KR20220124412A - Apparatus for manufacturing hydrogen and carbon product and a method using the same - Google Patents

Abstract

The present invention relates to an apparatus and a method for manufacturing hydrogen and a carbon body, and more specifically, to an apparatus and a method for manufacturing hydrogen and a carbon body, which can continuously manufacture high-purity hydrogen and a high-quality carbon body. The apparatus of the present invention includes a reactor, a first recovery unit, a second recovery unit, a separation unit, and a combustion unit.

Description

Apparatus for manufacturing hydrogen and carbon product and a method using the same}

The present invention relates to an apparatus and method for producing hydrogen and carbon, and more particularly, to a production apparatus and method for continuously producing high-purity hydrogen and high-quality carbon.

Hydrogen is widely used as a raw material for chemical products and as a process gas for chemical plants, and its demand is increasing recently as a raw material for fuel cells, a future energy technology. Although it is evaluated that it is preferable to produce such hydrogen from a renewable energy source because it does not generate carbon dioxide, it is currently the most economical to produce hydrogen from coal or natural gas, and it is preferable in that it also contributes to the purification of fossil fuels.

On the other hand, a carbon nanotube (Carbon Nanotube) has a shape in which one carbon atom is bonded to three adjacent carbon atoms to form a hexagonal ring, and a plane in which the hexagonal ring is repeated in a honeycomb shape is rolled to form a cylinder or tube. The carbon nanotube is a material with properties that can exhibit metallic or semiconducting conductivity depending on its structure, and can be widely applied in various technical fields, and thus is spotlighted as a new material for the future. For example, carbon nanotubes may be applied to an electrode of an electrochemical storage device such as a secondary battery, a fuel cell, or a supercapacitor, electromagnetic wave shielding, a field emission display, or a gas sensor.

As such, as mass production of hydrogen and carbon nanotubes has recently become an issue, a technology using a fluidized bed reactor advantageous for mass production has been highlighted. The technology using a fluidized bed reactor is a method of generating hydrogen and carbon nanotubes by dispersing and endothermic reaction of metal catalyst particles and hydrocarbon-based source gas in a high-temperature reactor. That is, while the metal catalyst is suspended by the source gas in the reactor, the source gas is thermally decomposed to grow carbon nanotubes on the metal catalyst.

In this regard, Korean Patent No. 10-0977147 discloses 'a fluidized bed carbon nanotube generating apparatus and a carbon nanotube generating facility and method using the same'. As such, in the conventional fluidized bed carbon nanotube generator, a heater is installed outside the fluidized bed reactor, which is a reactor, to supply thermal energy necessary for the endothermic reaction.

However, such a carbon nanotube generating device has a temperature gradient as heat energy is supplied to the inside of the reactor by heating the reactor using a heater installed on the outer surface of the reactor. Accordingly, as the heater must be heated to a temperature higher than the amount of heat required for the endothermic reaction, the efficiency in using thermal energy is lowered.

In addition, since the temperature of the inner wall of the reactor is different from the temperature of the center of the reactor, there is a disadvantage in that carbon nanotubes are not uniformly grown and thus relatively low-quality carbon nanotubes are formed.

In addition, there is a disadvantage in that the yield of high-quality carbon nanotubes is not good compared to the catalyst supply.

Accordingly, it is necessary to study not only the problem of supplying the reaction heat necessary for the reaction, but also the supply method including the proper activation and pre-treatment of the catalyst.

(Patent Document 1): Republic of Korea Patent Publication No. 10-0977147

An object of the present invention is to provide a manufacturing apparatus and a manufacturing method capable of continuously producing high-purity hydrogen and high-quality carbon material.

An apparatus for producing hydrogen and carbon according to the present invention comprises: a reactor in which a hydrocarbon-based source gas undergoes an endothermic reaction in the presence of a catalyst to generate a gaseous reaction product containing hydrogen and a solid reaction product containing a carbon body; a first recovery unit for recovering a gaseous reaction product from the reactor; a second recovery unit for recovering a solid reaction product from the reactor; a separation unit which partially separates the solid reaction product recovered to the second recovery unit and supplies it to the combustion unit; and a combustion unit for supplying reaction heat to the reactor by burning the solid reaction product supplied from the separation unit.

In the apparatus for producing hydrogen and carbon according to an embodiment of the present invention, the reactor may be a fluidized bed reactor.

In the apparatus for producing hydrogen and carbon according to an embodiment of the present invention, an active catalyst supply unit located at the front end of the reactor and continuously supplying the activated catalyst to the reactor by activating the catalyst; may further include have.

