KR100589202B1 - The synthesis gas preparing apparatus and method for controlling the composition of synthesis gas - Google Patents

Abstract

The present invention relates to a device for producing hydrogen and carbon monoxide (hereinafter referred to as "synthetic gas") that can control the composition of the synthesis gas from methane and oxygen compounds (hereinafter referred to as "reactant"), and a method for producing syngas using the same In the present invention, the apparatus of the present invention, through the respective introduction tubes (1 and 2), the introduction tubes (1 and 2) for introducing the reactant methane and oxygen compounds into the reactor, the reactant Position control valves 8a through 7a and 7b for controlling the flow rate of the gas and controlling the rate of the reaction products are connected to the inlet pipe 2 and arranged in the middle of the reactor to control the introduction of the reactants. 8f), the reaction tube (5) forming the body of the reactor and acting as a dielectric, the current to the inner electrode (3), the outer electrode (4) of the reactor, the inner electrode (3) and the outer electrode (4) To generate plasma It comprises a power source 6, electric wires 10 and 11 through which the current passes, a ground portion 12 of the electric current, and an outlet 9 for discharging the product (synthetic gas) produced after the reaction is completed to the outside. It is characterized by.

In addition, the production method of the present invention, by controlling the flow rate using the flow control valves (7a and 7b) while introducing the reactant methane and oxygen compounds into the reactor through the respective inlet pipe (1 and 2) A first step of adjusting the ratio; A second step of introducing a reactant introduced into the inlet pipe (2) in the first step into the reactor at a position selected by the position control valves (8a to 8f); Simultaneously with the first and second steps, a high voltage power supply 6 is applied to the inner electrode 3 of the reactor and the outer electrode 4 of the reactor to generate a plasma inside the reaction tube 5 to synthesize the same. A third step of producing a gas; And a fourth step of discharging the syngas obtained in the third step to the outside through the outlet 9 of the reactor.

By using the atmospheric barrier discharge reaction of the present invention using the apparatus and method for producing a synthesis gas capable of controlling the composition of the synthesis gas by reacting the reactant methane and the oxygen compound together, using the barrier discharge plasma at a low temperature In the production of syngas from oxygen-containing compounds, it is easy to make syngas with the composition required in the next step as desired. Therefore, instead of purchasing hydrogen and carbon monoxide separately from using syngas in another process using syngas, The ability to synthesize directly from the gases methane and carbon dioxide will allow the design of a very economical process for raw material costs.

Methane, Oxygen Compounds, Hydrogen, Carbon Monoxide, Syngas, Barrier Discharge, Plasma

Description

Synthesis gas production apparatus capable of controlling the composition of the synthesis gas and the synthesis gas production method using the same {The synthesis gas preparing apparatus and method for controlling the composition of synthesis gas}             

1 is a schematic cross-sectional view of a syngas production apparatus capable of controlling the composition of syngas used in the present invention.

2 is a view related to an example of a mixing method and a mixing position of reactants that can be combined in the apparatus of the present invention.

Figure 3 is a diagram showing the ratio of the synthesis gas produced using the method of the prior art.

4 is a diagram showing an example of a syngas composition produced using the apparatus of the present invention.

* Explanation of symbols for main parts of the drawings

1 and 2: Inlet tube 3: Internal electrode

4: external electrode 5: reaction tube

6: power supply 7a and 7b: flow control valve

8a to 8f: Position control valve 9: Outlet

10 and 11: wire 12: grounding current

The present invention relates to a device for producing hydrogen and carbon monoxide (hereinafter referred to as "synthetic gas") that can control the composition of the synthesis gas from methane and oxygen compounds (hereinafter referred to as "reactant"), and a method for producing syngas using the same It is about.

Natural gas is a natural gas from underground, which is one of the most useful resources because of its huge reserves and its wide distribution. Therefore, there is an active research to convert natural gas into more useful materials such as methanol or liquid fuel. Most of natural gas is made up of methane. Since methane is a very stable substance as saturated hydrocarbon, there are many difficulties in the conversion reaction. In general, natural gas can be converted to liquid fuels or useful compounds via synthesis gas or directly to C ₂ hydrocarbons or methanol. Most of the natural gas conversion processes that are operated commercially today convert natural gas into syngas by steam reforming and then synthesize methanol or gasoline as an intermediate.

