KR20140071033A - Method and apparatus for continuous catalytic decomposition of hydrocarbon - Google Patents

Abstract

The present invention, with regard to a method and an apparatus for continuously producing hydrogen without discharging carbon dioxide by catalytic decomposition of hydrocarbon using carbon black, relates to a method and an apparatus characterized by physically grinding carbon black generated as a result of catalytic decomposition of hydrocarbon into specific sizes to reuse the carbon black as a catalyst.

Description

METHOD AND APPARATUS FOR CONTINUOUS CATALYTIC DECOMPOSITION OF HYDROCARBON FIELD OF THE INVENTION [0001]

The present invention relates to a method and an apparatus for continuously producing hydrogen without carbon dioxide emission by catalytic cracking of hydrocarbon using carbon black, comprising the steps of physically crushing carbon black produced as a result of catalytic cracking of hydrocarbon to a specific size, ≪ / RTI >

Hydrogen is widely used as a raw material for chemical products and as a process gas in a chemical plant. Recently, the demand for hydrogen is increasing as a raw material for future energy technology, fuel cell. In addition, it is regarded as the most powerful and unique alternative that can solve the problems of environmental problems and fossil fuel price increase or depletion that are faced by humankind at present. Especially, in the 21st century, global warming and air pollution preparation, Researches on the production, storage and utilization of hydrogen are being actively carried out all over the world.

Hydrogen is ultimately produced from a renewable energy source and is evaluated to be preferable without generating carbon dioxide. However, at present, it is most economical to produce it from coal or natural gas, and it contributes to the purification of fossil fuel by removing a considerable amount of carbon dioxide and the like .

As a method for mass production of hydrogen from hydrocarbons, a steam reforming method of natural gas, a partial oxidation method of hydrocarbons and the like are known, but the conventional methods generate a large amount of carbon dioxide at the same time and cause environmental problems such as global warming There is a problem.

 Another method is the plasma decomposition method, which is being commercialized in Norway and some other countries. However, since the plasma decomposition method requires a large amount of electric power, it is not economical and environmental problems may arise because the emission of carbon dioxide is inevitable in electric power generation.

Another example is a process for producing carbon black and hydrogen by pyrolyzing natural gas, heavy oil, coal tar, etc. at high temperature. However, this method requires a very high reaction temperature of 1400 DEG C or more, and is a troublesome semi-continuous process in which two reactors are periodically used due to deposition of carbon produced. In addition, since the main product is carbon black, it is difficult to say that this method is suitable for hydrogen production.

As another method, there is a catalyst decomposition method using a metal catalyst as a method for lowering a high reaction temperature required for direct decomposition of hydrocarbons. However, there is a problem that the carbon produced in the catalytic cracking reaction lowers the activity of the catalyst, and a process of regenerating the metal catalyst using air or water vapor at a high temperature is further required in order to regenerate the metal catalyst having decreased activity , There is a problem that carbon dioxide, which is a greenhouse gas, is generated during the regeneration process.

Also, by Muradov et al., Activated carbon, carbon black, graphite and the like have been studied as catalysts. However, when a catalyst such as activated carbon, carbon black or graphite is used, carbon, which is a reaction product, is deposited on the catalyst. When the reaction proceeds for a long time in the fixed bed reactor, the entire reactor is accumulated as a catalyst, Clogging occurs. Therefore, there is a problem that the reaction is stopped, the catalyst deposited on the inner wall of the reactor is removed, and then the reaction is started again.

To solve this problem, Korean Patent No. 888247 discloses a method of catalytically decomposing hydrocarbons using a fluidized bed reactor. In the case of using a fluidized bed reactor, the carbon black catalyst on which the carbon is deposited maintains the fluidized state and is discharged to the outside of the reactor, so that accumulation in the reactor can be prevented to some extent. However, the size of the carbon black on which the carbon is deposited is increased and it is difficult to use the carbon black as a reaction catalyst again. Therefore, since the carbon black used as the catalyst must be continuously purchased, there is a problem that the catalyst is expensive to purchase, transport and store.

Accordingly, the present invention relates to a method and an apparatus for continuously producing hydrogen without carbon dioxide emission by catalytic cracking of hydrocarbon using carbon black, and a method and an apparatus for reusing carbon black produced as a result of the catalytic cracking reaction of hydrocarbon as a catalyst .

