KR101720577B1 - Fixed-bed reforming system and method using the oxygen transfer material - Google Patents

Abstract

The present invention relates to a modification device producing hydrogen by using fuel, and more specifically, to a modification device in which an oxygen carrier is fixed inside a chamber in the form of a catalyst, rather than through chemical looping, and allows air and fuel into the chamber alternately, and thus induces oxidation and reduction repeatedly. According to one embodiment of the present invention, a fixed-bed modification system using an oxygen carrier comprises: a reaction chamber coated with an oxygen carrier on the surface thereof; a first supply means for supplying air into the reaction chamber; and a second supply means for supplying fuel into the reaction chamber, wherein air supply by the first supply means and fuel supply by the second supply means are performed alternately, such that oxidation and reduction occur alternately.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a fixed bed reforming system and method using an oxygen transfer material,

The present invention relates to a reformer for producing hydrogen using a fuel, and more particularly, to a fuel reforming apparatus for reforming an oxygen carrier by fixing an oxygen carrier in the form of a catalyst rather than a medium circulation system, And the oxidation and reduction processes are repeated.

As fossil fuels used as fuels for combustion of engines are typically petroleum and natural gas, due to the limitations of these fossil fuel reserves and the environmental problems caused by pollutants during combustion, Research is actively underway. Currently known representative clean fuels include hydrogen, biodiesel, and bioethanol.

In particular, hydrogen has an advantage of being environmentally friendly because it does not contain carbon components contained in petroleum, and is advantageous in that it can improve the efficiency of the engine due to its fast combustion speed as a fuel and wide flammability limit. It has the greatest advantage of being infinite. Because of these advantages, hydrogen is receiving the greatest attention as a new clean fuel.

With growing interest in hydrogen as a fuel, hydrogen applications such as power generation systems, fuel cells, and transportation systems are rapidly expanding. Fuel reforming is widely used to efficiently produce hydrogen. It is a method of separating only hydrogen by oxidizing a hydrocarbon fuel under a rich condition.

Since the conventional reforming method uses air as the oxidizing gas, a step of separating nitrogen from the gas after the reaction is required, and a toxic nitrogen oxide is generated. In order to solve this problem, an oxygen generating device is added to induce a pure oxygen reaction. The proposed method is Chemical Loop Reforming (CLR).

The air circulation reforming system is divided into an air reactor and a fuel reactor, so that the metal oxygen donor particles circulate through the two reactors, adsorbing only oxygen from the air reactor and transferring the oxygen to the fuel reactor to cause a reforming reaction. Since the oxygen donor particles separate oxygen from the air and transfer it to the reformer, it is possible to completely remove the impurities that are not necessary for the reaction such as nitrogen and carbon dioxide mixed in the air. Since the flame is not generated in the fuel reactor, There is an advantage that it is blocked.

However, in the case of the medium circulation reforming method, since the metal oxygen donor particles directly move, the flow control of the particles is difficult and the volume of the system becomes very large. In addition, it is one of weaknesses that heat is required to be supplied to the oxidation process of the metal oxygen donor particles, which is an endothermic reaction, and that the fuel oxide reaction in the fuel reactor must maintain a high temperature.

On the other hand, in the conventional fuel reforming apparatuses known in the art, nitrogen oxides (NOx) are generated as a result of the reaction. The nitrogen oxides are generated by the combination of oxygen and nitrogen at high pressure and high temperature, Building corrosion and destruction of ecosystems, and the human body is attributed to various respiratory diseases such as bronchitis, pneumonia, and asthma.

In addition, in the conventional fuel reforming apparatuses, carbon monoxide or carbon dioxide is generated because hydrocarbon fuel is mainly used to produce hydrogen, and the remaining carbon particles are deposited on the surface of the reformer, and the reforming reaction gradually decreases with time . This is notable in a media circulation reformer where metal oxygen donor particles circulate by fluid flow.

As a solution to this problem, the present invention provides a concept of a fixed bed reformer which utilizes an oxygen transfer material similar to oxygen donor particles used in the medium circulation reforming but does not require direct flow. It is expected that this will not only miniaturize the device but also solve the various weaknesses of the media recycling method.

