KR102252636B1 - Hydrogen purification system - Google Patents

Abstract

Provides a hydrogen purification system. The hydrogen purification system uses plasma to reform hydrogen from a compound, and is connected with a first hydrogen purification device, a first hydrogen purification device including a cathode electrode, an anode electrode, and a neutral electrode disposed between the cathode and anode electrodes. The catalyst is used to purify hydrogen from the reformed hydrogen and by-products and regenerate the catalyst, and the first chamber, the first heating unit disposed outside the first chamber, the second chamber, and the second chamber disposed outside the second chamber. 2 a second hydrogen purification apparatus including a heating unit, a plurality of valves connected to the first hydrogen purification apparatus and connected to the first and second chambers, and a plurality of valves installed in the pipes, the first and second hydrogen A heat exchanger disposed between the purification devices to lower the temperature of the reformed hydrogen and by-products, and including a pipe connecting the first and second hydrogen purification devices, and a cooling unit that surrounds the outer wall of the pipe and provides a refrigerant, and And a pump disposed between the first and second hydrogen purification devices to transfer the reformed hydrogen and by-products to the second hydrogen purification device.

Description

Hydrogen purification system {HYDROGEN PURIFICATION SYSTEM}

The present invention relates to a purification system, and more particularly, to a hydrogen purification system.

Fuel cells generate electricity using a chemical reaction between hydrogen and oxygen. Not only does it not emit carbon dioxide during power generation, but 99% of the fine dust is purified as air passes through the fuel cell stack. Hydrogen is clean energy, and research on a system that produces and purifies hydrogen is being actively conducted.

The present invention is to solve the above-described technical problem, and an object of the present invention is to provide a hydrogen purification system for efficiently producing and purifying high-purity hydrogen.

The hydrogen purification system according to an embodiment of the present invention is a first hydrogen purification system including a cathode electrode, an anode electrode, and a neutral electrode disposed between the cathode and anode electrodes, and reforming hydrogen from a compound using plasma. Device; It is connected to the first hydrogen purification apparatus to purify hydrogen from reformed hydrogen and by-products using a catalyst and to regenerate the catalyst, and a first chamber, a first heating unit disposed outside the first chamber, and a second A chamber, a second heating unit disposed outside the second chamber, pipes connected to the first hydrogen purification device and connecting between the first and second chambers, and a plurality of valves installed in the pipes A second hydrogen purification device comprising; It is disposed between the first and second hydrogen purification devices to lower the temperature of the reformed hydrogen and the by-product, and a pipe connecting between the first and second hydrogen purification devices and a refrigerant surrounding the outer wall of the pipe A heat exchanger including a cooling unit that provides a; And a pump disposed between the first and second hydrogen purification devices to transfer the reformed hydrogen and the by-product to the second hydrogen purification device.

In one embodiment, the compound includes methane (CH4), and the by-product may include at least one selected from the group consisting of CO, CO2, H2O, and O2.

In an embodiment, in the second hydrogen purification apparatus, one of the first chamber and the second chamber may purify the hydrogen and the other may regenerate the catalyst.

A hydrogen purification system according to an embodiment of the present invention includes: a first hydrogen purification apparatus for reforming hydrogen from a compound using plasma; A second hydrogen purification device connected to the first hydrogen purification device to purify hydrogen from reformed hydrogen and by-products using a catalyst and to regenerate the catalyst; And a heat exchanger disposed between the first and second hydrogen purification devices and including a cooling unit configured to lower the temperature of the reformed hydrogen and the by-product.

In an embodiment, the second hydrogen purification apparatus includes: a first purification unit including a first chamber and a first heating unit disposed outside the first chamber; A second purification unit including a second chamber and a second heating unit disposed outside the second chamber; Pipes connected to the first hydrogen purification apparatus and connecting between the first and second chambers; And a plurality of valves installed in the pipes, wherein the first purification unit and the second purification unit may have the same structure.