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

One aspect of the present invention provides a method for the continuous catalytic cracking of hydrocarbons, comprising:

A first step of supplying a hydrocarbon with an inert gas into a fluidized bed reactor including a carbon black catalyst to catalytically decompose the hydrocarbon;

A second step of discharging and recovering the carbon black catalyst deposited from the catalyst decomposition reaction in the first step to a discharge pipe provided in the fluidized bed reactor;

A third step of grinding the carbon black catalyst recovered in the second step to a size having catalytic activity and re-supplying the carbon black catalyst into the fluidized bed reactor;

A fourth step of recovering a gaseous mixture comprising hydrogen, unreacted hydrocarbon, and entrained carbon produced from a catalytic cracking reaction in the first step into a cyclone provided at an outlet of the fluidized bed reactor;

Separating the entrained carbon from the recovered gas mixture, and transferring the mixture of hydrogen and unreacted hydrocarbon to the pressure conversion adsorption tower; And

And separating hydrogen from the mixture containing the transferred hydrogen and unreacted hydrocarbon.

In one embodiment of the present invention, the carbon black catalyst may be, but is not limited to, a carbon black injected into a discharge tube provided in the fluidized bed reactor when carbon is deposited in an amount of 15% to 25% .

In one embodiment of the invention, the catalytically active size of the carbon black catalyst recovered in the second step is in the range of about 200 nm to about 250 nm, such as a secondary particle size or aggregate size, But is not limited thereto.

In one embodiment of the present invention, the carbon black catalyst recovered in the second step may be pulverized at 150 rpm for about 3 hours to about 8 hours, but is not limited thereto.

In one embodiment of the present invention, the inert gas may include, but is not limited to, nitrogen gas or argon gas.

In one embodiment of the present invention, the discharge pipe may have a fine nozzle for flowing gas to the side of the pipe, but the present invention is not limited thereto.

In one embodiment of the present invention, the carbon black catalyst may include at least one selected from the group consisting of carbon black for rubber, carbon black for pigment, carbon black for electronic material, and combinations thereof, It is not.

In one embodiment of the present invention, the hydrocarbon may include, but is not limited to, at least one selected from the group consisting of natural gas, propane, butane, methane, liquefied petroleum gas and liquefied natural gas.

In one embodiment of the present invention, the first stage catalytic cracking reaction may be performed at a temperature of about 600 ° C to about 950 ° C, but is not limited thereto.

Another aspect of the invention is an apparatus for producing hydrogen and carbon through a catalytic cracking process of hydrocarbons,

A fluidized bed reactor having a discharge line for recovering carbon black produced from the catalytic cracking process of the hydrocarbon, the carbon black catalyst being loaded;

A feeder connected to the upper part of the fluidized bed reactor by a nozzle, for supplying a hydrocarbon and an inert gas;

A pulverizing device connected to the discharge pipe by a nozzle and pulverizing the recovered carbon black to a size having catalytic activity to re-supply the pulverized carbon black to the fluidized bed reactor;

A cyclone for recovering a gas mixture comprising hydrogen, unreacted hydrocarbon and entrained carbon produced in said fluidized bed reactor; And

A pressure conversion adsorption tower for separating hydrogen from the gas mixture recovered in the cyclone recoverer;

Wherein the catalytic cracking catalyst is a continuous catalytic cracking apparatus for hydrocarbons.

In one embodiment of the invention, the carbon black may be one that discharges and recovers the carbon black to the discharge pipe provided in the fluidized bed reactor when the carbon is deposited from about 15% to about 25% of the initial charged carbon black no.

In one embodiment herein, the recovered, catalytically active size of the carbon black may be, but is not limited to, a secondary particle size or aggregate size of from about 200 nm to about 250 nm.

In one embodiment herein, the recovered carbon-deposited carbon black may be milled at about 150 rpm for about 3 hours to about 8 hours, but is not limited thereto.

In one embodiment of the present invention, the discharge pipe may have a fine nozzle for flowing gas to the side of the pipe, but the present invention is not limited thereto.

In one embodiment of the present invention, the carbon black catalyst may include at least one selected from the group consisting of carbon black for rubber, carbon black for pigment, carbon black for electronic material, and combinations thereof, It is not.

In one embodiment of the present invention, the hydrocarbon may include, but is not limited to, at least one selected from the group consisting of natural gas, propane, butane, methane, liquefied petroleum gas and liquefied natural gas.