In addition, in this specification, a system in which the generation of nitrogen oxides is prevented in advance and a control operation thereof will be presented.

According to an embodiment of the present invention, there is provided a plasma processing apparatus comprising: a reaction chamber in which an oxygen transfer material is coated on a surface; A first supply means for supplying air into the reaction chamber, and a second supply means for supplying fuel into the reaction chamber, wherein the air supply by the first supply means and the fuel supply by the second supply means And the oxidizing and reducing processes are alternately performed. The present invention provides a stationary phase reforming system using an oxygen transfer material.

According to an embodiment of the present invention, the oxygen transfer material absorbs oxygen in the air at the time of supplying air by the first supply means, and discharges other gases including nitrogen. When the oxygen is supplied by the first supply means, And is a material that releases the product by reforming using oxygen.

Here, the air supply direction of the first supply means in the reaction chamber and the fuel supply direction of the second supply means may be the same.

On the other hand, a plurality of reaction chambers are provided, and one of the plurality of reaction chambers and the adjacent reaction chamber are characterized in that the order of supplying air and fuel of the first and second supplying means are opposite to each other You may.

According to one embodiment, the plurality of reaction chambers may be formed in a lattice form.

According to one embodiment, a wave pin, an offset fin, or a dimple may be formed in the reaction chamber.

The fixed-bed reforming system using an oxygen transfer material according to an embodiment of the present invention includes a first control unit for adjusting the amount of air supplied and the supply time of the first supply unit, a second control unit for adjusting the fuel supply amount and the supply time of the second supply unit The first control unit and the second control unit may be interlocked so that the remaining energy other than the energy required at the beginning of the operation of the reforming system may be received.

The stationary phase reforming system using the oxygen transfer material according to an embodiment may further include a coolant or coolant line connected to the reaction chamber to transfer heat through heat exchange and an auxiliary heat source disposed on the coolant or coolant line .

According to another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising the steps of: (a) supplying air into a reaction chamber coated with an oxygen transfer material to absorb oxygen on the surface of the oxygen transfer material; (b) stopping supply of air to the inside of the reaction chamber and discharging the gas other than the absorbed oxygen; (c) supplying fuel to the inside of the reaction chamber in which oxygen is absorbed to reform it; And (d) stopping the supply of fuel into the reaction chamber and discharging the product of the reforming reaction, wherein after the step (d), the steps (a) to (d) are repeated in sequence The present invention provides a fixed phase reforming method using an oxygen transfer material.

Here, the direction of supplying air into the reaction chamber and the direction of supplying fuel may be the same.

(E) calculating an oxidation heat and a reduction heat generated in the reaction chamber; and (f) calculating an oxidation heat and a reduction heat generated in the reaction chamber, And adjusting the supply flow rate and the supply time.

According to an embodiment, the oxidation heat and the reduction heat may be calculated using a flow rate of gas discharged to the outside of the first reaction chamber and a temperature measured in the first reaction chamber.

In the present invention, an autothermal reforming method in which heat energy generated in a reforming reaction is effectively recovered is used. Therefore, there is an advantage that the waste of heat is minimized and the supply of heat energy from the outside can be drastically reduced.

As a fixed-bed reforming system, it is possible to miniaturize, simplify, and increase the efficiency of the reforming apparatus, so that it can be attracting a great deal of attention in various fields where production and use of hydrogen have been difficult due to the spatial and cost constraints caused by the reactor and the post- .

In particular, since hydrogen can be produced using conventional fuels in the field of transportation, it will become a very popular technology from hydrogen fueling in internal combustion engines to future fuel cell vehicles.

1 is a conceptual diagram of a fixed bed reforming system using an oxygen transfer material according to an embodiment of the present invention.
FIG. 2 is a view showing a state where heat is transferred when a plurality of reaction chambers are provided in a fixed bed reforming system according to an embodiment of the present invention.
3 is a diagram illustrating oxidation and reduction processes of a stationary phase reforming system using an oxygen transfer material according to an embodiment of the present invention.
4 is a view illustrating a control operation when a plurality of reaction chambers are provided in a fixed bed reforming system according to an embodiment of the present invention.
FIG. 5 is a view showing a pin or dimple formed inside a reaction chamber of a fixed bed reforming system according to an embodiment of the present invention. FIG.
6 is a block diagram illustrating a fixed bed reforming system in accordance with an embodiment of the present invention.
7 is a block diagram illustrating a valve control operation of the fixed bed reforming system according to an embodiment of the present invention.
8 is a block diagram illustrating a fixed phase modifying method in accordance with an embodiment of the present invention.