According to an embodiment of the present invention, methane having a high capacity can be reformed into hydrogen, and heat exchange can be efficiently performed without contamination of cooling water. In addition, the configuration required for the process is economical, and operation costs are reduced compared to hydrogen production in the conventional method, and hydrogen purity and yield compared to impurities can be improved, thereby contributing to productivity improvement.

1 is a schematic diagram illustrating a hydrogen purification system according to an embodiment of the present invention.
FIG. 2 is a diagram illustrating a first hydrogen purification apparatus of the hydrogen purification system shown in FIG. 1.
3 is a view for explaining a second hydrogen purification apparatus of the hydrogen purification system shown in FIG. 1.
4 and 5 are diagrams for explaining a process of using the second hydrogen purification apparatus shown in FIG. 3.

Hereinafter, embodiments of the present invention will be described clearly and in detail to the extent that a person having ordinary knowledge in the technical field of the present invention can easily implement the present invention.

1 is a schematic diagram illustrating a hydrogen purification system according to an embodiment of the present invention.

The hydrogen purification system 1000 may include a first hydrogen purification device 100 and a second hydrogen purification device 200. The hydrogen purification system 1000 according to embodiments of the present invention may be a system 1000 that purifies hydrogen from methane (CH4), which is a main component of Liquerfied Natural Gas (LNG).

The first hydrogen purification apparatus 100 may decompose methane using plasma and perform reforming treatment. According to an embodiment, the first hydrogen purification apparatus 100 may be a plasma apparatus using argon (Ar) as an ignition gas and water vapor (H2O) as a source. When plasma is applied with methane using the first hydrogen purification apparatus 100, a chemical change may occur as shown in Formula 1 below.

As shown in Formula 1, one molecule of methane can react with one molecule of water to generate one molecule of carbon monoxide and three molecules of hydrogen.

FIG. 2 is a diagram illustrating a first hydrogen purification apparatus of the hydrogen purification system shown in FIG. 1. Referring to FIG. 2, the first hydrogen purification apparatus 100 may include a chamber 110, a cathode electrode 120, an anode electrode 130, and a neutral electrode 140.

The chamber 110 has a size and performance capable of processing a gas of 5Nm3/hr (88.33LPM), and can convert high-capacity methane into hydrogen. The cathode electrode 120, the anode electrode 130, and the neutral electrode 140 may be disposed in the chamber 110.

The cathode electrode 120 and the anode electrode 130 face each other, and may be insulated by being spaced apart from each other by the neutral electrode 140. The cathode electrode 120 may have a sharp structure at one end adjacent to the anode electrode 130. The anode electrode 130 has a through hole therein, and the through hole of the anode electrode 130 may be positioned to correspond to one end of the cathode electrode 120. The through hole of the anode electrode 130 may have a structure that decreases as the distance from the cathode electrode 120 increases.

The neutral electrode 140 is an electrode including an insulating material and may be a portion where an arc is generated when plasma is generated. For example, the neutral electrode 140 may include boron nitride and aluminum nitride.

When a predetermined voltage is applied to each of the cathode electrode 120 and the anode electrode 130 and an ignition gas such as argon is injected, an arc is generated in the neutral electrode 140 and water vapor is provided from the source, resulting in a reaction as shown in Formula 1 It may be generated in the first hydrogen purification device 100.

Referring back to FIG. 1, when methane passes through the first hydrogen purification apparatus 100, it may be decomposed into CO and H2 as shown in Chemical Formula 1. H2 is used as a fuel, but substances such as CO, CO2, H2O, and O2 are substances that must be purified as reaction by-products. The second hydrogen purification apparatus 200 may be used to purify the reaction by-product.

According to an embodiment, the materials that have passed through the first hydrogen purification device 100 are in a high temperature state, but when flowing into the second hydrogen purification device 200, they must be cooled and introduced to a room temperature. The system 1000 may further include a heat exchanger (HE) between the first hydrogen purification device 100 and the second hydrogen purification device 200.

