KR20210077262A - Hydrogen generator using hydrocarbon fuels and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a hydrogen generator using hydrocarbon-based fuels and a preparation method thereof, in which hydrocarbon-based fuels are heated to a reaction temperature, at which hydrogen is produced with the highest efficiency, within a short time by using a catalyst so as to obtain the highest hydrogen concentration. The present invention provides a hydrogen generator using hydrocarbon-based fuels, which comprises: a plasma reforming reaction unit configured to receive fuel and water vapor, thereby performing plasma reforming; a first catalyst reaction unit for generating hydrogen by selectively performing a steam reforming reaction or a water gas conversion reaction between the fuel and the water vapor according to a reaction temperature after receiving the fuel and water vapor from the plasma reforming reaction unit; a second catalyst reaction unit configured to receive the gas, on which the first catalytic reaction has been performed, from the first catalyst reaction unit, and then selectively perform a water gas conversion reaction or the water vapor reforming reaction so as to generate hydrogen; a final gas temperature reduction unit for cooling and exhausting the final gas discharged from the second catalytic reaction unit; and a hydrogen collecting unit for collecting and storing the final gas discharged from the final gas temperature reduction unit.

Description

Hydrogen generator using hydrocarbon fuels and manufacturing method thereof

The present invention relates to a hydrogen production technology, and more particularly, hydrogen using a hydrocarbon-based fuel capable of obtaining the highest hydrogen concentration by heating the hydrocarbon-based fuel to the reaction temperature of the highest hydrogen production efficiency within a short time using a catalyst. It relates to a manufacturing apparatus and a method therefor.

In general, a hydrogen production technology using a hydrocarbon-based fuel includes an aqueous phase reforming reaction, a steam reforming reaction, or a water gas shift reaction.

The water phase reforming reaction selectively produces hydrogen from polyols (glycerol, sorbitol, xylitol, etc.), which are oxygen-containing hydrocarbons in various types of aqueous solutions derived from cellulose and hemicellulose derived from biomass. manufacturing technology.

And the steam reforming reaction or water gas conversion reaction is a technique for synthesizing hydrogen or methane by reacting hydrocarbons and steam at high temperature in the presence of a catalyst.

In the case of the prior art described above, the catalyst for hydrogen production using hydrocarbon fuel raises the catalyst temperature to the hydrogen production temperature (about 400 to 500° C.) in the form of pellets, and when heated with an electric heater or heated by a catalytic combustion technique, about 20 to It took 30 minutes, and there was a problem that hydrogen production was impossible during this period.

Republic of Korea Patent Registration No. 10-1577432 Republic of Korea Patent Registration No. 10-1523122

The technical problem to be achieved by the present invention for solving the problems of the prior art described above is a plasma reforming device and a metal catalyst coated with a metal having strong thermal durability such as a catalytic material Ce or Cu, La, Ni, etc. on FeCrAl alloy. In the hydrogen production apparatus, the temperature of the metal catalyst is adjusted to the appropriate activation temperature for each of the steam reforming reaction or water gas shift (WGS) reaction for hydrocarbon-based fuel, using an induction heater to the maximum hydrogen production efficiency temperature within a short time. To provide an apparatus and method for producing hydrogen using hydrocarbon-based fuel so that the highest hydrogen concentration can be obtained by rapidly heating to a furnace.

In addition, another technical problem to be achieved by the present invention is to reduce the time it takes to rise to the steady state temperature, which is the hydrogen production temperature (about 400 to 500 ° C) of the metal catalyst, to within 2-3 minutes using an induction heater, and to control the temperature. It is to provide an apparatus and method for producing hydrogen using hydrocarbon-based fuel that can be easily performed.

In addition, another technical task to be achieved by the present invention is that, when hydrocarbons and water are decomposed with low-temperature plasma, high concentrations of CO or various hydrocarbons are generated, which contributes to the generation of CO by WGS reaction, and sequentially the next step It is to provide an apparatus and method for producing hydrogen using a hydrocarbon-based fuel so that various hydrocarbons contribute to hydrogen production by steam reforming (SR) reaction.

In addition, another technical problem to be achieved by the present invention is that the high-temperature waste heat after the hydrogen production reaction heats water required for hydrogen production using a heat exchanger to generate water vapor, thereby improving the thermal efficiency of the entire system. To provide an apparatus and a method therefor.

In order to achieve the above technical object, an embodiment of the present invention, a plasma reforming reaction unit for performing plasma reforming by receiving fuel and water vapor; a first catalyst reaction unit for generating hydrogen by selectively performing a steam reforming reaction or a water gas conversion reaction between the fuel and the water vapor according to a reaction temperature after receiving the fuel and water vapor from the plasma reforming reaction unit; a second catalyst reaction unit that receives the gas on which the first catalytic reaction has been performed from the first catalyst reaction unit, and then selectively performs the water gas conversion reaction or the steam gabil reaction to generate hydrogen; a final gas temperature reduction unit for cooling and exhausting the final gas discharged from the second catalytic reaction unit; and a hydrogen collecting unit for collecting and storing the end gas discharged from the end gas temperature reducing unit; provides a hydrogen production apparatus using a hydrocarbon-based fuel, characterized in that it comprises a.

The catalyst of the first catalytic reaction unit or the second catalytic reaction unit is Cu(10%)Ce(4%)/γ-Al ₂ O ₃ catalyst.

The first catalytic reaction unit or the second catalytic reaction unit. CuCePt / γ-Al ₂ O ₃ Characterized in that it further comprises a catalyst.

The plasma reforming reaction unit. plasma chamber; a swirler installed at the inner inlet side of the plasma chamber to support one end of the spiral anode and to rotate the supplied fuel and water vapor; a plasma spiral anode configured to apply plasma to a mixture of fuel and water vapor supplied by turning through the swirler; a tubular cathode installed outside the plasma chamber to form plasma in the plasma chamber together with the spiral anode; and a honeycomb-type support installed at the inner outlet side of the plasma chamber to support the other end of the spiral anode.