The embodiments described below are provided so that those skilled in the art can easily understand the technical idea of the present invention, and thus the present invention is not limited thereto. In addition, the matters described in the attached drawings may be different from those actually implemented by the schematic drawings to easily describe the embodiments of the present invention.

It is to be understood that when an element is referred to as being connected or connected to another element, it may be directly connected or connected to the other element, but it should be understood that there may be other elements in between. Also, throughout this specification, when a member is " on " another member, it includes the case where there is another member between the two members as well as when the member is in contact with the other member.

The term "connection" as used herein means a direct connection or an indirect connection between a member and another member, and may refer to all physical connections such as adhesion, attachment, fastening, bonding, bonding, and proximity.

Also, the expressions such as 'first, second', etc. are used only to distinguish a plurality of configurations, and do not limit the order or other features between configurations.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. The word "comprise" or "having" is used herein to mean that a feature, a number, a step, an operation, an element, a component or a combination thereof is disclosed in the specification, A step, an operation, an element, a part, or a combination thereof.

First, the construction and modification of the stationary phase reforming system of the present invention will be described in detail with reference to FIGS. 1 to 4. FIG.

1 is a conceptual diagram of a fixed bed reforming system using an oxygen transfer material according to an embodiment of the present invention. FIG. 2 is a view showing a state where heat is transferred when a plurality of reaction chambers are provided in a fixed bed reforming system according to an embodiment of the present invention. 3 is a diagram illustrating oxidation and reduction processes of a stationary phase reforming system using an oxygen transfer material according to an embodiment of the present invention. 4 is a view illustrating a control operation when a plurality of reaction chambers are provided in a fixed bed reforming system according to an embodiment of the present invention.

A fixed bed reforming system according to an embodiment of the present invention includes a reaction chamber 100 having an oxygen carrier 110 coated on a surface thereof; (121) for supplying air into the reaction chamber (100) and a second supply means (122) for supplying fuel into the reaction chamber, wherein the first supply means The air supply and the fuel supply by the second supply means 122 are alternately performed, so that oxidation and reduction processes are alternately performed.

In the present invention, the oxygen transfer material (Oxygen Carrier) 110 is formed by spraying or wash coating a coating liquid containing nickel on the inside of a reaction chamber 100 made of a metal surface, then removing the slurry and drying in an oven for several minutes to several minutes . Nickel is supported, but the present invention is not limited thereto. The oxygen transfer material 110 absorbs oxygen in the air when the air is supplied by the first supply means 121, and the other gas including nitrogen And may be any material other than nickel-supported material as long as it has a function of discharging a reformed product containing hydrogen by reforming it by using oxygen absorbed first at the time of fuel supply by the second supply means 122.

In the present invention, the reaction chamber 100 may have a circular cross section like a pipe pipe, or may have a rectangular cross section. The reaction chamber 100 may be a porous honeycomb structure of a metal or a ceramic monolith, but it is more preferable from the viewpoint of efficiency improvement to adopt a wave, offset fin or dimple shape described later.

The shape and size of the reaction chamber 100 may be varied depending on the demanded amount of the material to be reformed, so that the inlet 120 and the outlet 130 of the reaction chamber may also be of various sizes.

The present invention is characterized in that oxidation and reduction reactions are alternately performed in one reaction chamber 100. Referring to FIG. 1, the oxygen transfer material 110 does not flow but is fixed to the center side of the reaction chamber 100, and air and fuel pass therethrough. Air first flows through the inlet 120, reacts with the oxygen transfer material 110, and then flows toward the outlet 130. It is assumed that the inside of the reaction chamber 100 is the initial vacuum state.