In one embodiment herein, the catalytic cracking reaction may be performed at a temperature of from about 600 < 0 > C to about 950 < 0 > C, but is not limited thereto.

In one embodiment of the present invention, the inert gas may include, but is not limited to, nitrogen gas or argon gas.

According to the present invention, not only carbon dioxide but also hydrogen and carbon can be simultaneously produced from hydrocarbons, carbon black produced using a fluidized bed reactor is discharged continuously to the outside of the reactor, and pulverized Thereby reducing the cost of purchasing and storing the catalyst carbon black by reusing the used carbon black. The present invention relates to a process for producing a carbon black catalyst, Thereby improving the economical efficiency of the process, enabling continuous hydrogen production, and further applicable to a large-scale production process.

FIG. 1 is a schematic diagram of a device for catalytic cracking process for producing hydrogen and carbon from hydrocarbons and reusing the recovered carbon black through a physical grinding process, according to an embodiment of the present invention. FIG.
Figure 2 shows an apparatus for catalytic cracking process for producing hydrogen and carbon from hydrocarbons, according to one embodiment of the present invention.
FIG. 3 is a graph showing the results of methane decomposition experiments using fresh carbon black through physical pulverization according to one embodiment of the present invention. FIG.
FIG. 4 is a graph showing the results of methane decomposition test using a secondary (one-time-used carbon black catalyst) carbon black recovered in an apparatus for catalytic cracking according to one embodiment of the present invention through physical pulverization.
5 is a graph showing the relationship of methane conversion according to the size of the pulverized particles of the secondary carbon black recovered in the apparatus for catalytic cracking according to one embodiment of the present invention.

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains.

It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

The terms "about "," substantially ", etc. used to the extent that they are used herein are intended to be taken to indicate a manufacturing and material tolerance inherent in the stated sense, Accurate or absolute numbers are used to prevent unauthorized exploitation by unauthorized intruders of the mentioned disclosure. Also, throughout the present specification, the phrase " step "or" step "does not mean" step for.

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

The present invention relates to a method and an apparatus for continuously producing hydrogen without carbon dioxide emission by a catalytic cracking reaction of hydrocarbon using carbon black, which comprises physically pulverizing carbon black produced as a result of catalytic cracking of hydrocarbon to a specific size, And more particularly,

A method for the continuous catalytic cracking of hydrocarbons according to one embodiment herein may include:

A first step of supplying a hydrocarbon with an inert gas into a fluidized bed reactor including a carbon black catalyst to catalytically decompose the hydrocarbon;

A second step of discharging and recovering the carbon black catalyst deposited from the catalyst decomposition reaction in the first step to a discharge pipe provided in the fluidized bed reactor;

A third step of grinding the carbon black catalyst recovered in the second step to a size having catalytic activity and re-supplying the carbon black catalyst into the fluidized bed reactor;

A fourth step of recovering a gaseous mixture comprising hydrogen, unreacted hydrocarbon, and entrained carbon produced from a catalytic cracking reaction in the first step into a cyclone provided at an outlet of the fluidized bed reactor;

Separating the entrained carbon from the recovered gas mixture, and transferring the mixture of hydrogen and unreacted hydrocarbon to the pressure conversion adsorption tower; And

And separating hydrogen from the mixture containing the transferred hydrogen and unreacted hydrocarbon.

The method of continuous catalytic cracking of hydrocarbons according to one embodiment of the present invention may be performed through a device for catalytic cracking process as shown in FIG. 1, but the present invention is not limited thereto.

Figure 1 shows an apparatus for performing a continuous catalytic cracking process of hydrocarbons according to one embodiment of the present invention.

As shown in Figure 1, a continuous catalytic cracking apparatus for hydrocarbons according to an embodiment of the present invention may comprise:

A fluidized bed reactor (10) having a discharge line for recovering carbon black produced from a catalytic cracking process of hydrocarbons, the carbon black catalyst being loaded;

A feeder (20) connected to the upper part of the fluidized bed reactor by a nozzle, for supplying a hydrocarbon and an inert gas;

A pulverizing apparatus (30) for pulverizing the carbon black deposited through the discharge pipe to a size having catalytic activity and re-supplying the pulverized carbon black to the fluidized bed reactor;

A cyclone (50) for recovering a gaseous mixture comprising hydrogen, unreacted hydrocarbon and entrained carbon produced in said fluidized bed reactor; And

And a pressure conversion adsorption tower (60) for separating hydrogen from the recovered gas mixture in the cyclone recoverer.