The heat exchanger (HE) may include a pipe through which a high-temperature material flows from the first hydrogen purification device 100 and a cooling unit that surrounds an outer wall of the pipe and provides cooling water. The material in the high temperature state that has passed through the first hydrogen purification device 100 and the coolant in the cooling unit do not contact each other, and the material in the high temperature state that has passed through the first hydrogen purification device 100 flows inside the pipe and flows through the pipe. The temperature of the material discharged through the first hydrogen purification apparatus 100 may be reduced to room temperature by flowing a refrigerant such as cooling water from a cooling unit disposed on the outer wall of the pipe during the period. Therefore, heat exchange can be efficiently performed without contamination of the cooling water.

According to an embodiment, in the hydrogen purification system 1000, substances such as CO, CO2, H2O, and O2 as well as the target H2 from the first hydrogen purification device 100 to the second hydrogen purification device 200 are reaction by-products. It may further include a pump (PP) to move. For example, the pump PP may be disposed between the first hydrogen purification device 100 and the second hydrogen purification device 200. As another example, the pump PP may be disposed to be connected to one side of the second hydrogen purification apparatus 200.

3 is a view for explaining a second hydrogen purification apparatus of the hydrogen purification system shown in FIG. 1.

Referring to FIG. 3, the second hydrogen purification apparatus 200 may be a device for selectively discharging only H2 from among introduced H2, CO, CO2, H2O, and O2.

The second hydrogen purification apparatus 200 may include a plurality of purification units 210 and 220. For ease of explanation, the second hydrogen purification device 200 may include a first purification unit 210 and a second purification unit 220, and in the present invention, the purification unit of the second hydrogen purification device 200 The number of fields is not limited to this.

The first purification unit 210 may include a first chamber CH1 and a first heating unit HT1 disposed outside the first chamber CH1. The second purification unit 220 may include a second chamber CH2 and a second heating unit HT2 disposed outside the second chamber CH2. The first and second purification units 210 and 220 may have the same structure.

It may further include pipes connecting each of the first chamber CH1 and the second chamber CH2 or connecting the first chamber CH1 and the second chamber CH2. Valves for opening and closing the pipes may be installed in each of the pipes.

The pipes (IL, P1, P2, P3, P4, P5, P6, OL) are connected to the first hydrogen purification device 100 to receive materials such as H2, CO, CO2, H2O, and O2. ), the inlet pipe IL, the first pipe P1 connected to each of the first purification unit 210 and the second purification unit 220, and a second pipe P2 connecting between the first pipe P1 , A third pipe (P3) branching from the second pipe (P2), a discharge pipe (OL) through which the gas purified from the second hydrogen purification device 200 is discharged, the first purification unit 210 and the second purification unit The fourth pipe (P4) connected to 220 and connected to the discharge pipe (OL), the fifth pipe (P5) connecting the fourth pipe (P4), the discharge pipe (OL), and the fifth pipe (P5) It may include a sixth pipe (P6) connected to.

Valves (V1, V2, V3, V4, V5, V6, V7, V8, V9, V10) are the first valve (V1) and the second valve (V2) installed in the first pipe (P1), the second pipe In the third valve (V3) and fourth valve (V4) installed in (P2), the fifth valve (V5) and sixth valve (V6) installed in the fourth pipe (P4), and the fifth pipe (P5). It may include a seventh valve V7 and an eighth valve V8 installed, and a ninth valve V9 and a tenth valve V10 installed in the sixth pipe P6.

The inlet pipe (IL) connects between the first valve (V1) and the second valve (V2), and the third valve (V3) connects between the third valve (V3) and the fourth valve (V4), and discharges The pipe OL connects between the fifth valve V5 and the sixth valve V6, and the pipe connecting the fifth pipe P5 and the sixth pipe P6 is the fifth pipe P5 to the seventh pipe. The valve V7 and the eighth valve V8 may be connected, and the sixth pipe P6 may be connected between the ninth valve V9 and the tenth valve V10.