The oxygen transfer material 110 absorbs oxygen (in other words, chemically bonds with oxygen in the air) in the air, and discharges the remaining gas while oxygen is adsorbed on the surface of the oxygen transfer material 110. Here, the oxygen transfer material 110 requires a predetermined heat for oxidation because oxygen is adsorbed, that is, an oxidation reaction takes place. That is, an endothermic reaction occurs. In the fixed bed reforming system of the present invention, heat necessary for oxidation can be provided through the drive energy initially applied. This process can be represented as shown in Reaction Scheme 1 below. For reference, it is assumed that the air supplied here is dry air (N2 + O2 + CO2 + CO + Ne + He ...).

[Reaction Scheme 1]

_{2Ni + O 2 ↔ 2NiO, △} H298 = -Q1 kJ / mol

Further, when the fuel is supplied, the oxygen transfer material 110 separates the hydrogen particles contained in the fuel from the fuel, which is the polymer, to generate hydrogen. Since the fuel uses hydrocarbon (CnH2n + 2) fuel, carbon monoxide and carbon dioxide are generated and the remaining carbon can be deposited on the surface. In the present invention, since the stationary phase oxygen transfer material is used, the metal particles deposited on the surface can be quickly replaced have. Also, if necessary, the carbon deposited inside the reforming apparatus can be oxidized and removed by using air, and the oxidation heat generated at this time can be utilized for reforming. It is possible to reduce the cost of management and maintenance as compared with the medium cycle reforming apparatus.

[Reaction Scheme 2]

_{NiO + CH 4 ↔ Ni + 2H} 2 + CO, △ H298 = Q2 kJ / mol

As shown in Reaction Scheme 2, the reforming product containing hydrogen is discharged from the oxygen transfer material 110 during fuel supply. Partial oxidation, that is, reforming reaction occurs during the drop of oxygen from nickel, The predetermined heat is released. That is, an exothermic reaction occurs.

Since the oxidation process and the reduction process referred to herein are based on the oxygen transfer material, the reduction process corresponds to the oxidation (reforming) process of the fuel. The two processes are represented in Fig. 1 by seal and dashed lines, respectively.

It should be noted that the reaction at the surface of the oxygen transfer material 110 of the present invention is completely different from the reaction of the catalyst. Although the catalyst affects the change of the reaction rate only by participating in the chemical reaction and increasing or decreasing the reaction rate and remains as it is before and after the reaction, Is completely different from the catalyst in that the oxygen transfer material 110 itself reacts with air and fuel to obtain a reformed product and absorb and release thermal energy without much association.

In the case of the catalyst, any substance may be continuously flowed through the catalyst for the chemical reaction. However, in the case of the oxygen transfer material 110 of the present invention, when the oxygen adsorbed from the air is exhausted, A control operation such as adsorption of oxygen is required.

In the conventional reforming apparatus or system, various problems have arisen in the background art such as the generation of nitrogen oxides, the problem of ignition of the reforming apparatus and the system, and the environmental pollution at the time of nitrogen oxide emission. Therefore, one technical problem of the present invention is to reduce the generation of such nitrogen oxides.

To this end, in the present invention, the first supply means 121 for supplying air and the second supply means 121 for supplying fuel are sequentially controlled to filter out only oxygen particles in the air (nitrogen is discharged from the air) And is advantageous in minimizing the generation of nitrogen oxides by being used in the reaction with the fuel.

On the other hand, in the air inflow step, heat supply from the outside is required from the outside in order to sustain the reaction. In the present invention, the oxidation and reduction processes are operated in a cycle to oxidize the fuel in the reduction process, Is stored in the reaction chamber structure including the reaction chamber 110 so that it can be used in the oxidation process. That is, unlike the circulation reforming apparatus of the present invention, it is not necessary to externally supply the heat energy required for oxidizing the oxygen transfer material 110, or it is possible to utilize most of the energy required by the minimum energy supply, A modified autothermal reforming is implemented.

When one reaction chamber 100 using the oxygen transfer material 110 is provided, a storage unit (not shown) is further provided at a portion surrounding the oxygen transfer material 110 to store energy, Can be done.