In the continuous catalytic cracker for hydrocarbons, the fluidized bed reactor 10 is a double tube type reactor, and an internal heating system or an external heating system can be used. For example, in the case of an internal heating method, a heat transfer tube is provided inside a fluidized bed reactor to allow a high temperature combustion gas to flow. Also, in the case of the external heating method, a jacket is provided outside the fluidized bed reactor and a high-temperature combustion gas flows through the jacket. In the continuous catalytic cracker for hydrocarbons, the discharge pipe is provided on a wall surface or a lower portion of the fluidized bed reactor 10 to recover the carbon black deposited by the hydrocarbon decomposition reaction. Specifically, when the fluidized bed reactor 10 is applied to a catalytic cracking process of hydrocarbons for decomposing hydrocarbons to produce hydrogen and carbon, a discharge pipe is provided on the wall surface or the bottom of the fluidized bed reactor 10, Thereby preventing clogging of the reactor in which the carbon black is accumulated inside the reactor and discharging the carbon black to be supplied into the reactor so as to be reused as a catalyst. At this time, the discharge pipe may have a fine nozzle on the side of the discharge pipe to further facilitate discharge of the carbon black produced in the reactor. Because carbon black is a very cohesive solid particle, it can be easier to discharge by letting gas flow through the fine nozzles to allow them to flow better through the discharge tube. The continuous catalytic cracking apparatus for hydrocarbon may further include a gas supplier 70 for supplying gas to the discharge pipe through the fine nozzles to smooth the flow of the solid particles in the discharge pipe, 70 may be connected to the fine nozzles of the discharge pipe.

In the continuous catalytic cracking apparatus for hydrocarbon, the pulverizing apparatus is characterized in that the recovered carbon black is pulverized into a size having a catalytic activity of a secondary particle size or an aggregate size of about 200 nm to about 250 nm, And serves to re-supply carbon black. In one embodiment of the invention, the grinding apparatus can be, but is not limited to, a physical grinding apparatus commonly used in the art, such as, for example, a milling apparatus.

In one embodiment of the present invention, the milling apparatus may be milled at about 150 rpm for about 3 hours to about 5 hours to crush to a size having catalytic activity, but is not limited thereto.

Hereinafter, the catalyst decomposition process will be described in detail with reference to FIG.

The first step of the continuous catalytic cracking method of the present invention is a step of feeding a hydrocarbon into an fluidized bed reactor including a carbon black catalyst together with an inert gas to catalytically decompose the hydrocarbon. At this time, the inert gas supplied from the inert gas supplier 20 can be supplied together with the hydrocarbon.

In one embodiment of the present invention, the inert gas may include, but is not limited to, nitrogen gas or argon gas. The inert gas serves to improve the flow of the hydrocarbon, and the partial pressure of the total gas is lowered by injecting the inert gas.

Hydrocarbons are decomposed into gaseous hydrogen and solid carbon through an endothermic reaction that absorbs heat supplied from the outside in the presence of a carbon black catalyst. The carbon produced through the catalytic cracking reaction is deposited on the carbon black catalyst to form solid particles with strong cohesive force.

In one embodiment of the present invention, the carbon black catalyst may include at least one selected from the group consisting of carbon black for rubber, carbon black for pigment, carbon black for electronic material, and combinations thereof But is not limited thereto.

In one embodiment of the present invention, the carbon black catalyst may include, but is not limited to, carbon black for rubber, carbon black for pigment, carbon black for electronic material, and combinations thereof.

In one embodiment of the present invention, the hydrocarbon may include, but is not limited to, at least one selected from the group consisting of natural gas, propane, butane, methane, liquefied petroleum gas and liquefied natural gas.

In one embodiment herein, the catalytic cracking reaction may be performed at a temperature of from about 600 < 0 > C to about 950 < 0 > C, but is not limited thereto. For example, the catalytic cracking reaction may be carried out at a temperature of about 600 < 0 > C to about 950 [deg.] C, at about 700 [deg.] C to about 950 [deg.] C, at about 800 [deg.] C to about 950 [ From about 600 ° C to about 800 ° C, from about 600 ° C to about 900 ° C, or from about 700 ° C to about 800 ° C.