The plasma reforming reaction unit is characterized in that it further comprises a plasma power supply for supplying plasma power to the spiral anode and the tubular cathode.

The first catalytic reaction unit or the second catalytic reaction unit may include an insulating tube; a metal catalyst carrier coated with a catalyst on an outer surface and mounted inside the insulating tube to generate a vortex by external electromagnetic induced electromotive force and heat; and an induction coil wound on the outside of the insulating tube to receive power from an external induction heater power supply and generate electromagnetic induced electromotive force for generating an eddy current in the metal catalyst carrier.

The first catalytic reaction unit or the second catalytic reaction unit further comprises a first heat exchanger for cooling the fuel discharged after performing a steam reforming (SR) reaction and a gas containing water vapor and hydrogen characterized in that

The final gas temperature reduction unit, a second heat exchanger for exchanging heat of the gas introduced after the steam reforming reaction or the water gas conversion reaction; a second water tank for storing the condensed water of the second heat exchanger; a first on/off valve installed between the second heat exchanger and the second water tank to supply condensed water generated in the second heat exchanger to the second water tank; and a second on/off valve for supplying the water stored in the second water tank to the first heat exchanger of the first catalytic reaction unit or the second catalytic reaction unit.

The hydrogen collection unit, one or more low-pressure transport tanks; one or more high-pressure hydrogen tanks; a check valve for preventing a reverse flow of the final gas discharged through the final gas temperature reducing unit; a moisture trap installed on the downstream side of the check valve to remove moisture contained in the final gas; a third valve for selectively branching the final gas from which moisture has been removed to the low-pressure hydrogen tank or the high-pressure hydrogen tank; and a gas booster installed in the pipe between the moisture trap and the low-pressure hydrogen tank and the high-pressure hydrogen tank to pressurize the final gas supplied from the moisture trap or the low-pressure hydrogen tank and discharge it to one or more of the high-pressure hydrogen tanks; It is characterized in that it comprises.

The apparatus for producing hydrogen using the hydrocarbon-based fuel includes: an evaporation tube for accommodating water supplied from a first water tank; and an induction heater mounted on the evaporation tube to heat the water in the evaporation tube to convert it into water vapor.

The evaporation tube, an external insulating material tube; And it is characterized in that it comprises a; corrosion resistance and electromagnetic induction heating metal mesh mounted inside the insulating material is heated and heated.

In order to achieve the above technical problem, another embodiment of the present invention is a plasma reforming reaction unit; A first catalytic reaction unit and a second catalytic reaction unit for selectively performing a steam reforming reaction or a water gas conversion reaction; a final gas temperature reduction unit for cooling and exhausting the final gas containing the generated hydrogen; and a hydrogen collecting unit for collecting and storing the final gas; in the method for producing hydrogen by a hydrogen production apparatus using a hydrocarbon-based fuel configured to include, in a state in which the plasma reforming reaction of the plasma reforming reaction unit is stopped, the steam supply unit a steam reforming reaction step of supplying steam and hydrocarbon-based fuel supplied in the first catalytic reaction unit and then performing a steam reforming reaction; a water gas conversion reaction step of performing a water gas conversion reaction after the second catalyst reaction unit receives the gas discharged from the steam reforming reaction step; a final gas temperature reduction step in which the final gas temperature reduction unit cools and discharges the final gas discharged from the second catalyst reaction unit; and a hydrogen capture step of collecting the final gas, the temperature of which has been reduced by the hydrogen collecting unit, and storing it in a storage tank. It provides a method for producing hydrogen using a hydrocarbon-based fuel, characterized in that it comprises a.

In order to achieve the above technical problem, another embodiment of the present invention is a plasma reforming reaction unit; A first catalytic reaction unit and a second catalytic reaction unit for selectively performing a steam reforming reaction or a water gas conversion reaction; a final gas temperature reduction unit for cooling and exhausting the final gas containing the generated hydrogen; and a hydrogen collecting unit for collecting and storing the final gas; in the method for producing hydrogen by a hydrogen production apparatus using a hydrocarbon-based fuel configured to include, in a state in which the plasma reforming reaction of the plasma reforming reaction unit is stopped, the steam supply unit a steam reforming reaction step of supplying steam and hydrocarbon-based fuel supplied from the to the first catalytic reaction unit and then performing a steam reforming reaction; a water gas conversion reaction step of performing a water gas conversion reaction after the second catalyst reaction unit receives the gas discharged from the steam reforming reaction step; a final gas temperature reduction step in which the final gas temperature reduction unit cools and discharges the final gas discharged from the second catalyst reaction unit; and a hydrogen capture step of collecting the final gas, the temperature of which has been reduced by the hydrogen collecting unit, and storing it in a storage tank. It provides a method for producing hydrogen using a hydrocarbon-based fuel, characterized in that it comprises a.

In an embodiment of the present invention, in a hydrogen production apparatus including a plasma reforming apparatus and a metal catalyst coated with a metal having strong thermal durability such as Cu or Ce, La, Ni, etc. as a catalyst material on FeCrAl alloy, the temperature of the metal catalyst is controlled by hydrocarbon The steam reforming reaction or water gas shift (WGS: Water Gas Shift) reaction for system fuel is rapidly heated to the maximum hydrogen production efficiency temperature within a short time by using an induction heater to the appropriate activation temperature to obtain the highest hydrogen concentration. provides an effect.