However, in the case of a method of storing energy in the reaction chamber 100 with a heat storage unit, a heat loss phenomenon occurs in which heat is released to the outside as time passes, and energy generated from the surface of the oxygen transfer material 110 is effectively stored And there is a problem that it is practically difficult to use.

In this case, as shown in FIG. 2, a plurality of reaction chambers provided with the oxygen transfer material 110 are provided so that heat transfer can be performed between adjacent reaction chambers 100 and 100 ', thereby preventing loss of heat energy And heat energy can be utilized most efficiently.

Referring to FIG. 2, air and fuel (gaseous fuel) are shown around the reaction chambers 100 and 100 ', and first supply means 121 and 121' And second supply means 122 and 122 'are provided. The first supply means 121 and 121 'and the second supply means 122 and 122' may include a variety of flow path opening and closing means such as a poppet valve or a butterfly valve. However, a butterfly valve (Or flap valve) is preferably employed.

Although the first reaction chamber 100 and the second reaction chamber 100 'are shown in the figure, this is only one example, and the third, fourth, It should be noted that the nth reaction chamber may be further provided.

Air is first introduced into the first reaction chamber 100 and one of the second reaction chambers 100 '. For example, the air introduced into the second reaction chamber 100 reacts with the oxygen transfer material 110 'and oxygen is adsorbed on the surface. At this time, when air is introduced into the first reaction chamber 100 and fuel is introduced into the second reaction chamber 100 ', heat required for the oxidation reaction in the first reaction chamber 100 is generated in the second reaction chamber 100' It can be supplied by heat. Thus, by providing a self-heating reforming system that recovers the heat generated in any one of the reaction chambers and supplies the same to the adjacent reaction chambers, it is possible to minimize the waste of heat and drastically reduce the supply of heat energy from the outside. In the above example, an oxidation reaction occurs in the first reaction chamber 100 and a reduction reaction occurs in the second reaction chamber 100 '. However, as a process after the reaction, the first reaction chamber 100 is subjected to a reduction reaction When the oxidation reaction occurs in the second reaction chamber 100 ', the autothermal reforming reaction can be continued. In other words, when it is assumed that the first supply means 121 and the second supply means 122 connected to any one of the reaction chambers and the reaction chamber adjacent thereto are provided, the first supply means 121 and the second supply means 122, 2 and the supply order of the air and the fuel of the supply means 122 are made to be opposite to each other, the heat is recovered and utilized continuously between the adjacent reaction chambers, so that a considerable amount of heat energy can be saved.

In the meantime, the present invention is characterized in that the air supply direction of the first supply means 121 and the fuel supply direction of the second supply means 122 are the same in the reaction chamber 100. For example, the air supply direction and the fuel supply direction may be specifically directed from the upstream side to the downstream side along the longitudinal direction of the reaction chamber 100.

Referring to FIG. 3, FIG. 3 (a) shows the inflow of air, and FIG. 3 (b) shows the inflow of fuel. 3 (a), oxygen particles m1 are adsorbed on the surface of the oxygen-transferring material 110 when a certain amount of air is introduced. Experimentally, as the oxygen- m1) is adsorbed. Accordingly, the majority of the endothermic reaction occurs near the front of the oxygen transfer material 110.

As shown in FIG. 3 (b), when a certain amount of fuel flows, the oxygen particles adsorbed on the surface of the oxygen transfer material 110 react with the fuel to generate a reformed product m2. A large number of oxygen particles are generated on the front surface of the oxygen-transferring material 110, and the concentration of the reforming product m2 is also reduced on the rear surface of the oxygen-containing material.

3, if the direction of air flow is different from the direction of flow of fuel, the reactivity with the fuel is high in the region where the oxygen particles on the surface of the oxygen transfer material 110 are not rich, while in the rich region, And the degree of reactivity decreases. As a result, there is a difference in the amount of the reformed product (m2), that is, the amount of produced hydrogen.

In this respect, it is a significant embodiment that the air supply direction of the first supply means 121 and the fuel supply direction of the second supply means 122 in the reaction chamber 100 are the same.