According to an embodiment, each of the purification units 210 and 220 receives a reformed material from the first hydrogen purification device 100 and uses a catalyst to purify H2 in the material or a catalyst used during purification. At least one of the functions of reproducing may be performed.

4 and 5 are diagrams for explaining a process of using the second hydrogen purification apparatus shown in FIG. 3.

As shown in FIG. 4, when the first purification unit 210 performs the function of purification, the first valve V1 is turned on, and the second valve V2 and the third valve V3 are respectively By off, the material provided from the first hydrogen purification apparatus 100 may be provided to the first chamber CH1. A catalyst is provided to the first chamber CH1, and the catalyst may be combined with a by-product in the hydrogen gas to purify the hydrogen gas. For example, the catalyst includes nickel (Ni) and M/S, and may be combined with CO, CO2, H2O, and O2 introduced into the first purification unit 210 to purify H2. CO, CO2, H2O, and O2 may be combined with Ni and M/S as shown in Formula 2, Formula 3, Formula 4, and Formula 5 below.

Gas purified from the first chamber CH1, that is, hydrogen gas of 99.999% purity, is discharged through the discharge pipe OL, the fifth valve V5 is turned on, and the sixth valve V6 and the seventh valve ( V7) Each can be turned off. While the first purification unit 210 performs the function of purification, the states of the fourth valve V4, the eighth valve V8, and the tenth valve V10 do not affect the first purification unit 210. I can't. In this case, the first heating unit HT1 may be turned off and may be in a room temperature state.

While the first purification unit 210 performs a purification function, the second purification unit 220 may perform a regeneration function. In this case, the tenth valve V10 is turned on, the ninth valve V9 is turned off, the eighth valve V8 is turned on and the seventh valve V7 is turned off, Hydrogen gas sequentially passing through the pipe P5 is provided to the second chamber CH2, and in this case, the second heating unit HT2 is turned on and may be in a high temperature state of 250°C. Accordingly, the catalyst may be regenerated in the second chamber CH2. NiO combines with H2 and is reduced to Ni, and M/S-H2O and M/S-CO2 can be converted into M/S by separating H2O and CO2 at high temperature. See Formula 6, Formula 7, and Formula 8 below.

The catalyst regenerated in the second chamber (CH2) is discharged to the outside through the second pipe (P2) and the third pipe (P3) by turning on the fourth valve (V4) and turning off the third valve (V3), and reused. Can be.

As shown in FIG. 5, when the first purification unit 210 performs the function of regeneration, the first valve V1 is turned off to cut off the connection with the inlet pipe IL, and the tenth valve V10 Is turned on, the ninth valve (V9) is turned off, the injected hydrogen gas is sent to the fifth pipe (P5), the seventh valve (V7) is turned on, and the eighth valve (V8) and the fifth valve (V5) May be provided to the first chamber CH1 through the fifth pipe P5. In this case, the first heating unit HT1 is in an on state and may be in a high temperature state of 250°C. In the first purification unit 210, a reaction as described in Formula 6, Formula 7, and Formula 8 may occur, and the fourth valve V4 may be turned off to discharge the catalyst through the third pipe P3.

While the first purification unit 210 performs a regeneration function, the second purification unit 220 may perform a purification function. In this case, the first valve V1 and the fourth valve V4 are turned off, and the second valve V2 is turned on to communicate the inlet pipe IL and the second chamber CH2. The second heating unit HT2 may be in an off state and the second chamber CH2 may be in a room temperature state. In the second chamber CH2, the reaction of Chemical Formula 1, Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 may occur and purified hydrogen gas may be discharged through the discharge pipe OL. To this end, each of the eighth valve V8 and the fifth valve V5 may be in an off state, and the sixth valve V6 may be in an on state.

As described above, since the first purification unit 210 and the second purification unit 220 have the same structure, the purification function or the regeneration function can be performed flexibly, so that the process can be performed more efficiently.