In addition, an embodiment of the present invention uses an induction heater to shorten the time it takes to rise to the steady state temperature, which is the hydrogen production temperature (about 400 to 500 ° C) of the metal catalyst, to within 2-3 minutes and to easily perform temperature control. make it possible

In addition, in one embodiment of the present invention, when hydrocarbons and water are decomposed with low-temperature plasma, high concentrations of CO or various hydrocarbons are generated, which contributes to the generation of CO by WGS reaction, and sequentially steam reforming in the next step (SR: steam reforming) provides the effect of significantly improving hydrogen production efficiency by allowing various hydrocarbons to contribute to hydrogen production.

In addition, an embodiment of the present invention provides an effect of improving the thermal efficiency of the entire system by generating steam by heating water required for hydrogen generation using a heat exchanger for high-temperature waste heat after the hydrogen generation reaction.

In addition, in an embodiment of the present invention, the DME fuel is Cu (10%) Ce (4%) / γ-AL ₂ 0 _{3 H 2} production concentration for each reaction temperature in the SR catalyst is the highest concentration to 80.6% at 425 ℃ indicated. As described above, it is possible to efficiently generate hydrogen fuel from hydrocarbon-based fuel.

1 is a functional block diagram of an apparatus for producing hydrogen using a hydrocarbon-based fuel according to an embodiment of the present invention.
Figure 2 is a detailed configuration diagram of the plasma reforming unit 2 of the hydrogen production apparatus using a hydrocarbon-based fuel according to an embodiment of the present invention.
Figure 3 is a DME fuel Cu (10%) Ce (4%) / γ-Al ₂ O ₃ Hydrogen production concentration by reaction temperature in the steam reforming (SR) reaction catalyst, DME (dimetyl-ether, CH ₃ OCH ₃ ) The emission concentration, the concentration of CO and CH ₄ as intermediate products of the reaction (SV (Space Velocity, space velocity = (mass flow rate of the reactant passing through the catalyst (L/h) / the volume of the catalyst (L))), 7100 1/h condition).
4 is a DME fuel Cu (10%) Ce (4%) / γ-Al ₂ O _{3 H 2} production concentration for each reaction temperature in the steam reforming (SR) reaction catalyst, DME (dimetyl-ether, CH ₃ OCH ₃ ) Graph showing the effect of emission concentration and the concentration of CO and CH _{4, which are intermediate products of the reaction.}
Figure 5 is a graph showing the optimum temperature of the water gas shift (WGS) reaction.
6 is a detailed configuration diagram of the steam reforming (SR) reaction unit (3) and the water gas conversion (WGS) reaction unit (4).
7 is a hydrogen gas production process diagram by steam reforming (SR) reaction and water gas conversion (WGS) reaction.
Figure 8 is a hydrogen gas production process diagram by plasma reforming reaction, water gas conversion (WGS) reaction and steam reforming (SR) reaction.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be embodied in several different forms, and thus is not limited to the embodiments described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the specification, when a part is said to be “connected (connected, contacted, coupled)” with another part, it is not only “directly connected” but also “indirectly connected” with another member interposed therebetween. "Including cases where In addition, when a part "includes" a certain component, this means that other components may be further provided without excluding other components unless otherwise stated.

The terms used herein are used only to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In this specification, terms such as "comprises" or "have" are intended to designate that the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification exist, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 to 8 and below in the description of the hydrogen production apparatus of an embodiment of the present invention, the first catalytic reaction unit of the present invention is a steam reforming reaction unit (3), and the second catalytic reaction unit is a water gas conversion reaction unit (4) to be explained.

1 is a functional block diagram of a hydrogen production apparatus (hereinafter, referred to as a 'hydrogen production apparatus') using a hydrocarbon-based fuel according to an embodiment of the present invention.

As shown in FIG. 1 , the hydrogen production apparatus includes a steam supply unit 1 , a plasma reforming reaction unit 2 , and a steam reforming (SR) reaction unit 3 that heat supplied water to generate steam and then supply it. ), water gas shift (WGS: Water Gas Shift) may be configured to include a reaction unit (4), a final gas temperature reduction unit (4) and a hydrogen collection unit (6).

The water vapor supply unit 1 includes an evaporation tube 100 for accommodating the water supplied from the first water tank 30 and the evaporation tube 100 to heat the water in the evaporation tube by being heated and convert it into water vapor. ) may be configured to include an induction heater 120 mounted on. In this case, the evaporation tube 100 is composed of an insulating material tube, and is composed of an induction heating metal mesh 110 that is corrosion-resistant and electromagnetic induction heated therein. In the case of FIG. 1, as an example of the induction heating metal mesh 110, it is shown as a stainless steel (STS, SUS) mesh. The induction heater 120 may be configured as an induction coil heated by induction power by power supplied through the induction heater power supply 900 .

The above-described aqueous water vapor supply unit 1 is the first water tank 30 having a cooling fin, and the supply amount is controlled for hydrogen generation through the valve 40 and the mass flow meter 20, and the supplied water is transferred to the evaporation pipe 100 . After being supplied through the ), rapid heating by electromagnetic induction action of the heater 120 supplied with power supplied by the induction heater power supply 900 of the induction heating metal mesh 110 such as the SUS network inside the evaporation tube. to generate water vapor and supply it to the plasma reforming reaction unit 2 . The induction coil has a higher heating rate than a conventional electric heating wire, for example, an iron nichrome wire, so that water vapor can be supplied quickly after starting. The evaporation tube 100 is made of an insulating material, for example, a glass tube or a ceramic tube, and the induction heating metal mesh 110 is heated by electromagnetic induction by the induction coil of the induction heater 120, and is heated by water or the like. The non-corrosive, corrosion-resistant stainless steel may be selected from among conductor metals.