According to an embodiment of the present invention, the plurality of reaction chambers are stacked or arranged in a lattice shape, and the oxidation and reduction processes of adjacent reaction chambers are alternately performed in an opposite order. 4 (a) and 4 (b) illustrate a conceptual diagram of a stationary phase reforming apparatus in which stacked layers are formed, and FIG. 4 (c) and FIG. 4 4 (d) shows a conceptual diagram of a fixed bed reforming apparatus arranged in a lattice form. As shown in the figure, the oxidation and reduction reactions are reversed in the adjacent reaction chambers and alternately.

Next, the reaction chamber of the fixed bed reforming system according to one embodiment of the present invention will be described in more detail with reference to FIG.

An oxygen transfer material 110 is coated on the inner surface of the reaction chamber 100. In order to increase the reactivity of the reaction chamber 100, a fin shape and a dimple shape . The fin may be, for example, a wave fin or an offset fin formed in a predetermined thickness and pattern, but the present invention is not limited thereto, and heat transfer performance and volume efficiency such as heat absorption and heat dissipation Any fin and dimple of any shape and size will be included within the scope of the present invention if it is formed excellently. As shown in the figure, a pin or a pin in the form of a wave or an offset may be seated and inserted into the reaction chamber 100 and then connected by a method such as Laser Welding.

Hereinafter, the control operation of the fixed bed reforming system according to one embodiment of the present invention will be described with reference to FIG. 6 is a block diagram illustrating a fixed bed reforming system in accordance with an embodiment of the present invention. 7 is a block diagram illustrating a valve control operation of the fixed bed reforming system according to an embodiment of the present invention.

As described above, the fixed bed reforming system of the present invention may be composed of a plurality of reaction chambers (two reaction chambers 100 and 100 'are shown in FIG. 6). The first supply means 121 and 121 'and the second supply means 122 and 122' may be connected to the respective reaction chambers. For example, the first supply means 121 and 121 ' 122 and 122 'may be an On / Off valve for opening and closing a flow path through which the fluid flows. The first supply means 121 and 121 'and the second supply means 122 and 122' may be connected to the first storage unit S1 and the second storage unit S2, respectively, S1 may serve to store air, and the second storage unit S2 may serve to store fuel.

The first and second discharge means 131 and 131 'and the second discharge means 132 and 132' may be connected to the respective reaction chambers. The first and second discharge means 131 and 131 ' (132, 132 ') Also, an On / Off valve may be applicable. The first discharge means 131 and 121 'and the second discharge means 132 and 132' may be connected to the third storage S3 and the third storage S3, respectively, S3 may serve to store the remaining gas after oxygen is adsorbed to the oxygen transfer material 110, and the fourth storage unit S4 may serve to store modified hydrogen and the like. The fourth storage unit S4 may store only hydrogen that is connected to a gas or gas-liquid separator (not shown in the figure) so as to separately store the reformed hydrogen.

7, the controller 300 includes a first controller 310 for adjusting the amount of air supplied and a supply time of the first supply unit 121, a second controller for controlling the second supply unit 122, The first control unit 310 and the second control unit 320 may control the fuel supply amount and the supply time of the reforming system 1 so that the energy remaining in the reforming system 1, (320) are interlocked with each other.

The first control unit 310 and the second control unit 320 are components included in the configuration of the ECU of the vehicle or the control panel of the construction machine and are provided with the air supply amounts U1 and U2 and the supply times t1 and t2 .

In order to continuously operate the autothermal reforming apparatus, the first control unit 310 and the second control unit 320 (or the first control unit 310 and the second control unit 320) ) Is required.

The oxidation heat is a parameter determined by factors such as the supply amount U1 of the air and the supply time t1 with reference to the oxidation heat Q1 and the reduction heat Q2, It is possible to control the system by separately monitoring the supply amounts U1 and U2 and the supply times t1 and t2 of the air and the fuel, because the parameters are determined by factors such as the supply time t2.

On the other hand, the oxidation heat (Q1) and the reduction heat (Q2) may be determined from the reaction temperatures (T1 and T2) of the reaction chamber.

Therefore, the reaction temperatures (T1, T2) during the oxidation and reduction reactions of the reaction chamber with the supply amounts of the air and fuel (U1, U2) and the supply times (t1, t2) The first control unit 210 and the second control unit 220 can be adjusted so that the oxidation column Q1 and the reduction column Q2 detected by the chamber coincide with each other.