As described above, reforming, separation, and removal processes are performed using the first hydrogen purification apparatus 100 and the second hydrogen purification apparatus 200 to obtain high purity (99.999%) hydrogen gas, thereby obtaining a water gas transition (water gas). It is possible to omit post-stage processes such as shift) reaction process and pressure swig absorption. Accordingly, the configuration required for the process is economical and not only reduces operating costs compared to hydrogen production in the conventional method, but also improves the purity and yield of hydrogen relative to impurities, thereby contributing to productivity improvement.

The above-described contents are specific examples for carrying out the present invention. In addition to the above-described embodiments, the present invention will include simple design changes or embodiments that can be easily changed. In addition, the present invention will also include techniques that can be easily modified and implemented using the embodiments. Therefore, the scope of the present invention is limited to the above-described embodiments and should not be defined, and should be determined by the claims and equivalents of the present invention as well as the claims to be described later.

1000: hydrogen purification system
100: first hydrogen purification device
200: second hydrogen purification device
HE: heat exchanger
PP: pump
110: chamber
120: cathode electrode
130: anode electrode
140: neutral electrode
210: first purification unit
220: second purification unit
CH1, CH2: chamber
HT1, HT2: heating part
IL, OL, P1, P2, P3, P4, P5, P6: piping
V1, V2, V3, V4, V5, V6, V7, V8, V9, V10: valve

Claims (5)

Hydrogen is reformed from the compound using plasma, and a cathode electrode having a sharp structure at one end, and a through hole having a structure that decreases as the distance from the cathode electrode increases at a position corresponding to one end of the cathode electrode. A first hydrogen purification apparatus including an anode electrode disposed to be spaced apart from the cathode electrode, a neutral electrode disposed between the cathode electrode and the anode electrode;
It is connected to the first hydrogen purification device to purify hydrogen from reformed hydrogen and by-products using a catalyst and to regenerate the catalyst, and a first chamber, a first heating unit disposed outside the first chamber, and a second A chamber, a second heating unit disposed outside the second chamber, pipes connected to the first hydrogen purification device and connecting between the first and second chambers, and a plurality of valves installed in the pipes A second hydrogen purification device comprising;
It is disposed between the first and second hydrogen purification devices to lower the temperature of the reformed hydrogen and the by-product, and a pipe connecting between the first and second hydrogen purification devices and a refrigerant surrounding the outer wall of the pipe A heat exchanger including a cooling unit providing a; And
A pump disposed between the first and second hydrogen purification devices to move the reformed hydrogen and the by-product to the second hydrogen purification device,
The second hydrogen purification device,
A first purification unit including a first chamber and a first heating unit providing heat to the first chamber;
A second purification unit disposed to be spaced apart from the first purification unit and including a second chamber and a second heating unit providing heat to the second chamber;
An inlet pipe for providing a process gas to at least one of the first and second chambers;
A first pipe connected to the inlet pipe and the first and second chambers;
A second pipe connected to the first pipe;
A third pipe connected to the second pipe;
A discharge pipe for discharging purified hydrogen from at least one of the first and second chambers;
A fourth pipe connected to the discharge pipe and the first and second chambers;
A fifth pipe connected to the fourth pipe;
A sixth pipe connected to each of the discharge pipe and the fourth and fifth pipes;
A first valve and a second valve installed in the first pipe and spaced apart by the inlet pipe;
A third valve and a fourth valve installed in the second pipe and spaced apart by the third pipe;
A fifth valve and a sixth valve installed in the fourth pipe and spaced apart by the discharge pipe;
A seventh valve and an eighth valve installed in the fifth pipe and spaced apart by the sixth pipe; And
A hydrogen purification system including a ninth valve and a tenth valve installed in the sixth pipe and spaced apart by the fifth pipe. The method of claim 1,
The compound includes methane (CH ₄ ),
The by-product is a hydrogen purification system comprising at least one selected from the group consisting _{of CO, CO 2} , H ₂ O, and O _2. The method of claim 1,
In the second hydrogen purification apparatus, one of the first chamber and the second chamber purifies the hydrogen and the other regenerates the catalyst. delete delete

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