Meanwhile, methane and carbon dioxide among natural gases are representative greenhouse gases, and researches for dealing with them due to global warming problems have been conducted in various aspects. In particular, carbon dioxide has emerged as a problem that needs to be addressed urgently in accordance with the carbon tax imposed by international conventions.

Syngas is a compound of hydrogen and carbon monoxide, specifically called syngas to distinguish it from fuel gas. At present, the most representative manufacturing method is ① water gasification method in which solid fuel such as coke or coal is heated in incandescent state using oxygen (or air), and steam is injected simultaneously or intermittently, ② lower hydrocarbon gas ( Steam reforming method (referred to as steam reforming) to react fluid fuels such as methane, ethane, propane, butane, naphtha, heavy oil and so on with steam at high temperature. Nickel-based catalyst for lower hydrocarbon gas naphtha and no catalyst for heavy oil. React under high pressure). In either case, a mixed gas mainly containing hydrogen, carbon monoxide and carbon dioxide is produced. The mixed gas is subjected to various purification steps to remove impurities, and then adjusted to a gas composition suitable for the synthesis reaction.

In the conventional steam reforming method, nickel catalysts are traditionally used to use a catalyst at a high temperature. As shown in Korean Patent Registration No. 0246079 and Korean Patent Application Publication No. 1996-0009892, a precious metal catalyst such as Pd, Rd, or an alkali metal and Alkaline earth metal catalysts may also be used.

In addition, instead of using steam in the steam reforming method, there is a carbon dioxide reforming method of methane using carbon dioxide. The carbon dioxide reforming reaction of methane proceeds with the following reaction formula and is a strong endothermic reaction.

[Chemical Scheme 1]

_{CH 4 + CO 2 ↔2CO + 2H} 2 △ H = 247 kJ / mol

The reaction takes place in the presence of a catalyst at a high temperature at atmospheric pressure, and a nickel-based catalyst is mainly used at a temperature of about 800 ° C. similarly to steam reforming.

On the other hand, low-temperature plasma can be used as a method for decomposing stable methane. Methane activation by plasma not only has the advantage of easily obtaining methyl radicals by the high energy of the plasma, but also is very useful in that it can induce various chemical reactions.

Plasma can be classified into a high temperature plasma and a low temperature plasma, and mainly used is a low temperature plasma, and among them, barrier discharge. The barrier discharge is the most widely used silent discharge electric discharge, a typical example of this is a coaxial generator in which metal electrodes such as stainless steel are concentrically arranged on both the inside and the outside of a glass or ceramic dielectric. Various methods have been proposed as a method of preparing a synthesis gas using this method, and as representative examples thereof, US Pat. Nos. 6,162,277, 60,607,632,407, 6,628,105, 6,676,278, 6,363,407. Etc.

However, these methods are merely related to the production of syngas using electric discharge, and there is no particular control method for the composition of the syngas produced. In the case of US Pat. No. 6,284,157, a method of controlling the composition of syngas generated by controlling the ratio of carbon dioxide and methane introduced is presented, and this can be expressed by an empirical formula to produce syngas having various compositions. However, this method is a method of controlling only the flow rate of the introduced gas, which is limited in the scope of application and a more advanced method is required for more flexible adjustment.

The composition of the produced syngas is important because it is necessary to use syngas having different compositions depending on the desired product in producing different compounds from the syngas. In other words, when synthesizing methanol with syngas, the molar ratio of hydrogen and carbon monoxide to be introduced should be 2: 1.