In the apparatus for producing hydrogen and carbon according to an embodiment of the present invention, the active catalyst supply unit may be an upflow-reactor.

In the hydrogen and carbon production apparatus according to an embodiment of the present invention, a hydrogen supply unit for supplying a portion of the hydrogen separated from the gaseous reaction product recovered to the first recovery unit to the lower portion of the active catalyst supply unit; may include

In the hydrogen and carbon production apparatus according to an embodiment of the present invention, hydrogen is separated and purified from the gaseous reaction product recovered to the first recovery unit, and the remaining unreacted source gas is re-supplied to the reactor. It may further include;

In the apparatus for producing hydrogen and carbon according to an embodiment of the present invention, it is located in the reactor, the pressure difference between the upper and lower parts of the reactor, the temperature in the reactor, and the concentration of the unreacted source gas discharged from the reactor group a sensing unit for sensing one or two or more conditions selected from; and a control unit that compares the sensed value measured by the sensing unit with a set design value to control the amount of the reaction product separated by the separation unit.

The method for producing hydrogen and carbon material according to the present invention comprises the steps of (S1) supplying a catalyst and a hydrocarbon-based source gas to a reactor to generate a gaseous reaction product containing hydrogen and a solid reaction product containing carbon; (S2) recovering the reaction product in the solid phase and the reaction product in the gas phase, respectively; (S3) supplying a portion of the recovered solid reaction product to a combustion unit and burning; and (S4) supplying the heat generated in the combustion unit to the reactor; includes

In the method for producing hydrogen and carbon material according to an embodiment of the present invention, before the step (S1), (S0) activating the catalyst; may further include.

In the method for producing hydrogen and carbon material according to an embodiment of the present invention, the steps (S0) to (S4) may be continuously performed.

In the method for producing hydrogen and carbon material according to an embodiment of the present invention, the reactor may be a fluidized bed reactor.

In the method for producing hydrogen and carbon according to an embodiment of the present invention, hydrogen is obtained by separating hydrogen from the gaseous reaction product recovered in step (S2), and the gaseous reaction product from which hydrogen is separated is transferred to the reactor Re-supplying; may further include.

In the method for producing hydrogen and carbon material according to an embodiment of the present invention, the step (S3) includes a pressure difference between the upper and lower sides of the reactor, a temperature in the reactor, and a concentration of unreacted source gas discharged from the reactor. By sensing any one or two or more conditions selected from the group, the amount of the combustion solid reaction product may be controlled.

In the method for producing hydrogen and carbon according to an embodiment of the present invention, in the step (S1), the catalyst is (Fe), molybdenum (Mo), titanium (Ti), vanadium (V), chromium (Cr), Manganese (Mn), nickel (Ni), cobalt (Co), copper (Cu), cadmium (Cd), zinc (Zn), ruthenium (Ru), lead (Pd), silver (Ag), platinum (Pt) and It may be any one of gold (Au) or an alloy thereof.

In the method for producing hydrogen and carbon material according to an embodiment of the present invention, the source gas may include methane gas.

The apparatus for producing hydrogen and carbon according to the present invention can directly supply the amount of heat required when the hydrocarbon-based gas undergoes an endothermic reaction in the presence of a catalyst, thereby producing high-purity hydrogen and high-quality carbon.

In addition, the present invention can efficiently supply the required amount of heat to the inside of the reactor without the need to input an external material as the required amount of heat is supplied by burning a part of the product.

In addition, the present invention can control the conversion rate of hydrocarbon-based gas by controlling the amount of heat supplied to the reactor, and can control the yield and characteristics of the carbon body produced.

In addition, the catalyst is activated by a reducing gas (hydrogen or hydrogen-rich gas) in a space maintained at a certain temperature range and then transferred to the reactor, so that the yield of high-quality carbon material can be increased, and the economic feasibility of the process can be improved. have.

1 is a schematic diagram schematically illustrating an apparatus for producing hydrogen and carbon according to an embodiment of the present invention.

Unless otherwise defined in technical terms and scientific terms used in this specification, those of ordinary skill in the art to which this invention belongs have the meanings commonly understood, and in the following description and accompanying drawings, the subject matter of the present invention Descriptions of known functions and configurations that may unnecessarily obscure will be omitted.

Also, the singular form used herein may be intended to include the plural form as well, unless the context specifically dictates otherwise.

In addition, in the present specification, the unit used without special mention is based on the weight, for example, the unit of % or ratio means weight % or weight ratio, and weight % means any one component of the entire composition unless otherwise defined. It means % by weight in the composition.