According to another embodiment of the present invention, the first control unit 210 and the second control unit 220 control the first and second discharge units 131 and 131 'and the second discharge unit 132 and 132', respectively It can also play a role. In other words, the first control unit 210 may control the first supply unit 121 and 121 'and the first discharge unit 131 and 131', and the second control unit 220 may control the second supply unit 122 , 122 'and the second discharge means 132, 132'. In this case, not only the control of the supply amounts U1 and U2 and the supply times t1 and t2 of air and fuel but also the discharge amount U3 of remaining residual gas after oxygen adsorption to the oxygen transfer material 110, The discharge time t3 for the discharge amount U3 and the discharge time t4 for the discharge amount U4 can be adjusted.

By more actively controlling the emission amounts U3 and U4 and the emission times t3 and t4, it becomes possible to control finer control of the oxygen adsorption amount within the reaction chambers 100 and 100 'and the concentration of the reformed hydrogen. For example, as shown in FIG. 3, it has been experimentally found that the concentration of the oxygen particles m1 adsorbed on the surface of the oxygen transfer material 110 decreases toward the downstream side of the reaction chamber. It is possible to increase the concentration at which the oxygen particles m1 on the downstream side of the reaction chamber are adsorbed. Through such fine adjustment, the transfer of the oxidizing heat and the reducing heat between the adjacent plurality of reaction chambers can be made equivalent.

Meanwhile, the fixed bed reforming system according to an embodiment of the present invention may further include a supplementary heat source 210 as shown in FIG. 6 to transfer heat to the reaction chamber. Here, the auxiliary heat source 210 may be, for example, waste heat of an engine, waste heat of an electrical component, waste heat of an electric motor, exhaust heat, and the like. The auxiliary heat source 210 can transfer heat through heat exchange with the reaction chamber through the refrigerant (ex supercritical fluid) line or the cooling water line 200. At this time, the compressor 220 and the directional control valve 230 may be disposed on the refrigerant line or the cooling water line 200 and may be configured to exchange heat with the reaction chamber through a chiller (not shown). A temperature sensor 240 may also be provided on the refrigerant line or the cooling water line 200 to determine whether the heat of the auxiliary heat source is suitable for heat exchange.

That is, in this embodiment, the efficiency of the fixed bed reforming reaction using the oxygen transfer material of the present invention can be improved by supplementing the heat in the reaction chamber through the auxiliary heat source 200. In particular, heat required for oxygen adsorption during the initial reaction of the stationary phase reforming system using the oxygen transfer material can be supplied through the auxiliary heat source 210. After the heat supply required for the initial reaction, the heat from the auxiliary heat source 210 may be bypassed through the directional control valve 230, for example, opening degree adjustment of the three-way valve, so as to allow only heat exchange between adjacent reaction chambers.

As a result, all the columns used in the operation of the fixed bed reforming system of the present invention can be provided by itself, thereby making it possible to construct an ideal reforming system.

The ideal control of the fixed bed reforming system using the oxygen transfer material of the present invention can be actively controlled by the control unit 300 provided at one side of the system. For example, the control unit 300 receives signals (referenced by reference numeral 301) from the sensors 140 and 140 'provided in the reaction chambers 100 and 100', and receives signals from the first and second supply means, (Refer to reference numeral 303) the signal of the sensor 240 provided on the refrigerant or cooling water line 200 and receives the signal from the direction switching valve 230, Can be controlled. The sensors 140, 140 ', 240 here are preferably temperature sensors.

Finally, referring to FIG. 8, the fixed phase modifying method according to an embodiment of the present invention will be described in detail. 8 is a block diagram illustrating a fixed phase modifying method in accordance with an embodiment of the present invention.

Referring to FIG. 8, (a), air is supplied into a reaction chamber coated with an oxygen transfer material to absorb oxygen on the surface of the oxygen transfer material; (b) stopping supply of air to the inside of the reaction chamber and discharging the gas other than the absorbed oxygen; (c) supplying fuel to the inside of the reaction chamber in which oxygen is absorbed to reform it; And (d) stopping the supply of fuel into the reaction chamber and discharging the product of the reforming reaction. After step (d), the steps (a) to (d) may be repeated in sequence.