[Chemical Scheme 2]

2H ₂ + CO ↔CH ₃ OH

In another example, Korean Patent Laid-Open Publication No. 2004-0012837 used gas of H ₂ / CO (molar ratio) = 4 to prepare 1,3-propanol in syngas, and Korean Patent Laid-Open Publication No. 2000-0076574 Used H ₂ / CO (molar ratio) = 2.75 to synthesize dimethylether (DME). In addition, the Republic of Korea Patent Publication No. 199-0000475 suggests that H ₂ / CO (molar ratio) = 5 or less in the preparation of the symmetrical N, N'-substituted aromatic urea, and in the Republic of Korea Patent Publication No. 1984-0002259 For this purpose, H ₂ / CO (molar ratio) = 0.2 to 10 is specified.

As such, the composition varies depending on the type of material to be produced, but in the case of using the conventional method, a process of separating the generated syngas into hydrogen and carbon monoxide and then adjusting the composition to a desired composition should be added. To reduce this process, it is economically advantageous to tailor the resulting syngas to the desired composition.

Accordingly, the present invention has been made to solve the above problems, and an object of the present invention is to provide an apparatus and method capable of arbitrarily controlling the composition of syngas produced in syngas production using a barrier electric discharge. This is characterized by controlling the composition of the syngas generated in a finer and wider range than the method proposed in US Pat. To this end, in the present invention, the composition control of the synthesis gas is controlled by controlling not only the composition of the gas to be introduced but also the position to be introduced in the production of the synthesis gas from methane and an oxygen compound such as carbon dioxide using a barrier electric discharge. It is an object of the present invention to provide an apparatus and method for producing possible syngas.

In order to achieve the above object, the present invention is a device for producing a synthesis gas capable of controlling the composition of the synthesis gas, the respective inlet pipe (1 and 2) for introducing the reactant methane and oxygen compounds into the reactor, In order to control the flow rate of the reactant introduced into the reactor through the inlet pipe (1 and 2) and to control the ratio of the respective flow control valves (7a and 7b), connected to the inlet pipe (2) and in the middle of the reactor Positioning valves (8a to 8f) arranged to control the position where the reactants are introduced, the reaction tube (5) forming the body of the reactor and acts as a dielectric, the inner electrode (3) of the reactor, the outer electrode (4) of the reactor ), A power supply 6 for supplying current to the internal electrode 3 and the external electrode 4 to generate a plasma, wires 10 and 11 through which the current passes, a ground portion 12 of the current, and a reaction The finished product (synthetic gas) to the outside It provides an outlet (9), synthesis gas production unit is controlling the composition of the synthesis gas capable of being configured including for Ex.

The reactant introduced into the inlet pipe (2) can be introduced into the reactor using any one selected from the group consisting of the position control valve (8a to 8f).

The oxygen compound may be any one selected from the group consisting of carbon dioxide, water and air, preferably carbon dioxide.

The conductive metal may be used as the electrode, and the internal electrode 3 may be used in various forms, and any one selected from the group consisting of a general metal wire, a thin metal tube, or a spring shape may be used.

The external electrode 4 may be coated with a thin metal plate or a metal paste.

The reaction tube 5 may be any one selected from the group consisting of quartz tube, aluminum tube, zirconia tube and mullite tube.

The power supply 6 may be an alternating current or pulsed power supply, preferably a high voltage or high frequency AC power supply.

The position control valve (8a to 8f) is characterized in that the closing valve.

The number and spacing of the position control valves 8a to 8f can be changed as necessary.

The reaction occurs when a reactant passes through this section due to the generation of plasma in the space between the inner electrode 3 and the outer electrode 4 inside the tube 5, which forms the body of the reactor and serves as a dielectric.

In addition, the present invention is a method for producing a synthesis gas controllable composition of the synthesis gas, the flow control valve 7a and the introduction of the reactant methane and oxygen compounds into the reactor through the inlet pipe (1 and 2), respectively A first step of controlling the flow rate by controlling the flow rate using 7b); A second step of introducing a reactant introduced into the inlet pipe (2) in the first step into the reactor at a position selected by the position control valves (8a to 8f); Simultaneously with the first and second steps, a high voltage power supply 6 is applied to the inner electrode 3 of the reactor and the outer electrode 4 of the reactor to generate a plasma inside the reaction tube 5 to synthesize the same. A third step of producing a gas; And a fourth step of discharging the syngas obtained in the third step to the outside through the outlet port 9 of the reactor.