In addition, the numerical range used herein includes the lower limit and upper limit and all values within the range, increments logically derived from the form and width of the defined range, all values defined therein, and the upper limit of the numerical range defined in different forms. and all possible combinations of lower limits. Unless otherwise defined in the specification of the present invention, values outside the numerical range that may occur due to experimental errors or rounding of values are also included in the defined numerical range.

As used herein, the term 'comprising' is an open-ended description having an equivalent meaning to expressions such as 'comprising', 'containing', 'having' or 'characterized', and elements not listed in addition; Materials or processes are not excluded.

As used herein, the term 'carbon body' refers to a nano-sized carbon structure having various shapes, such as carbon nanotubes, carbon nanofibers, fullerenes, carbon nanocones, carbon nanohorns, and carbon nanorods.

The present invention provides a method for producing hydrogen and carbon, comprising the steps of: (S1) supplying a catalyst and a hydrocarbon-based source gas to a reactor to produce a gaseous reaction product containing hydrogen and a solid reaction product containing carbon; (S2) recovering the reaction product in the solid phase and the reaction product in the gas phase, respectively; (S3) supplying a part of the recovered solid reaction product to a combustion unit to burn it; and (S4) supplying heat generated in the combustion unit to the reactor; includes

In the conventional method for producing hydrogen and carbon, the amount of heat required for the endothermic reaction of the source gas in the presence of a catalyst is supplied through the preliminary heating step of the source gas and the reactor heating step. Accordingly, the design of supplying the amount of heat required for the endothermic reaction was complicated, and it was difficult to precisely control it, and the efficiency in using heat energy was lowered as the amount of heat had to be supplied more than necessary. In addition, there is a disadvantage in that relatively low-quality carbon nanotubes are formed because heat supply in the reactor is not uniformly made.

However, in the method for producing hydrogen and carbon according to the present invention, a portion of the recovered solid reaction product is supplied to the combustion unit and burned, and then the generated heat is supplied to the reactor, so that the amount of heat required for the endothermic reaction is directly transferred into the reactor. It can be supplied, so the efficiency of using heat energy is very high, and the endothermic reaction of hydrocarbon-based hydrogen gas occurs uniformly, so that high-purity hydrogen and high-quality carbon can be produced.

In addition, as a necessary amount of heat is supplied by burning a part of the product, there is no need for separately inputting and burning combustion materials, and since there is no need for a preliminary heating step of the source gas and a reactor heating step, the manufacturing method is relatively simple.

Preferably, the hydrogen and carbon material production method may be performed by a hydrogen and carbon material production apparatus, which will be described later, but is not limited thereto.

Specifically, (S1) the step of supplying a catalyst and a hydrocarbon-based source gas to the reactor to produce a gaseous reaction product containing hydrogen and a solid reaction product containing a carbon body, the hydrocarbon-based source gas in the presence of a catalyst It is a step of obtaining a gaseous and solid phase reaction product by endothermic reaction.

The catalyst may be a metal catalyst, specifically iron (Fe), molybdenum (Mo), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), nickel (Ni), cobalt (Co), Copper (Cu), cadmium (Cd), zinc (Zn), ruthenium (Ru), lead (Pd), silver (Ag), platinum (Pt) and gold (Au) any one metal or alloys thereof It can be any one. In addition, of course, the catalyst may further include a support such as silica, zeolite, etc. known in the art for supplying the catalyst in the reactor.

The hydrocarbon-based source gas includes a carbon source for producing a carbon body as a product, and specifically, may include a compound having 6 or less carbon atoms, or a compound having 4 or less carbon atoms, or a compound having 2 or less carbon atoms. More specifically, one or two or more selected from the group consisting of carbon monoxide, methane, ethane, ethylene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, benzene and toluene may include Preferably, it may include methane, and in one embodiment, it may be a natural gas containing methane or an off-gas of a petrochemical/refining process. Such hydrocarbon-based source gas may undergo an endothermic reaction in the reactor in the presence of the above-described catalyst, and may be converted into high value-added products of carbon such as hydrogen and carbon nanotubes.

In step (S1), the reactor is preferably a fluidized bed reactor in which the contact between the catalyst and the hydrocarbon-based source gas is excellent.

In step (S1), the reactor internal pressure may be normal pressure or 0.2 ~ 20 barg (gauge pressure), preferably 0.5 ~ 5 barg. In addition, in step (S1), the reactor internal temperature may be 500 to 1200 ℃, specifically 600 to 900 ℃, but is not limited thereto. In addition, the endothermic reaction in the reactor may be performed for 1 to 120 minutes, specifically 30 to 80 minutes, but is not limited thereto.