The second step of the continuous catalytic cracking method of the present invention is a step of recovering carbon black prepared from the catalytic cracking reaction using a discharge pipe provided on the wall or the bottom of the fluidized bed reactor 10, May be discharged to the separation tank 40 through a nozzle and recovered. However, the present invention is not limited thereto.

The carbon produced through the catalytic cracking reaction in the first step is deposited on a carbon black catalyst to form solid particles having strong cohesive force or mixed. In the case of using a conventional fixed-bed reactor, clogging of the reactor in which the solid particles are accumulated in the reactor occurs, and the reaction is stopped, and the solid carbon particles accumulated in the reactor are removed, and then the reaction is started again. In the case of using a fluidized bed reactor, the above problems can be improved to some extent, but the solid particles have strong cohesive force and are not easily discharged to the outside of the reactor. In consideration of this point, a fluidized bed reactor having a discharge pipe is used herein.

In one embodiment of the invention, the carbon-deposited carbon black may be withdrawn from the carbon black when it is deposited from about 15% to about 25% carbon to the discharge tube provided in the fluidized bed reactor, It is not. For example, the carbon black may contain from about 15% to about 25%, from about 17% to about 25%, from about 19% to about 25%, from about 21% to about 25% About 15% to about 21%, about 15% to about 17%, about 17% to about 19%, about 17% to about 21%, about 17% About 23%, from about 19% to about 21%, or from about 19% to about 23% of the deposition.

In one embodiment of the present invention, the discharge pipe may be provided with a fine nozzle for supplying a gas to the side of the pipe, but the present invention is not limited thereto. Specifically, the discharge pipe may be provided with a fine nozzle on the side of the discharge pipe to further facilitate discharge of the carbon black. Because carbon black is a very cohesive solid particle, it is possible to flow the gas from the gas feeder 70 through the fine nozzles so that they flow better in the discharge pipe, thereby facilitating the discharge.

The fine nozzles may have a diameter of about 1 mm or less, but the present invention is not limited thereto. For example, the fine nozzles may have a diameter of from about 0.5 to about 1 mm, from about 0.6 to about 1 mm, from about 0.7 to about 1 mm, from about 0.8 to about 1 mm, from about 0.9 to about 1 mm, from about 5 to about 0.9 From about 0.5 to about 0.8 mm, from about 0.5 to about 0.8 mm, from about 0.5 to about 0.7 mm, from about 0.5 to about 0.6 mm, from about 0.6 to about 0.7 mm, from about 0.6 to about 0.8 mm, or from about 0.7 to about 0.8 mm, But is not limited to.

The outlet pipe may include a valve for regulating the discharge of carbon black.

The third step of the continuous catalytic cracking method of the present invention is a step of pulverizing the carbon black deposited carbon recovered in the second step to a catalytically active size and re-feeding the carbon black into the fluidized bed reactor.

In one embodiment of the present invention, the recovered, carbon-deposited carbon black is about < RTI ID = 0.0 > But is not limited to, pulverization at 150 rpm for about 3 hours to about 5 hours.

In one embodiment of the present invention, the recovered carbon-deposited carbon black may be pulverized by, for example, a physical pulverizing process commonly used in the art, such as a milling method, But is not limited to.

In one embodiment herein, the recovered, carbon-deposited carbon black is re-fed into the fluidized bed reactor as a post-milling secondary particle size or agglomerate size having a catalytic activity size of about 200-250 nm, .

The fourth step is a step of recovering the gas mixture containing hydrogen, unreacted hydrocarbon and entrained carbon produced from the catalytic cracking reaction in the first step to the cyclone 50 through the nozzle provided in the fluidized bed reactor 10 to be.

In the fifth step, the gas mixture recovered in the cyclone 50 is separated, the entrained carbon is transferred to the separation tank 40 through the nozzle, and a mixture of hydrogen and unreacted hydrocarbon is supplied to the pressure conversion adsorption tower 60 .

The sixth step is a step of separating a mixture of hydrogen and unreacted hydrocarbon transferred to the pressure conversion adsorption tower 60 into pure hydrogen and hydrocarbon.

The unreacted hydrocarbon separated in the sixth step may be used as a raw material gas after being compressed by a compressor, or may be used as a combustion gas for supplying a reaction heat required for a catalytic cracking reaction.