The oxygen compound may be used any one selected from the group containing carbon dioxide, water, air.

The conductive metal may be used as the electrode, and the internal electrode 3 may be used in various forms, and any one selected from the group consisting of a general metal wire, a thin metal tube, or a spring shape may be used.

The external electrode 4 may be coated with a thin metal plate or a metal paste.

The reaction tube 5 may be any one selected from the group consisting of quartz tube, aluminum tube, zirconia tube and mullite tube.

The power supply 6 may be an alternating current or pulsed power supply, preferably a high voltage or high frequency AC power supply.

The position control valve (8a to 8f) is characterized in that the closing valve.

The number and spacing of the position control valve (8a to 8f) is characterized in that it can be changed as necessary.

In the above apparatus and method of the present invention, the reactor may be variously combined according to the number of the inlet pipes, and the combination may control the composition of the synthesis gas as a reaction product. For example, if there are three inlet tubes in the middle of the reactor, as shown in FIG. 2, there are seven introduction paths, and in each case, the composition of reactants methane and carbon dioxide can be changed. In addition, increasing the number of incoming pipes will result in more cases.

The present invention will be described in more detail with reference to the following Examples. However, the following examples are provided only for the purpose of illustration in order to facilitate the understanding of the present invention, and the scope and scope of the present invention is not limited thereto.

Comparative Example 1

In order to compare the case of using the method of the present invention and the case of the prior art, in Comparative Example 1, the experiment was performed in the same manner as in the following example by adjusting the concentration of methane and carbon dioxide at the inlet of the reactor, The results are shown in FIG. In FIG. 4, the x axis is the ratio of H ₂ / CO and the y axis is the concentration of carbon dioxide in the mixed gas.

If, as shown in Figure 3, in a concentration in the case of the experiment, while the composition of the reaction of methane and carbon dioxide changes when the concentration of carbon dioxide at 20% by volume of a molar ratio of H ₂ / CO 2.5, CO 80 vol% H ₂ / The molar ratio of CO showed a value of 0.53. This can be seen that the adjustment is not easy if you want a value of 2.5 or more as shown in the US patent.

Example

  Embodiments 1 to 24 were performed using a syngas production apparatus capable of controlling composition of the syngas of FIG. 1.

At this time, the reactor was used as the external electrode 4 by silver plating the outside of the quartz tube 5 having an outer diameter of 8 mm and a thickness of 1 mm with a predetermined length. A spring having a diameter of 5 mm was used as the internal electrode 3. Used. The length of the reaction zone was 20 cm, and three position control valves were made in the reactor in order to perform the reaction experiment while changing the part where gas was introduced by attaching a valve in the middle of the reaction zone. The respective position control valves were installed at positions 2, 1/4 and 3/4. As a result, the number of cases where the reaction experiment is possible is a total of seven cases as shown in Figure 2, in each case the reaction experiment was performed while changing the flow rate ratio of the introduced gas. The power source 6 used an AC power source, and the frequency was 20 kHz and the voltage could be adjusted within 0-10 kV. In this experiment, the voltage was fixed at 3 kV and the frequency was fixed at 20 kHz. The input power was about 80 W. Input power was measured using a power meter (Metax M3860M), and the capacitance according to the spring spacing and external diameter in each reactor was measured by an RCL meter (Fluke, PM6304). GC (TCD, Youngin 680D, Porapak Q, R (1: 1) + Molecular sieve 5A) was used. The gas flow rate (ml / min) was tested at a flow rate of 0.5, 1, or 2 with a CH ₄ / CO ₂ ratio. A total of 21 cases were identified by varying three flow ratios and seven feed types.