The plasma reforming reaction unit 2 is installed to support the plasma chamber 201 and one end of the plasma spiral anode 210 at the inner inlet side of the plasma chamber 201 to rotate the supplied fuel and water vapor. The helical anode 210 is installed outside the plasma chamber 201 and the plasma spiral anode 210 for applying plasma to the fuel and water vapor mixture supplied by turning through the swirler 230 , and the spiral anode 210 is installed outside the plasma chamber 201 . ) together with a tubular cathode 220 for forming plasma inside the plasma chamber 201, and a honeycomb-type support installed at the inner outlet side of the plasma chamber 201 to support the other end of the spiral anode 210 240 and a plasma power supply 200 for supplying plasma power to the spiral anode 210 and the tubular cathode 220 .

2 is a detailed configuration diagram of the plasma reforming unit 2 of the apparatus for producing hydrogen using a hydrocarbon-based fuel according to an embodiment of the present invention.

Referring to FIGS. 1 and 2 , the plasma reforming reaction unit 2 having the above-described configuration includes steam supplied from the previous stage steam evaporation tube 100 and a fuel tank 10 that is quantitatively controlled and supplied through a mass flow meter 20 . ) is supplied with fuel. The supplied fuel and water vapor are mixed while swirling around the swirler 230 at the inlet of the plasma reforming reaction unit 2, and the plasma generated by being energized by the plasma power supply 200 in the plasma spiral anode 210 and the tubular cathode 220. The reforming reaction proceeds as it is supplied between them. The spiral anode 41 is supported by a honeycomb type support 240 . At this time, as shown in Scheme 1, hydrocarbon fuel and water are reformed as shown to hydrogen (H ₂ ), carbon monoxide (CO), carbon dioxide (CO ₂ ) and other various hydrocarbons (hydrocarbons, HCs, CxHy(CH ₄ , C ₂ H _{4 )} , C ₃ H ₆ , C ₃ H ₈ , C ₄ H ₁₀ ….), etc.). At this time, the amount of water supplied is about twice the theoretically required amount depending on the type of fuel.

CxHy + zH ₂ O-> aH ₂ + bCO + dCO ₂ + HCs ----- (Scheme 1) (z, a, b, d are coefficients)

Again, referring to FIG. 1 , the steam reforming (SR) reaction unit 3 is coated with a catalyst that induces a catalytic reaction depending on the fuel on the first insulating tube 330 and the outer surface. A first metal catalyst carrier 320 such as a FeCrAl metal carrier mounted inside the first insulating pipe 330, and the induction heater power supply 900 wound around the outside of the first insulating pipe 330 It is configured to include a first induction coil 310 heated by the supplied power.

An example of the coating method of the catalyst to cause the catalytic reaction to form a carrier by heating a FeCrAl alloy, the surface of the carrier _{Ce (NO 3) 3 · 6H} 2 O, Cu (NO 3) 2 · 3H 2 O , La(NO ₃ ) ₃ .6H ₂ O, NiCl ₂ .6H ₂ O, or NiSO ₄ .6H ₂ O, coated with a solution of at least one material mixed in distilled water and at a temperature of 110 to 130 ℃ for 3 to 5 hours After drying for a while, heat treatment at a temperature of 400 to 600 ° C. for 1 to 5 hours to form a promoter material layer, and _{a sol (sol) containing γ-Al 2} O ₃ and a noble metal material on the promoter material layer ) coated and dried at a temperature of 110 to 130 ° C. for 3 to 5 hours, and then heat-treated at a temperature of 400 to 600 ° C. for 1 to 5 hours to form a catalyst layer. Here, the promoter material layer adheres the surface of the carrier to the catalyst layer. In the step of forming the carrier, the heat treatment may be performed at a temperature of 950 ~ 1050 ℃ for 10 ~ 17 hours. A plurality of protrusions are formed on the surface of the carrier by such heat treatment, and the protrusions may include γ-Al ₂ O ₃ . In the step of forming the catalyst layer, sol _{Ce (NO 3) 3 · 6H} 2 O, Cu (NO 3) 2 · 3H 2 O, La (NO 3) 3 · 6H 2 O, NiCl 2 · 6H 2 O, Or NiSO ₄ ·6H ₂ O may further include one or more of the material.

In the step of forming the cocatalyst material layer, before the heat treatment, the coating and drying processes may be repeatedly performed two or more times. The step of forming the promoter material layer may be repeated two or more times.

In the catalyst layer forming step, before the heat treatment, the coating and drying processes may be repeatedly performed twice or more. The catalyst layer forming step may be repeated two or more times.

In the above configuration, the catalyst coated on the first metal catalyst carrier 320 may be a Cu-Ce/γ-Al2O _{3 catalyst in the case of dimetyl-ether, CH 3} OCH _{3 (DME) fuel.}

In the steam reforming reaction unit 3 having the above configuration, the power supplied by the control of the induction heater power supply 900 is a catalyst-coated first metal catalyst by electromagnetic induction by the first induction coil 310 . A vortex current is generated in the carrier 320 to generate Joule heat. As a result, the first metal catalyst carrier 320 is rapidly heated to rapidly increase the temperature (within 2 to 3 minutes) to a set temperature between 400 and 500° C., which is an optimum temperature for hydrogen generation. CO and HCs generated in the plasma reforming unit 2 of the previous stage react in the steam reforming reaction unit 3 to increase the hydrogen production concentration. At this time, the basic reaction equation of the steam reforming reaction unit 3 is the same as [Reaction Equation 2], which is the following steam reforming reaction equation.

HCs + wH ₂ O -> eH ₂ + fCO + gCO ₂ --------- (Scheme 2) (w, e, f, g are coefficients)

3 is a DME fuel with Cu(10%)Ce(4%)/γ-Al ₂ O ₃ (γ-Al ₂ O ₃ , 10(Cu) - 4(Ce) = 80 to 90%, preferably 86%) In the steam reforming (SR) reaction catalyst, the concentration of hydrogen production by reaction temperature, the concentration of DME (dimetyl-ether, CH ₃ OCH ₃ ) emission, and the concentration of CO and CH ₄ as intermediate products of the reaction (SV=7100) 1/h) is a graph showing.