Step (S2) is a step of recovering the reaction product in the solid phase and the reaction product in the gas phase generated in the step (S1), respectively. The reaction product in the solid phase contains carbon, and the reaction product in the gas phase contains hydrogen.

In one embodiment of the present invention, it is obtained by separating hydrogen from the gaseous reaction product recovered in step (S2), and the hydrogen-separated gaseous reaction product may be re-supplied to the reactor. The reaction product in the gas phase from which hydrogen is separated is an unreacted source gas, that is, as a raw material. .

Step (S3) is a step of supplying a part of the recovered solid reaction product to the combustion unit to burn it. As the solid reaction product is burned, heat may be generated, and the amount of the solid reaction product moved to the combustion unit may be appropriately adjusted in proportion to the amount of heat required for the endothermic reaction in the reactor. In this case, the solid reaction product may include a part of the catalyst as well as the carbon body.

In an embodiment of the present invention, in step (S3), any one or two or more conditions selected from the group consisting of the pressure difference between the upper and lower parts of the reactor, the temperature in the reactor, and the concentration of the unreacted source gas discharged from the reactor are sensed. Thus, the amount of the solid reaction product moving to the combustion unit may be controlled, and thus, the amount of the solid reaction product combusted in the combustion unit may be adjusted.

For example, when the concentration value of the unreacted source gas discharged from the reactor is lower than the design value, it is possible to reduce the amount of the combustion reaction product by reducing the amount of the solid reaction product moving to the combustion unit, and the concentration value of the unreacted source gas If it is higher than this design value, it is possible to increase the amount of reaction products to be burned by increasing the amount of solid reaction products moving to the combustion unit.

Step (S4) is a step of supplying the heat generated in the combustion unit to the reactor, and provides the heat required in step (S1). In step (S4), the amount of heat required for the endothermic reaction of step (S1) can be directly supplied into the reactor, so that the efficiency of using heat energy can be very high.

Specifically, step (S4) may be performed by supplying a heating medium including a solid reaction product burned in the combustion unit to the reactor. The heating medium may further include flowing particles for efficient heat supply as well as a solid reaction product including a carbon medium and a catalyst. Specifically, the fluid particles may include a layer material such as alumina, zirconia and silica.

In step (S4), the supply of the heating medium is not specifically limited as long as it is a conventionally known supply method, but may be supplied through a loop seal as a non-limiting example.

In addition, in the step (S4), a reducing gas may be further supplied as a carrier gas for smooth transfer of the heating medium.

In one embodiment of the present invention, before step (S1), the step of (S0) activating the catalyst may be further included. As the catalyst activated by the step (S0) is supplied to the reactor, the endothermic reaction of the hydrocarbon-based source gas in the presence of the catalyst in step (S1) can be promoted. Accordingly, it is possible to manufacture a large amount of product within a relatively short time.

Activation of the catalyst in step (S0) may be achieved by reducing the catalyst by a reducing gas. The reducing gas is not limited as long as it is a gas capable of reducing the input metal catalyst, but may be preferably hydrogen, and more preferably hydrogen separated from the gaseous product recovered in step (S2) may be partially used.

The activation of the catalyst in step (S0) is preferably performed in an upflow reactor in view of the contact efficiency of the catalyst and the reducing gas, and the catalyst activation may be performed for 1 to 60 seconds, but is not limited thereto.

In one embodiment of the present invention, the above-described steps (S0) to (S4) can be performed continuously, so that high-value-added carbon bodies such as carbon nanotubes and high-purity hydrogen can be mass-produced for industrial use. Very likely.

Hereinafter, an apparatus for producing hydrogen and carbon according to a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings.

1 is a schematic diagram of an apparatus for producing hydrogen and carbon according to an embodiment of the present invention.

Referring to FIG. 1, the hydrogen and carbon body manufacturing apparatus 1 is a reactor in which a hydrocarbon-based source gas undergoes an endothermic reaction in the presence of a catalyst to generate a gaseous reaction product containing hydrogen and a solid reaction product containing a carbon body ( 10); a first recovery unit 30 for recovering a gaseous reaction product from the reactor 10; The second recovery unit 35 for recovering the solid reaction product from the reactor 10, the separation unit 50 for partially separating the solid reaction product recovered to the second recovery unit 35 and supplying it to the combustion unit 70 ); and a combustion unit 70 for supplying thermal energy to the reactor 10 by burning the solid reaction product supplied from the separation unit 50 .