<Examples 1 to 7>

Examples 1 (1a and 1b) to Example 7 are seven types that are possible when the CH ₄ / CO ₂ ratio to be introduced is 0.5. Examples 1a and Examples 2 to 4 show that methane is introduced into the inlet pipe (1). And carbon dioxide is introduced into the inlet pipe 2 and injected at a position selected by the position control valve. In Examples 1b and 5 to 7, carbon dioxide is introduced into the inlet pipe 1, and methane is introduced. In the case of being introduced into the pipe (2) and injected at the position selected by the position control valve. Here, Examples 1a and 1b is a case where methane and carbon dioxide are introduced into the reactor together at the reactor introduction portion, and the experimental results are the same.

The results of Examples 1 to 7 are summarized in Table 1 and Table 2 below. In this case, the selectivity of hydrogen in Table 1 and Table 2 was based on the hydrogen water of methane, the selectivity of carbon monoxide was based on the carbon number of methane and carbon dioxide.

Example Distance of inlet pipe [cm] Conversion rate [%] Selectivity [%] H ₂ / CO methane carbon dioxide Hydrogen carbon monoxide Example 1a 0 45.1 30.0 64.4 37.1 1.74 Example 2 5 42.3 25.6 70.2 32.7 2.14 Example 3 10 42.0 22.6 65.6 25.8 2.54 Example 4 15 38.2 13.5 64.7 13.5 4.81

Example Distance of inlet pipe [cm] Conversion rate [%] Selectivity [%] H ₂ / CO methane carbon dioxide Hydrogen carbon monoxide Example 1b 0 45.1 30.0 64.4 37.1 1.74 Example 5 5 37.4 32.4 58.8 40.3 1.46 Example 6 10 31.4 36.3 46.1 39.2 1.17 Example 7 15 24.3 35.0 38.6 39.8 0.97

<Examples 8 to 14>

Examples 8 (8a and 8b) to 14 are seven types that are possible when the CH ₄ / CO ₂ ratio to be introduced is 1.0, and Examples 8a and 9 to 11 show that methane is introduced into the inlet tube 1 , When carbon dioxide is introduced at the position selected by the position control valve through the inlet pipe (2), in Examples 8b and Examples 12 to 14 carbon dioxide is introduced into the inlet pipe (1), methane is introduced into the inlet pipe (2) This is the case where it is introduced at) and injected at the position selected by the position control valve. Here, Examples 8a and 8b are the case where methane and carbon dioxide are introduced into the reactor together at the reactor introduction portion, and the experimental results are the same.

The results of Examples 8 to 14 are summarized in Tables 3 and 4 below. In this case, the selectivity of hydrogen in Table 3 and Table 4 was based on the hydrogen number of methane, the selectivity of carbon monoxide was based on the carbon number of methane and carbon dioxide.

Example Distance of inlet pipe [cm] Conversion rate [%] Selectivity [%] H ₂ / CO methane carbon dioxide Hydrogen carbon monoxide Example 8a 0 43.1 30.3 62.9 57.1 1.10 Example 9 5 42.6 18.5 75.8 56.4 1.35 Example 10 10 40.2 11.8 85.4 51.6 1.65 Example 11 15 41.1 9.5 79.5 25.1 3.17

Example Distance of inlet pipe [cm] Conversion rate [%] Selectivity [%] H ₂ / CO methane carbon dioxide Hydrogen carbon monoxide Example 8b 0 43.1 30.3 62.9 57.1 1.10 Example 12 5 34.0 19.8 69.1 73.8 0.94 Example 13 10 28.2 24.9 49.1 68.4 0.72 Example 14 15 16.5 24.3 38.5 71.2 0.54

<Examples 15 to 21>

Examples 15 (15a and 15b) to 21 are seven types that are possible when the CH ₄ / CO ₂ ratio to be introduced is 2.0. Examples 15a and Examples 16 to 18 show that methane is introduced into the inlet tube 1 , When carbon dioxide is introduced at the position selected by the position control valve through the inlet pipe (2), in Examples 15b and 19 to 21, carbon dioxide is introduced into the inlet pipe (1), methane is introduced into the inlet pipe (2) This is the case where it is introduced at) and injected at the position selected by the position control valve. Here, Examples 15a and 15b are cases in which methane and carbon dioxide are introduced into the reactor together at the reactor introduction portion, and the experimental results are the same.