In addition, the pure hydrogen separated in the sixth step can be used as a fuel cell, and a part thereof can be used as a combustion gas for supplying a reaction heat after being compressed by a compressor.

According to the present invention, it is possible not only to produce hydrogen and carbon simultaneously from hydrocarbons without generating carbon dioxide, but also to continuously discharge the carbon-deposited carbon black produced using a fluidized bed reactor to the outside of the reactor, To solve the clogging of the reactor in which the carbon catalyst is deposited in the reactor, which is a problem of the technique using the conventional carbon catalyst, and to reuse the used carbon black, so that the purchase cost of the catalyst carbon black and the storage cost , It is possible to increase the economical efficiency of the process, to continuously produce hydrogen, and to be applied to a large-scale production process.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

[ Example ]

Example  1. Physically ground primary ( Fresh ) Degradation Experiment of Methane Using Carbon Black Catalyst

An experiment was conducted using an apparatus as shown in Fig. The reactor used was a quartz reactor with a diameter of 5.5 cm. The reaction temperature was set to 900 ° C, flow rates were set to 1.2 cm / s, and 1.8 cm / s, respectively. N330 pellet type carbon black was used as the catalyst, and the ball miller was used for grinding by varying the milling conditions while varying the rotation speed (rpm) and the milling time (h) of the ball miller. Methane decomposition experiments were carried out using the pulverized carbon black as a catalyst. Methane conversion rates according to the milling conditions of the carbon blacks are shown in FIG. 3 and Table 1.

As shown in FIG. 3 and Table 1, when the carbon black was subjected to the milling process at 150 rpm for 4 hours and the milling process for 8 hours, the conversion rates of methane were 10.6 and 10.4%, respectively, Methane conversion (10.1%) obtained using black.

However, when the carbon black subjected to the pulverization process for 12 hours at 300 rpm, which is the maximum rotation speed of the ball miller, was used, the conversion rate of methane was lower. This is probably due to the channeling phenomenon rather than the fluidization, as the carbon black particles become close to the fluffy type after a long physical grinding process.

From this, it can be seen that the carbon black can maintain the catalytic activity even after the appropriate physical pulverization process.

Example  2. Experiments on the decomposition of methane using physically pulverized secondary (immersed) carbon black catalysts

When methane is decomposed using a carbon black catalyst, new carbon is deposited on the catalyst carbon black as methane decomposes. The carbon black on which the carbon is immersed is generally discarded because the catalytic activity is lowered. In this case, the carbon black immersed in carbon is subjected to a physical pulverizing process and then recycled as a catalyst to conduct a methane decomposition test .

In the apparatus as shown in Fig. 2, the reactor used was a quartz reactor having a diameter of 5.5 cm, a methane decomposition experiment was carried out using a N330 pellet type carbon black at a reaction temperature of 900 DEG C, a flow rate of 1.8 cm / s, 10% and 20% carbon-immersed carbon black (hereinafter, secondary carbon black) was obtained. The reaction time was controlled through real-time G / C analysis until 10% and 20% of the new carbon had been deposited in the catalyst carbon black. The obtained secondary carbon black was divided into three groups and milled under different milling conditions while varying the rotational speed (rpm) and milling time (h) of the ball miller using a ball miller. Methane decomposition experiments were carried out using a part of the pulverized secondary carbon black as a catalyst, and a part of the pulverized secondary carbon black was measured for particle size. The particle size and methane conversion according to the milling conditions of the secondary carbon black are shown in FIG. 4 and Table 2.

10%, and 20% sedimentation showed methane conversions of mostly 7% to 8% lower than that of primary carbon black catalysts. However, when the 20% immersed carbon black was milled for 4 hours, the methane conversion was about 10%, and the methane conversion was similar to that of the primary carbon black catalyst.