Figure 3 is an embodiment of the hydrocarbon fuel of the present invention DME (dimetyl-ether, CH ₃ OCH ₃ ) Cu (10%) Ce (4%) / γ-Al ₂ O ₃ The reaction temperature in the steam reforming catalyst of O 3 Concentration of H ₂ production, concentration of DME emission, CO and CH ₄ as intermediate products of the reaction | Each concentration is shown. Here, S (Space Velocity) is a value obtained by dividing the mass flow rate of the reactant passing through the catalyst by the bulk volume of the catalyst, and represents the load of the catalyst. DME is completely eliminated to 0%, H ₂ is the highest concentration, CO and CH ₄ The optimal condition when the concentration of the lowest. Therefore, the reaction temperature at which DME is 0% is 450 °C, and the highest H ₂ production concentration is 80.371% at 500 °C. This concentration is theoretically equivalent to the amount of H _{2 that DME can produce in the reforming reaction.} The highest concentration is 5.371% higher than 75%. The reason is that because the concentration of supplied steam was supplied at twice the theoretical amount, some of the surplus steam and the intermediate product, CO, reacted, and the water gas conversion (WGS (Water (Water) Gas Shift) reaction, that is, the used steam reforming reaction catalyst Cu(10%)Ce(4%)/γ-Al ₂ O ₃ is steam reforming (SR) reaction for hydrogen generation and water gas conversion It can be seen that the (WGS) reaction can be performed simultaneously.

CO + H ₂ O -> H ₂ + CO ₂ ------------- (Scheme 3)

In the case of this embodiment, the optimum temperature for the SR reaction may be 450 to 500° C., and may change around this reaction temperature depending on the type of fuel used.

4 is a DME fuel Cu (10%) Ce (4%) / γ-Al ₂ O _{3 H 2} production concentration for each reaction temperature in the steam reforming (SR) reaction catalyst, DME (dimetyl-ether, CH ₃ OCH ₃ ) is a graph showing the effect of the _{emission concentration and the production concentration (SV) of CO and CH 4} , which are intermediate products of the reaction.

4 is a case in which the amount of the catalyst is increased by about 29% while the amount of the reactant is the same as compared to SV-7100 1/h of FIG. 3 . In this case, the reactivity is improved and the DME fuel is completely removed to 0% at 400°C, the CO production concentration is the lowest at 400°C, and the hydrogen production rate is the highest at 425°C at 80.6%. In this embodiment, the optimum steam reforming (SR) reaction temperature can be said to be 425 ℃.

At the rear end of the steam reforming reaction, a heated high-temperature reaction gas flows out. This high-temperature waste heat is recovered by water circulation passing through the first heat exchanger 340, and the heated water is supplied to the evaporator to minimize energy required for water evaporation, thereby improving the thermal efficiency of the entire hydrogen production apparatus. The supplied water is condensed by the second heat exchanger 570 of the last stage to condense the water vapor remaining after the reaction, and is recovered and reused in the second water tank 500. At this time, the water passes through the second on/off valve 564. Then, it is sent to the first heat exchanger 340 by the second water circulation pump 750 to recover waste heat, and after adjusting to a predetermined flow rate by the mass flow meter 20, the evaporation tube ( 100) is supplied. At this time, the remaining or insufficient water after being used for the reaction is supplied through the 3-way first valve 40 mounted on the pipe of the first water tank 30 or the excess water is supplied to the first water tank 30 . control is sent to In addition, when water is insufficient in the entire hydrogen production apparatus, water for replenishment is supplied to the first water tank 30 through the second valve 50 from the outside.

Referring back to FIG. 1 , the water gas conversion reaction unit 4 is coated with a second insulating pipe 432 and a catalyst that induces a catalytic reaction depending on the fuel on the outer surface of the second insulating pipe 432 . ), a second metal catalyst carrier 422 such as a FeCrAl metal carrier mounted inside, and the second insulating tube 432 wound around the outside of the induction heater power supply 900, which is heated by the power supplied from As configured including the second induction coil 412 , it has the same configuration as the steam reforming reaction unit 3 as a whole. And the catalyst for the water gas conversion reaction of the water gas conversion reaction unit may be Cu(10%)Ce(4%)/γ-Al ₂ O ₃ or CuCePt/γ-Al ₂ O ₃ catalyst.

The water gas conversion reaction unit 4 of the above configuration is an electromagnetic induction phenomenon of the second induction coil 412 by the power supplied by the adjustment of the induction heater power supply 900, the second metal catalyst carrier 422 It is heated and maintained at a temperature between 200 and 350° C., which is the optimum temperature for hydrogen generation by the water gas shift reaction by the eddy current generated on the surface of the . Thereby, the CO generated at a high concentration in the front end plasma reforming unit 1 and introduced produces hydrogen by a water gas conversion reaction such as [Reaction Equation 4].

fH₂ + fCO₂ ---------(반응식 4)(f는 계수)fCO + fH ₂ O

fH ₂ + fCO ₂ --------- (Scheme 4) (f is the coefficient)

5 is a graph showing the optimum ring temperature of the water gas shift (WGS) reaction.

In order to find the optimum reaction temperature for the steam reforming reaction catalyst reaction formula [Reaction Equation 3] and the water gas conversion reaction equation [Reaction Equation 4], Cu(10%)Ce(10%)Ce( 4%)/γ-Al ₂ O ₃ catalyst is used, and CuCePt/γ-Al ₂ O ₃ catalyst as water gas shift reaction (WGS) catalyst (catalyst capacity: 20 to 30% of the steam reforming reaction catalyst, preferably 25 %), and the steam reforming (SR) reaction temperature is 450°C. It can be seen that the optimum reaction temperature for the water gas shift (WGS) reaction with the highest hydrogen production concentration is 250 °C. That is, using platinum (Pt) with high oxidation reactivity as a catalyst for water gas shift (WGS) reaction, the total hydrogen production concentration is Cu(10%)Ce(4%)/γ for the steam reforming reaction (SR) of FIG. -Al ₂ O ₃ is lower than when only the catalyst is used, and accordingly, when the CuCePt/γ-Al ₂ O ₃ catalyst is used as a water gas shift reaction (WGS) catalyst and the reaction temperature is around 250℃, the final hydrogen production concentration is more was confirmed to increase.