The results of Examples 15 to 21 are summarized in Tables 5 and 6 below. In this case, the selectivity of hydrogen in Table 5 and Table 6 was based on the hydrogen water of methane, the selectivity of carbon monoxide was based on the carbon number of methane and carbon dioxide.

Example Distance of inlet pipe [cm] Conversion rate [%] Selectivity [%] H ₂ / CO methane carbon dioxide Hydrogen carbon monoxide Example 15a 0 47.2 29.1 56.3 71.6 0.79 Example 16 5 52.3 24.3 58.1 63.1 0.92 Example 17 10 53.5 19.6 61.0 54.4 1.12 Example 18 15 52.5 15.4 60.8 36.1 1.68

Example Distance of inlet pipe [cm] Conversion rate [%] Selectivity [%] H ₂ / CO methane carbon dioxide Hydrogen carbon monoxide Example 15b 0 47.2 29.1 56.3 71.6 0.79 Example 19 5 38.7 22.8 54.2 83.8 0.65 Example 20 10 35.5 24.5 37.6 75.3 0.50 Example 21 15 25.8 27.1 19.5 68.9 0.28

As can be seen from Table 1 to Table 6, when looking at the overall trend, when methane is introduced first and carbon dioxide is introduced later, the conversion rate of methane and carbon dioxide gradually decreases as the introduction of carbon dioxide is delayed, but synthesis It can be seen that the ratio of gas (H ₂ / CO) gradually increases on the contrary (see Tables 1, 3 and 5). On the other hand, when carbon dioxide is introduced first and methane is introduced later, the conversion rate of methane decreases and the conversion rate of carbon dioxide increases or is constant as methane is introduced (see Tables 2, 4 and 6). As the flow rate of carbon dioxide increases, the conversion rate of carbon dioxide increases in this case, and as the rate of introduction flow increases to 2.0, the conversion rate of carbon dioxide also decreases. The ratio of syngas decreased gradually as opposed to the previous case.

In addition, the phenomenon common to all experiments is that the overall conversion rate increases as the fraction of carbon dioxide increases, and the ratio of syngas decreases, thereby increasing the amount of CO generated.

In terms of the amount of product, in the case of syngas, the desired product, the ratio of H ₂ / CO was generated in a wide range from about 0.3 to 4.8 in each case. This means that the synthesis gas of the desired composition can be obtained by controlling the introduction position and flow rate well. For example, in order to obtain a synthesis gas ratio of 1.7, two gases may be simultaneously added and reacted at an introduction flow rate of 0.5. When the introduction flow rate is 1, carbon dioxide may be introduced in the middle of the reactor. It can be seen that the introduction in the latter half of the reactor.

In addition, the results of Tables 1 to 6 are collectively shown in FIG. 4. In FIG. 4, the x-axis is the distance from the beginning of the reaction zone to where the inlet pipe is located and the y-axis is the ratio of the generated H ₂ / CO.

In FIG. 4,? Indicates that when the molar ratio of reactant methane / carbon dioxide is 0.5, methane is introduced into the inlet tube 1, and carbon dioxide is introduced into the inlet tube 2 and injected at a position selected by the position control valve. In this case, the molar ratio of H ₂ / CO according to the introduction position is indicated, and the mark indicates that when the molar ratio of reactant methane / carbon dioxide is 1.0, methane is introduced into the inlet tube 1 and carbon dioxide is introduced into the inlet tube 2. The molar ratio of H ₂ / CO according to the introduction position in the case of being injected at the position selected by the position control valve, the ▲ mark indicates that when the molar ratio of the reactant methane / carbon dioxide is 2.0, methane is introduced into the inlet pipe (1), The molar ratio of H ₂ / CO according to the introduction position when carbon dioxide is introduced into the inlet pipe 2 and injected at the position selected by the position control valve is shown.