In the conventional hydrogen and carbon body manufacturing apparatus, a heater is installed outside a fluidized bed reactor used as a reactor to supply thermal energy necessary for an endothermic reaction of a hydrocarbon-based source gas. However, such a manufacturing apparatus uses a heater installed on the outer surface of the reactor 10 to supply thermal energy to the inside of the reactor, thereby having a temperature gradient. Accordingly, as the heater must be heated to a temperature higher than the amount of heat required for the endothermic reaction, the efficiency in using thermal energy is lowered. In addition, since the temperature of the inner wall of the reactor 10 is different from the temperature of the center of the reactor, there is a disadvantage in that the carbon body is not uniformly grown inside the reactor, so that a carbon body of relatively low quality is formed.

However, since the apparatus for producing hydrogen and carbon according to the present invention includes the combustion unit 70 , it is possible to directly supply the amount of heat required when the hydrocarbon-based gas undergoes an endothermic reaction in the presence of a catalyst into the reactor 10 . That is, as only the required amount of heat is directly supplied into the reactor 10, the efficiency of using heat energy is very high. In addition, as the required amount of heat is directly supplied to the inside of the reactor 10, there is almost no temperature difference in the reactor 10, so the endothermic reaction of hydrocarbon-based hydrogen gas occurs uniformly at any position in the reactor 10, so that high-purity hydrogen and high-quality of carbon bodies can be produced. In addition, in the present invention, there is no need for a facility for separately inputting an external material as the required heat is supplied by burning a portion of the product separated through the separation unit 50, and a preliminary heating device and a heater for the source gas are not required. The manufacturing equipment facility is relatively simple. In addition, the present invention can control the conversion rate of the hydrocarbon-based gas by controlling the amount of heat supplied to the reactor 10, it is possible to control the yield and characteristics of the carbon body produced.

Specifically, the reactor 10 provides an accommodating space in which the catalyst and the source gas can be accommodated therein, and the hydrocarbon-based source gas undergoes an endothermic reaction in the presence of the catalyst to form a gaseous reaction product containing hydrogen and carbon. A solid reaction product is formed.

The reactor 10 provides an accommodation space in which the hydrocarbon-based source gas can undergo an endothermic reaction, and is a chemical vapor deposition reactor 10, preferably a fluidized bed reactor 10 (Fluidized Bed). reactor) can be

In order to generate a carbon body by the chemical vapor deposition (CVD) method, a reaction time between the source gas and the catalyst is required for a certain amount of time or more. It has a major impact on purity and yield.

In the fluidized bed reactor 10, the gas source gas is in contact with the particulate solid material catalyst, and the source gas flows at a speed sufficient to suspend the catalyst, so that the solid catalyst may behave similarly to the gas source gas. . Accordingly, the source gas and the catalyst can be mixed and contacted relatively homogeneously, and it is possible to secure the growth time of the carbon body in the reactor 10, so that the carbon body production ratio is high compared to the catalyst input amount, so that the carbon body can be produced with a high yield can

The reactor 10 may have a longitudinal direction in a direction perpendicular to the ground, and a catalyst supply port 11 is provided at the upper portion so that the catalyst can be supplied into the reactor 10 .

The catalyst supplied to the catalyst supply port 11 may be a metal catalyst, specifically iron (Fe), molybdenum (Mo), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), nickel Any of (Ni), cobalt (Co), copper (Cu), cadmium (Cd), zinc (Zn), ruthenium (Ru), lead (Pd), silver (Ag), platinum (Pt), and gold (Au) It may be any one selected from one metal or an alloy thereof.

The reactor 10 may be provided with a gas supply port 13 at the lower portion to supply the source gas in an upward flow manner from the lower part to the upper part.

The hydrocarbon-based source gas supplied to the gas supply port 13 contains a carbon source for producing a carbon body as a product, and specifically, a compound having 6 or less carbon atoms, or a compound having 4 carbon atoms or less, or a compound having 2 carbon atoms or less may include More specifically, one or two or more selected from the group consisting of carbon monoxide, methane, ethane, ethylene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, benzene and toluene may include In one embodiment, it may be natural gas containing methane. Such hydrocarbon-based source gas may undergo an endothermic reaction in the reactor 10 in the presence of a catalyst, and may be converted into high value-added products of carbon such as hydrogen and carbon nanotubes.

The source gas may further include one or more of an inert gas or a reducing gas. Nitrogen, helium, argon, neon, etc. may be used as an inert gas, and hydrogen etc. may be used as a reducing gas. Such an inert gas or reducing gas prevents the carbon nanotubes from falling in the gravity direction due to the increase in weight as they grow, and expands the fluidization area in the reactor 10 to activate the endothermic reaction between the catalyst and the hydrocarbon-based source gas. have. In particular, when a reducing gas is included, it is possible to further improve the yield of carbon products by increasing the catalyst activity in the reactor.