6 is a detailed configuration diagram of the steam reforming (SR) reaction unit (3) and the water gas conversion (WGS) reaction unit (4).

In FIG. 6 , the control of the first induction coil 310 and the second induction coil 412 may be performed by a single control device or may be configured to be performed by using an individual control device.

The final gas temperature reducing unit 5 will be described with reference to FIG. 1 again.

The final gas temperature reduction unit 5 includes a second heat exchanger 570 that exchanges heat from the gas introduced after the steam reforming reaction or the water gas conversion reaction through the water of the first water tank 30, and the second The second water tank 500 for storing the condensed water of the heat exchanger 570 is installed between the second heat exchanger 570 and the second water tank 500 and is generated in the second heat exchanger 570 . The steam reforming reaction unit 3 through the first on/off valve 562 for supplying the condensed water to the second water tank and the water stored in the second water tank 500 through the second water circulation pump 750 . ) may be configured to include a second on/off valve 564 that opens and closes to supply to the first heat exchanger 340 .

The temperature of the final gas discharged from the hydrogen production apparatus of the present invention should be reduced to room temperature. The reaction gas is usually discharged to 200 to 500 ℃, is cooled to some extent by the first heat exchanger 340, then heated again by the water gas conversion reaction unit 4, or is maintained at about the water gas conversion reaction temperature. Therefore, in order to lower the temperature of the final gas, it is necessary to lower the temperature to the room temperature by the second heat exchanger 570 . At this time, the second heat exchanger 570 is equipped with an external cooling fan to help dissipate heat, and performs heat exchange by circulating water, which is an internal heat exchange medium. The circulation of water is performed by circulating the water of the first water tank 30 equipped with a cooling fan through the first water circulation pump 710 . The waste heat recovered from the second heat exchanger 570 is partially discharged from the second water tank 30 to the outside, unlike the cooling fins. In the final second heat exchanger 570 , after heat exchange, the temperature of water vapor drops below the condensation temperature and the water vapor is condensed to generate water. When this water is filled to a predetermined water level in the second heat exchanger 570 , the first on/off It is collected in the second water tank 500 under the control of the valve 562 .

The hydrogen collection unit 6 includes one or more low-pressure transport tanks 630 , one or more high-pressure hydrogen tanks 650 , and hydrogen produced at a concentration of 75% or more and then discharged through the final gas temperature reduction unit 5 . A check valve 600 for preventing backflow of gas, a moisture trap 610 installed on the downstream side of the check valve 600 to remove moisture inside the hydrogen gas, and a low-pressure hydrogen tank ( 630) or a third valve 620, such as a three-way valve selectively branching to the high-pressure hydrogen tank 650, and the moisture trap 610, the low-pressure hydrogen tank 630, and the high-pressure hydrogen tank 650. A gas booster 640 that is installed in the pipe of the water trap 610 or pressurizes the gas supplied from the low-pressure hydrogen tank 630 (about 50 MPa or more) and discharges it to one or more of the high-pressure hydrogen tanks 650 . is comprised of

The hydrogen collecting unit 6 having the above configuration receives the hydrogen gas discharged through the final gas temperature reducing unit 5 so as not to flow backward through the check valve 600 . After that, while passing through the moisture trap 610, the moisture contained in the hydrogen gas is removed to a level of almost 0%. Next, the third valve 620 is first supplied to one or more low-pressure hydrogen tanks 630 and stored. When one or more low-pressure hydrogen tanks 630 are provided, when one low-pressure hydrogen tank 630 is filled with a predetermined pressure, hydrogen is supplied and filled to the other low-pressure hydrogen tank 630 by switching the flow path of the valve. Hydrogen in the filled low-pressure hydrogen tank 640 is supplied to the gas booster 640 through the third valve 620, such as a three-way valve, and then pressurized to a pressure of about 50 MPa or more and stored in one or more high-pressure hydrogen tanks 650. . At this time, the number of the low-pressure hydrogen tank 630 and the high-pressure hydrogen tank 650 may be increased according to the required capacity.

<Operating Example of Hydrogen Production Apparatus>

1. Hydrogen production by performing steam reforming (SR) reaction and water gas shift (WGS) reaction

7 is a process diagram of hydrogen gas production by steam reforming (SR) reaction and water gas conversion (WGS) reaction.

As shown in FIG. 7 , in the hydrogen production apparatus of FIG. 1 , the plasma reformer 2 is set to perform only the function of transferring water vapor and hydrocarbon-based fuel without performing the plasma reforming operation.

In this operating method, since the hydrocarbon-based fuel is not partially reformed in the plasma, the reforming reaction between the steam supplied from the steam supply unit 1 and the hydrocarbon-based fuel is performed at a reforming temperature of 400 by a dedicated reforming catalyst in the steam reforming reaction unit 3 . to 500°C. At this time, CO generated by this primary steam reforming reaction is a component to be removed. In particular, when hydrogen is used in a fuel cell, since CO gas causes poisoning of the Pt catalyst, resulting in rapid performance degradation, the concentration of CO in hydrogen must be maintained at 10 ppm or less. The CO discharged from the steam reforming reaction unit 3 is adjusted to a reaction temperature of 200 to 350 ° C. by a dedicated water gas conversion reaction catalyst in the water gas conversion reaction unit 4, and a catalytic reaction by a water gas reforming reaction catalyst (reaction formula) By 4), hydrogen is produced by the reaction of water vapor and CO, and CO is reduced. If the concentration of CO is more than 10 ppm in the subsequent reaction, the oxidation reaction can be performed using a non-noble metal-based catalyst. In this oxidation reaction, low-concentration oxygen generated as a by-product in the steam reforming (SR) reaction and water gas conversion (WGS) reaction is used.