(E) calculating an oxidation heat and a reduction heat generated in the reaction chamber, and (f) supplying the oxidation heat and the reduction heat generated in the reaction chamber to the inside of the reaction chamber so as to be equal to each other And adjusting the supply flow rate and the supply time of the air and the fuel to control the oxidation and reduction reaction of the stationary reforming system of the present invention to be continuously performed.

Also in this embodiment, when a plurality of reaction chambers are provided, the reaction chambers of one of the plurality of reaction chambers and the adjacent reaction chambers are arranged such that the order of supply of air and fuel of the first and second supply means is opposite . For example, if one reaction chamber is driven in the sequence of (a) - (b) - (c) - (d) -> (d) -> (a) -> (b). It is possible to complementarily utilize the oxidation heat and the reduction heat generated in the adjacent reaction chambers.

The above description is only illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention.

Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments.

The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

100: reaction chamber
110: oxygen transfer material
120: inlet
130: Outlet
121: first supply means
122: second supply means
140, 240: sensor
200: Refrigerant or coolant line
210: Auxiliary heat source
220: Compressor
230: Directional switching valve
300:

Claims (12)

A reaction chamber in which an oxygen transfer material is coated on the surface;
A first supply means for supplying air into the reaction chamber;
And second supply means for supplying fuel into the reaction chamber,
The air supply by the first supply means and the fuel supply by the second supply means are alternately performed,
Wherein the oxidizing and reducing processes are alternately performed. The method according to claim 1,
Wherein the oxygen transfer material absorbs oxygen in the air when the air is supplied by the first supply means and does not absorb other gases including nitrogen,
Wherein the reforming material is a material which is modified by using oxygen absorbed at the time of fuel supply by the second supply means to thereby discharge the reformed product including hydrogen. The method according to claim 1,
Wherein the air supply direction of the first supply means and the fuel supply direction of the second supply means in the reaction chamber are the same. The method of claim 3,
A plurality of reaction chambers are provided,
Wherein one of the plurality of reaction chambers and the reaction chamber adjacent to the one of the plurality of reaction chambers has a reverse order of supply of air and fuel of the first supply means and the second supply means. 5. The method of claim 4,
Wherein the plurality of reaction chambers are formed in a lattice shape. 6. The method of claim 5,
And a wave pin, an offset fin, or a dimple is formed in the reaction chamber. 5. The method of claim 4,
Further comprising a first control unit for adjusting an air supply amount and a supply time of the first supply unit, and a second control unit for adjusting a fuel supply amount and a supply time of the second supply unit,
Wherein the first control unit and the second control unit are interlocked with each other so that the remaining energy other than the energy required at the beginning of the operation of the reforming system is received and supplied. The method according to claim 1,
A coolant or coolant line connected to the reaction chamber and transferring heat through heat exchange; and an auxiliary heat source disposed on the coolant or coolant line. (a) supplying air into a reaction chamber coated with an oxygen transfer material to absorb oxygen on the surface of the oxygen transfer material;
(b) stopping supply of air to the inside of the reaction chamber and discharging the gas other than the absorbed oxygen;
(c) supplying fuel to the inside of the reaction chamber in which oxygen is absorbed to reform it; And
(d) stopping the supply of fuel into the reaction chamber and discharging the product of the reforming reaction,
After the step (d)
Wherein the steps (a) to (d) are repeated in sequence. 10. The method of claim 9,
Wherein the direction of supplying air into the reaction chamber and the direction of supplying fuel are the same. 10. The method of claim 9,
(e) calculating an oxidation heat and a reduction heat generated in the reaction chamber;
(f) adjusting a supply flow rate and a supply time of air and fuel supplied to the inside of the reaction chamber so that the oxidation heat generated in the reaction chamber and the heat of reduction become equal to each other, Modification method. 12. The method of claim 11,
Wherein the oxidation heat and the reduction heat are calculated using a flow rate of gas discharged to the outside of the reaction chamber and a temperature measured in the reaction chamber.

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