As such, the catalyst and the source gas respectively supplied into the reactor 10 through the catalyst supply port 11 located at the upper portion of the reactor 10 and the gas supply port 13 located at the lower portion of the reactor 10 are transferred to the reactor ( 10) Mixed in the inner accommodation space and in the presence of a catalyst, the source gas undergoes an endothermic reaction to form a gaseous reaction product including hydrogen and a solid reaction product including carbon.

The receiving space in the reactor 10 may be divided into an upper space and a lower space. Specifically, the lower space is adjacent to the floor surface, and a source gas and heat energy (heat amount) to be described later may be supplied. On the other hand, in the upper space, the source gas supplied with sufficient thermal energy from the lower space is in contact with the catalyst, and an endothermic reaction of the source gas may occur. The reactor 10 is located at the boundary between the upper space and the lower space, is installed to partition the upper space and the lower space, and may include a dispersion plate (not shown) in which a plurality of holes are formed. The source gas may be distributed to the upper space through the dispersion plate. In addition, the dispersion plate may serve to prevent the carbon body generated by the catalyst or reaction from falling to the bottom of the fluidized bed reactor 10 .

The reactor 10 is provided with an exhaust port 15 at the top so that the gaseous reaction product can be discharged to the outside of the reactor 10, and the discharge port 17 is provided on at least one side of the upper part, the lower part, or the side The solid reaction product can be discharged to the outside of the reactor (10). In addition, the reactor 10 may be provided with a connection port 19 to receive thermal energy from the combustion unit 70 to be described later on the other side.

The gaseous reaction product generated by the endothermic reaction may be discharged to the outside of the reactor 10 through the exhaust port 15 by the first recovery part 30, and the solid reaction product is the second recovery part 35 may be discharged to the outside of the reactor 10 through the discharge port 17 by the

The first recovery unit 30 recovers a gaseous reaction product from the reactor 10 , and a recovery line 31 connected to the exhaust port 15 of the reactor 10 and a gas purification located in the recovery line 31 . It may include a device (not shown) and the like, and high-purity hydrogen generated in the reactor 10 may be recovered through the recovery line 31 . In addition, the first recovery unit further includes a cyclone installed in the upper end of the reactor, so that the reaction product in the gas phase can be smoothly recovered.

The second recovery unit 35 recovers the solid reaction product from the reactor 10, and is located in the discharge recovery line 36 and the discharge recovery line 36 connected to the discharge port 17 of the reactor 10. It may include a gas phase separator (not shown). The gas phase separator may remove gas components mixed with the solid reaction product recovered through the exhaust recovery line 36, such as unreacted source gas.

The separation unit 50 partially separates the solid reaction product recovered through the second recovery unit 35 and supplies it to the combustion unit 70 . The remaining products except for some solid reaction products supplied to the combustion unit 70 by the separation unit 50 are final products, and may be discharged to the outside.

The combustion unit 70 burns the solid reaction product supplied from the separation unit 50 to supply thermal energy to the reactor 10 . The combustion unit 70 is a conventionally known combustor, and may generate thermal energy using a solid reaction product including a carbon body and a catalyst as a fuel. The combustor may be provided with an oxygen supply port through which air containing oxygen or oxygen itself can be supplied from the outside, and a carbon dioxide discharge port through which carbon dioxide generated after combustion can be discharged.

The thermal energy generated as the solid reaction product containing carbon is burned by the combustion unit 70 is supplied to the reactor 10 through the heating medium, and the amount of heat required for the endothermic reaction of the hydrocarbon-based gas in the presence of a catalyst is returned to the reactor ( 10) It can be supplied directly inside.

Specifically, the heating medium may include a combustion solid reaction product and flowing particles, and may be supplied through a heating medium supply pipe 71 connecting the combustor and the reactor 10 . The heat medium supply pipe 71 has a loop seal structure, and the discharge portion is inclined downward in the direction of the reactor 10 to be supplied using gravity. In this case, the combustion unit 70 may further include a fluidized gas supply unit (not shown) capable of supplying a reducing gas to the heating medium supply pipe to facilitate the supply of the heating medium.