2. Plasma reforming, water gas conversion (WGS) and the use of steam reforming reactions

8 is a hydrogen gas production process diagram by plasma reforming reaction, water gas conversion (WGS) reaction and steam reforming (SR) reaction.

As shown in FIG. 8 , hydrogen gas may be produced by plasma reforming, water gas conversion (WGS) reaction, and steam reforming (SR) reaction for a mixture of water vapor and hydrocarbon-based fuel using the hydrogen production apparatus of FIG. 1 .

At this time, since the steam reforming reaction unit 3 and the water gas conversion reaction unit 4 use the same catalyst, the applied power of the first induction coil 310 is controlled to increase the induction heating temperature of the steam reforming reaction unit 3 in water. When the gas shift (WGS) reaction temperature is maintained at a temperature between 200 and 350 ° C., the steam reforming reaction unit 3 is driven as a water gas conversion (WGS) reaction unit, and the water gas conversion (WGS) reaction unit 4 of the Water gas conversion (WGS) when the induction heating temperature of the water gas conversion (WGS) reaction unit 4 is maintained at a temperature between 400 and 500 ℃, which is the steam reforming reaction temperature, by controlling the applied power of the second induction coil 412 ) Since the reaction conversion unit 4 is driven as a steam reforming reaction unit, it can be performed without replacing the positions of the steam reforming reaction unit 3 and the water gas conversion reaction unit 4 . In this case, if the catalyst is different, the catalyst may be replaced.

In the case of hydrogen production by performing sequential plasma reforming, water gas conversion (WGS) reaction, and steam reforming (SR) reaction of the hydrogen production apparatus having the above configuration, water vapor supplied from the water vapor supply unit 1 and the fuel tank 10 ), the reforming reaction of the hydrocarbon fuel supplied from the first generates hydrogen, CO, CO ₂ , and various hydrocarbon fuels (HCs) by plasma decomposition of fuel and water vapor in the plasma reforming unit 2 . In particular, since the CO generated at this time has a high concentration, the water gas conversion (WGS) reaction step is performed before the steam reforming (SR) reaction step, which is the next step of the plasma reforming reaction in the steam reforming (SR) reaction unit 3, and the dedicated water gas While adjusting the reaction temperature in the range of 200 to 350 ℃ by the conversion (WGS) catalyst, as in [Reaction Equation 3] of the water gas conversion reaction, hydrogen is generated by the reaction of CO and water vapor, and CO is reduced. As a next step, HCs that have not been reformed in the water gas conversion (WGS) reaction step by the steam reforming (SR) reaction unit 3 are dedicated to the steam reforming (SR) reaction in the water gas conversion (WGS) reaction unit 4 The final concentration of hydrogen is maximized by generating hydrogen by performing a reforming reaction at a reforming temperature of 400 to 500° C. by a reforming catalyst.

The above description of the present invention is for illustration, and those of ordinary skill in the art to which the present invention pertains can understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and likewise components described as distributed may be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present invention.

10: fuel tank
20: mass flow meter
30: first water tank
40: first valve
50: second valve
1: water vapor supply
100: evaporation tube
110: induction heating metal mesh
120: induction heater
2: Plasma reforming reaction unit
200: plasma power supply
201: plasma chamber
210: spiral anode
220: tubular cathode
222: tubular negative terminal
230: turning machine
240: honeycomb type support
3: Steam reforming reaction unit (SR: Steam Reforming)
310: first induction coil
320: first metal catalyst support (FeCrAl support)
330: first insulating tube
340: first heat exchanger
4: Water gas shift reaction part (WGS: Water Gas Shift)
412: second induction coil
422: second metal catalyst carrier
432: second insulating tube
5: Final gas temperature reduction part
500: second water tank
562: first on/off valve
564: second on/off valve
570: second heat exchanger
6: Hydrogen collection unit
600: check valve
610: moisture trap
620: third valve
630: low pressure hydrogen tank
640: gas booster
650: high-pressure hydrogen tank
710: second first water circulation pump
750: second water circulation pump
900: induction heater power supply

Claims (13)

