-heating reforming apparatus according to claim 1, wherein the first through hole is formed in plurality radially with respect to the center of the first inner cap.
15. The method of claim 14,

The autothermal reforming device, characterized in that the first through hole has a tapered shape with a diameter extending from one end to the other end.
13. The method of claim 12,

The autothermal reforming apparatus according to claim 1, wherein the second inner cap has a second fastening hole to which the other end of the heat transfer member is fastened and a second through hole through which the hydrogen generated in the reaction tube is transferred.
17. The method of claim 16,

The self-thermal reforming device, characterized in that the thread is formed on the inner peripheral surface of the second fastening hole.
18. The method of claim 17,

The self-thermal reforming apparatus according to claim 1, wherein the second through hole is formed in plurality radially with respect to the center of the second inner cap.
The method according to claim 1,

The inlet is an autothermal reforming device, characterized in that it is composed of a first inlet for supplying a raw material to the inside of the reaction tube, and a second inlet for supplying air into the inside of the reaction tube.
The method according to claim 1,

An autothermal reforming device, characterized in that a heat transfer coil is wound around the reaction tube.
21. The method of claim 20,

The heat transfer coil is an autothermal reforming device, characterized in that it is wound in a spiral shape along the longitudinal direction of the reaction tube.