Therefore, it can be confirmed that the secondary carbon black subjected to the milling process under a specific condition exhibits catalytic activity equivalent to that of the primary carbon black catalyst, and thus can be recycled. In this case, the particle size of the ground carbon black is not limited to secondary particle size or aggregates size was from about 200 nm to about 250 nm. It was confirmed from FIG. 5 that the carbon black having the above particle size exhibited a high methane decomposition rate.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

10: Fluidized bed reactor 20: Inert gas feeder
30: physical grinding apparatus 40: carbon black separation tank
50: Cyclone 60: Pressure conversion adsorption tower
70: gas supply

Claims (18)

A first step of supplying a hydrocarbon with an inert gas into a fluidized bed reactor including a carbon black catalyst to catalytically decompose the hydrocarbon;
A second step of discharging and recovering the carbon black catalyst deposited with the carbon produced from the catalyst decomposition reaction in the first step to a discharge pipe provided in the fluidized bed reactor;
A third step of grinding the carbon black catalyst recovered in the second step to a size having catalytic activity and re-supplying the carbon black catalyst into the fluidized bed reactor;
A fourth step of recovering a gaseous mixture comprising hydrogen, unreacted hydrocarbon, and entrained carbon produced from a catalytic cracking reaction in the first step into a cyclone provided at an outlet of the fluidized bed reactor;
Separating the entrained carbon from the recovered gas mixture, and transferring the mixture of hydrogen and unreacted hydrocarbon to the pressure conversion adsorption tower; And
A sixth step of separating hydrogen from the mixture containing the transferred hydrogen and unreacted hydrocarbon,
≪ / RTI >
The method according to claim 1,
Wherein the carbon black catalyst is discharged to the discharge pipe provided in the fluidized bed reactor and recovered when carbon is deposited by 15 to 25% with respect to carbon black initially injected.
The method according to claim 1,
Wherein the size of the carbon black catalyst recovered in said second step having catalytic activity of the carbon deposited catalyst is a secondary particle size or aggregate size of 200 nm to 250 nm.
The method according to claim 1,
Wherein the carbon black catalyst recovered in the second step is milled at 150 rpm for 3 hours to 8 hours.
The method according to claim 1,
Wherein the inert gas comprises nitrogen gas or argon gas.
The method according to claim 1,
Wherein the discharge tube comprises a fine nozzle for flowing gas to a side of the tube.
The method according to claim 1,
Wherein the carbon black catalyst comprises at least one selected from the group consisting of carbon black for rubber, carbon black for pigment, carbon black for electronic material, and combinations thereof.
The method according to claim 1,
Wherein the hydrocarbon comprises at least one selected from the group consisting of natural gas, propane, butane, methane, liquefied petroleum gas and liquefied natural gas.
The method according to claim 1,
Wherein the first stage of the catalytic cracking reaction is carried out at a temperature between 600 and 950 < 0 > C.
An apparatus for producing hydrogen and carbon through catalytic cracking of hydrocarbons,
A fluidized bed reactor having a discharge line for recovering carbon black produced from the catalytic cracking process of the hydrocarbon, the carbon black catalyst being loaded;
A feeder connected to the upper part of the fluidized bed reactor by a nozzle, for supplying a hydrocarbon and an inert gas;
A pulverizing device for pulverizing the carbon black recovered through the discharge pipe to a size having catalytic activity to supply pulverized carbon black to the fluidized bed reactor;
A cyclone for recovering a gas mixture comprising hydrogen, unreacted hydrocarbon and entrained carbon produced in said fluidized bed reactor; And
A pressure conversion adsorption tower for separating hydrogen from the gas mixture recovered in the cyclone recoverer
≪ / RTI >
11. The method of claim 10,
Wherein the carbon black is discharged to the discharge pipe provided in the fluidized bed reactor and recovered when carbon is deposited by 15 to 25% with respect to the initial charged carbon black.
11. The method of claim 10,
The recovered, catalytically active size of the carbon black has a secondary particle size or aggregate size of 200 nm to 250 nm.
11. The method of claim 10,
Wherein the recovered carbon-deposited carbon black is pulverized at 150 rpm for 4 hours to 8 hours.
11. The method of claim 10,
Wherein the discharge tube comprises a fine nozzle for flowing gas to a side of the tube.
11. The method of claim 10,
Wherein the carbon black catalyst comprises at least one selected from the group consisting of carbon black for rubber, carbon black for pigment, carbon black for electronic material, and combinations thereof.
11. The method of claim 10,
Wherein the hydrocarbon comprises at least one selected from the group consisting of natural gas, propane, butane, methane, liquefied petroleum gas and liquefied natural gas.
11. The method of claim 10,
Wherein the catalytic cracking reaction is carried out at a temperature of 600 < 0 > C to 950 < 0 > C.
12. The method of claim 11,
Wherein the inert gas comprises nitrogen gas or argon gas.

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