The prior art consumes a large amount of thermal energy to supply the required amount of heat as the heat energy is supplied through the heater and the preliminary heating device installed outside the reactor 10, but the present invention includes the combustion unit 70, the required amount of heat Only as much as it is directly supplied in the reactor 10, the efficiency of using heat energy is very high. In addition, since there is almost no temperature difference in the reactor 10, the endothermic reaction of hydrocarbon-based hydrogen gas occurs uniformly at any position in the reactor 10, and uniform growth of carbon bodies such as carbon nanotubes occurs to produce high-purity hydrogen and high-quality Carbon bodies can be formed. In addition, the combustion unit 70 burns a portion of the product separated through the separation unit 50 to supply the required amount of heat in the reactor 10 , so there is no need for a facility for separately inputting an external material, and heat energy efficiently to be able to supply

In one embodiment of the present invention, as shown in the drawing, it may further include a circulation unit 90 located in the recovery line 31 . The circulation unit 90 separates and purifies hydrogen from the gaseous reaction product recovered by the first recovery unit 30 , and re-supply the remaining unreacted source gas to the reactor 10 . Accordingly, not only can hydrogen of higher purity be obtained, but also the unreacted source gas can be recycled to obtain a product with a high yield compared to the input amount of the source gas. Specifically, the circulation unit 90 may separate and purify hydrogen through pressure swing adsorption (PSA) or a polymer membrane. PSA does not require a heat exchanger essential for cooling the reactor 10 when separating the mixed gas, thereby reducing the investment cost of equipment and reducing the size of the manufacturing apparatus. In addition, by recirculating the high-temperature reaction product through the recirculation line connected to the reactor 10 without cooling, it is possible to reduce the amount of heat required and the size of the preheater. The PSA device and the polymer separation membrane may be used without limitation by means known in the art.

In one embodiment of the present invention, as shown in the drawings, the active catalyst supply unit 20 located in front of the reactor 10 may be further included. The active catalyst supply unit 20 activates the catalyst and continuously supplies the activated catalyst to the reactor 10 , and as the activated catalyst is supplied to the reactor 10 , the endothermic reaction can be promoted. Accordingly, it is possible to manufacture a large amount of product within a relatively short time. Activation of the catalyst may be achieved by reduction with a reducing gas.

The active catalyst supply unit 20 is not limited as long as it is a catalytically active reactor known in the art, but preferably an upflow-reactor. In the upflow reactor, the catalyst is reduced and activated by flowing from the bottom to the top by the reducing gas flowing from the bottom to the top. Compared to the downflow reactor, the upflow reactor facilitates control of the residence time of the catalyst flowing in the reactor 10, and thus the degree of activation of the catalyst can be easily controlled. For example, conductivity) may be adjustable. In addition, since continuous catalyst input is easy, continuous production of the product is easy. At this time, the catalyst supply port 11 positioned above the upper portion of the active catalyst supply unit 20 and the reactor is connected by the catalyst supply line 21 so that the activated catalyst can be supplied into the reactor 10 .

In one embodiment of the present invention, it may further include a hydrogen supply unit 40 located in the recovery line (31). The hydrogen supply unit 40 may supply a portion of hydrogen separated from the gaseous reaction product recovered to the first recovery unit 30 to the lower portion of the active catalyst supply unit 20 . Specifically, the hydrogen supply unit 40 may include a gas separator 41 and a hydrogen supply line 43 connecting the gas separator 41 and the lower end of the catalytic activity supply unit 30 . The active catalyst supply unit 20 does not require a separate reducing gas for activating the catalyst, and makes it possible to utilize a part of the product generated after the reaction, thereby further increasing the manufacturing efficiency of the manufacturing apparatus.

In one embodiment of the present invention, the sensing unit 80 located in the reactor 10 and the control unit 85 for controlling the amount of the reaction product separated from the separation unit 50 through this may further include. The sensing unit 80 is a sensor for sensing various conditions in the reactor 10 , specifically, the pressure difference between the upper and lower portions in the reactor 10 , the temperature in the reactor 10 , and the unreacted source discharged from the reactor 10 . One or more conditions selected from the group consisting of a concentration of a gas are sensed.

The control unit 85 may control the amount of the reaction product separated by the separation unit 50 by comparing the sensing value measured by the sensing unit 80 with a set design value.

For example, when the temperature in the reactor 10 sensed through the temperature sensor installed in the reactor 10 is higher than the design value, the amount of reaction products separated from the separation unit 50 and delivered to the combustion unit 70 can be reduced. In addition, when the temperature in the reactor 10 is lower than the design value, the amount of reaction products separated from the separation unit 50 and delivered to the combustion unit 70 may be increased. Accordingly, it is possible to control the amount of the reaction product combusted by the combustion unit 70, and finally it is possible to control the amount of heat transferred in the reactor (10).