a plasma reforming reaction unit receiving fuel and water vapor to perform plasma reforming;
a first catalyst reaction unit for generating hydrogen by selectively performing a steam reforming reaction or a water gas conversion reaction between the fuel and the water vapor according to a reaction temperature after receiving the fuel and water vapor from the plasma reforming reaction unit;
a second catalyst reaction unit that receives the gas on which the first catalytic reaction has been performed from the first catalyst reaction unit, and then selectively performs the water gas conversion reaction or the steam gabil reaction to generate hydrogen;
a final gas temperature reduction unit for cooling and exhausting the final gas discharged from the second catalytic reaction unit; and
Hydrogen production apparatus using hydrocarbon-based fuel, characterized in that it comprises a; hydrogen collecting unit for collecting and storing the final gas discharged from the final gas temperature reducing unit. According to claim 1,
The catalyst of the first catalytic reaction unit or the second catalytic reaction unit is Cu (10%) Ce (4%) / γ-Al ₂ O ₃ Hydrogen production apparatus using a hydrocarbon fuel, characterized in that the catalyst. According to claim 2, wherein the first catalytic reaction unit or the second catalytic reaction unit,
CuCePt/γ-Al ₂ O ₃ Hydrogen production apparatus using hydrocarbon fuel, characterized in that it further comprises a catalyst. According to claim 1, wherein the plasma reforming reaction unit
plasma chamber;
a swirler installed at the inner inlet side of the plasma chamber to support one end of the spiral anode and to rotate the supplied fuel and water vapor;
a plasma spiral anode configured to apply plasma to a mixture of fuel and water vapor supplied by turning through the swirler;
a tubular cathode installed outside the plasma chamber to form plasma in the plasma chamber together with the spiral anode; and
Hydrogen production apparatus using hydrocarbon fuel, characterized in that it comprises; a honeycomb-type support installed on the inner outlet side of the plasma chamber to support the other end of the spiral anode. 5. The method of claim 4,
The plasma reforming reaction unit, Hydrogen production apparatus using a hydrocarbon-based fuel, characterized in that it further comprises a plasma power supply for supplying plasma power to the spiral anode and the tubular cathode. According to claim 1, wherein the first catalytic reaction part or the second catalytic reaction part,
insulated tube;
a metal catalyst carrier coated with a catalyst on an outer surface and mounted inside the insulating tube to generate a vortex by external electromagnetic induced electromotive force and heat; and
An induction coil wound on the outside of the insulating tube to receive power from an external induction heater power supply and generate electromagnetic induced electromotive force for generating an eddy current in the metal catalyst carrier; hydrocarbon-based fuel comprising a Hydrogen production device using. The method of claim 6, wherein the first catalytic reaction unit or the second catalytic reaction unit,
Hydrogen production apparatus using hydrocarbon-based fuel, characterized in that it further comprises a first heat exchanger for cooling the fuel discharged after performing a steam reforming (SR) reaction and a gas containing water vapor and hydrogen. According to claim 1, wherein the final gas temperature reduction unit,
a second heat exchanger for exchanging the heat of the gas introduced after the steam reforming reaction or the water gas conversion reaction;
a second water tank for storing the condensed water of the second heat exchanger;
a first on/off valve installed between the second heat exchanger and the second water tank to supply condensed water generated in the second heat exchanger to the second water tank; and
Hydrogen production using hydrocarbon-based fuel, characterized in that it comprises; a second on/off valve for supplying the water stored in the second water tank to the first heat exchanger of the first catalytic reaction unit or the second catalytic reaction unit Device. According to claim 1, wherein the hydrogen collection unit,
one or more low-pressure transport tanks;
one or more high-pressure hydrogen tanks;
a check valve for preventing a reverse flow of the final gas discharged through the final gas temperature reducing unit;
a moisture trap installed on the downstream side of the check valve to remove moisture contained in the final gas;
a third valve for selectively branching the final gas from which moisture has been removed to the low-pressure hydrogen tank or the high-pressure hydrogen tank; and
A gas booster installed in the pipe between the moisture trap and the low-pressure hydrogen tank and the high-pressure hydrogen tank to pressurize the final gas supplied from the moisture trap or the low-pressure hydrogen tank and discharge it to one or more of the high-pressure hydrogen tanks; includes; Hydrogen production apparatus using hydrocarbon-based fuel, characterized in that configured to. According to claim 1,
an evaporation pipe accommodating the water supplied from the first water tank; and
Hydrogen production apparatus using hydrocarbon-based fuel, characterized in that it further comprises a water vapor supply unit comprising; an induction heater mounted on the evaporation tube to heat the water in the evaporation tube to convert it into water vapor. The method of claim 13, wherein the evaporation tube,
outer insulation tube; and
Hydrogen production apparatus using hydrocarbon-based fuel, characterized in that it comprises a; corrosion-resistant and electromagnetic induction heating metal mesh mounted on the inside of the insulating material tube is heated. plasma reforming reaction unit; A first catalytic reaction unit and a second catalytic reaction unit for selectively performing a steam reforming reaction or a water gas conversion reaction; a final gas temperature reduction unit for cooling and exhausting the final gas containing the generated hydrogen; In the hydrogen production method by a hydrogen production apparatus using a hydrocarbon-based fuel comprising a; and a hydrogen collection unit for collecting and storing the final gas,
a steam reforming reaction step of supplying steam and hydrocarbon-based fuel supplied from the steam supplying unit to the first catalytic reaction unit with the plasma reforming reaction stopped in the plasma reforming reaction unit, and then performing a steam reforming reaction;
a water gas conversion reaction step of performing a water gas conversion reaction after the second catalyst reaction unit receives the gas discharged from the steam reforming reaction step;
a final gas temperature reduction step in which the final gas temperature reduction unit cools and discharges the final gas discharged from the second catalyst reaction unit; and
Hydrogen production method using hydrocarbon-based fuel, characterized in that it comprises a; hydrogen capture step of collecting the final gas of the reduced temperature of the hydrogen collecting unit and storing it in a storage tank. plasma reforming reaction unit; A first catalytic reaction unit and a second catalytic reaction unit for selectively performing a steam reforming reaction or a water gas conversion reaction; a final gas temperature reduction unit for cooling and exhausting the final gas containing the generated hydrogen; In the hydrogen production method by a hydrogen production apparatus using a hydrocarbon-based fuel comprising a; and a hydrogen collection unit for collecting and storing the final gas,
a steam reforming reaction step of supplying steam and hydrocarbon-based fuel supplied from the steam supplying unit to the first catalytic reaction unit with the plasma reforming reaction stopped in the plasma reforming reaction unit, and then performing a steam reforming reaction;
a water gas conversion reaction step of performing a water gas conversion reaction after the second catalyst reaction unit receives the gas discharged from the steam reforming reaction step;
a final gas temperature reduction step in which the final gas temperature reduction unit cools and discharges the final gas discharged from the second catalyst reaction unit; and
Hydrogen production method using hydrocarbon fuel, characterized in that it comprises a; hydrogen collection step of collecting the final gas, the temperature of which has been reduced by the hydrogen collection unit, and storing it in a storage tank

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