In this way, the hydrogen and carbon body manufacturing apparatus including the sensing unit 80 and the control unit 85 adjusts the amount of the reaction product delivered to the combustion unit 70 through the conditions in the reactor 10 such as temperature, etc., so that the reactor (10) You can easily control the amount of heat supplied inside.

As described above, the present invention has been described with specific matters and limited examples and drawings, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is not limited to the above embodiments. Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims described below, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

10: reactor 11: catalyst supply port
13: gas supply port 15: exhaust port
17: exhaust port 19: connection port
20: catalytic activity supply unit 21: catalyst supply line
30: first recovery unit 31: recovery line
35: second recovery unit 36: exhaust recovery line
40: hydrogen supply unit 41: gas separator
43: hydrogen supply line 50: separation unit
70: combustion part 71: heat medium supply pipe
90: circulation part

Claims (15)

a reactor in which a hydrocarbon-based source gas undergoes an endothermic reaction in the presence of a catalyst to produce a gaseous reaction product containing hydrogen and a solid reaction product containing a carbon body;
a first recovery unit for recovering a gaseous reaction product from the reactor;
a second recovery unit for recovering a solid reaction product from the reactor;
a separation unit which partially separates the solid reaction product recovered to the second recovery unit and supplies it to the combustion unit; and
a combustion unit for supplying reaction heat to the reactor by burning the solid reaction product supplied from the separation unit; Hydrogen and carbon body manufacturing apparatus comprising a.
According to claim 1,
The reactor is a fluidized bed reactor, an apparatus for producing hydrogen and carbon.
3. The method of claim 2,
The apparatus for producing hydrogen and carbon body further comprising a; located at the front end of the reactor, the active catalyst supply unit for continuously supplying the activated catalyst to the reactor by activating the catalyst.
3. The method of claim 2,
The active catalyst supply unit is an upflow-reactor, an apparatus for producing hydrogen and carbon.
5. The method of claim 4,
Hydrogen and carbon body production apparatus further comprising a; hydrogen supply unit for supplying a portion of the hydrogen separated from the gaseous reaction product recovered to the first recovery unit to the lower portion of the active catalyst supply unit.
According to claim 1,
and a circulation unit for separating and purifying hydrogen from the gaseous reaction product recovered to the first recovery unit and re-supplying the remaining unreacted source gas to the reactor.
According to claim 1,
a sensing unit positioned in the reactor to sense one or more conditions selected from the group consisting of a pressure difference between the upper and lower portions of the reactor, a temperature in the reactor, and a concentration of an unreacted source gas discharged from the reactor; and
The apparatus for producing hydrogen and carbon body further comprising; a control unit for controlling the amount of the reaction product separated by the separation unit by comparing the sensed value measured by the sensing unit with a set design value.
(S1) supplying a catalyst and a hydrocarbon-based source gas to the reactor to generate a gaseous reaction product containing hydrogen and a solid reaction product containing carbon;
(S2) recovering the solid reaction product and the gas phase reaction product, respectively;
(S3) supplying a portion of the recovered solid reaction product to a combustion unit to burn it; and
(S4) supplying the heat generated in the combustion unit to the reactor; A method for producing hydrogen and a carbon body comprising a.
9. The method of claim 8,
Before step (S1),
(S0) activating the catalyst; Hydrogen and carbon body production method further comprising a.
10. The method of claim 9,
The step (S0) to (S4) is a method for producing hydrogen and carbon body is carried out continuously.
9. The method of claim 8,
The reactor is a fluidized bed reactor, hydrogen and carbon body production method.
9. The method of claim 8,
Hydrogen and carbon body production method further comprising a; separating and obtaining hydrogen from the gaseous reaction product recovered in step (S2), and re-supplying the gaseous reaction product from which the hydrogen is separated to the reactor.
9. The method of claim 8,
The step (S3) is,
Controlling the amount of the combustion solid reaction product by sensing any one or two or more conditions selected from the group consisting of the pressure difference between the upper and lower parts of the reactor, the temperature in the reactor, and the concentration of the unreacted source gas discharged from the reactor Method for producing hydrogen and carbon body.
9. The method of claim 8,
In the step (S1), the catalyst is (Fe), molybdenum (Mo), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), nickel (Ni), cobalt (Co), copper ( Cu), cadmium (Cd), zinc (Zn), ruthenium (Ru), lead (Pd), silver (Ag), platinum (Pt), and gold (Au) of any one metal or alloys thereof hydrogen and carbon sieve manufacturing method.
9. The method of claim 8,
The source gas is a method for producing hydrogen and a carbon body including methane gas.

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