In addition, in Fig. 4, the symbol O indicates that when the molar ratio of methane / carbon dioxide which is a reactant is 0.5, carbon dioxide is introduced into the inlet pipe 1, and methane is introduced into the inlet pipe 2 at the position selected by the position control valve. The molar ratio of H ₂ / CO according to the introduction position in the case of injection is indicated by □, and when the molar ratio of methane / carbon dioxide as a reactant is 1.0, carbon dioxide is introduced into the inlet tube 1 and methane is introduced into the inlet tube 2. The molar ratio of H ₂ / CO according to the introduction position in the case of being introduced and injected at the position selected by the position control valve, and the △ mark, the carbon dioxide is introduced into the inlet pipe (1) when the molar ratio of the reactant methane / carbon dioxide is 2.0 And the molar ratio of H ₂ / CO according to the introduction position when methane is introduced into the inlet pipe 2 and injected at the position selected by the position control valve, respectively.

At this time, it can be represented by the following equations 1 to 6 from the top line of Figure 4 (in the following equation, x, in common, x is the distance from the beginning of the reaction zone to the inlet pipe in cm unit).

H ₂ / CO ratio = 1.734 + 0.06e ^0.26x

H ₂ / CO ratio = 1.06 + 0.062e ^0.24x

H ₂ / CO ratio = 0.76 + 0.047e ^0.2x

H ₂ / CO ratio = 1.73-0.052x

H ₂ / CO ratio = 1.1-0.038x

H ₂ / CO ratio = 0.81-0.034x

From the results of this experiment, the H ₂ / CO ratio can be controlled in the range of 0.28 to 4.8.

On the other hand, since the present embodiment is the case of using only three inlet tubes in the unit of the reactor in a quarter unit, and the flow rate ratio of the reactants is also used only three cases, according to the change in the number of inlet pipes and the reactant flow rate H ₂ It can be seen that the / CO ratio is sufficiently controllable in the case of 0.3 or less and 4.8 or more.

<Examples 22 to 24>

Examples 22 to 24 show the effects of using carbon dioxide, air (oxygen), and water as oxygen-containing compounds, respectively, under the same conditions, except that the test method uses a voltage of 6 kV. Same as the example.

Example 22 is a case where carbon dioxide is used, when the molar ratio of CH ₄ / CO ₂ is 1, when methane and carbon dioxide are introduced into the reactor together at the reactor inlet, Example 23 is when air (oxygen) is used In this case, when the molar ratio of CH ₄ / O ₂ introduced is 2, methane and air (oxygen) are introduced together into the reactor at the reactor inlet, and Example 24 is the case of using water, and CH ₄ / H introduced _When the molar ratio of ₂ O is 0.8, methane and water are introduced together into the reactor at the reactor inlet. On the other hand, in Example 23, the result of the reaction with oxygen as air was described, because oxygen actually reacts in the air.

The results of Example 22 are shown in Table 7 below, the results of Example 23 are shown in Table 8 below, and the results of Example 24 are shown in Table 9 below. In this case, in Tables 7 to 9, the selectivity of hydrogen was based on the hydrogen number of methane, and the selectivity of carbon monoxide was based on the carbon number of methane and carbon dioxide.

Example Distance of inlet pipe [cm] Conversion rate [%] Selectivity [%] H ₂ / CO methane carbon dioxide Hydrogen carbon monoxide Example 22 0 34.4 13.0 71.3 51.5 1.38

Example Distance of inlet pipe [cm] Conversion rate [%] Selectivity [%] H ₂ / CO methane Oxygen Hydrogen carbon monoxide Example 23 0 57.2 100.0 62.3 63.9 0.98

Example Distance of inlet pipe [cm] Conversion rate [%] Selectivity [%] H ₂ / CO methane water Hydrogen carbon monoxide Example 24 0 45.3 - 75.6 21.0 3.6 * The conversion rate of water was not accurate due to condensation.

As can be seen in Tables 7 to 9, it was confirmed that the same product, that is, synthesis gas, can be obtained when carbon dioxide, air (oxygen), and water are used as the oxygen compound.

Although the invention has been described in detail above, it will be apparent to the inventors that various modifications and changes are possible within the scope and spirit of the invention, and it is obvious that such modifications and modifications fall within the scope of the appended claims.

By using the synthesis gas production apparatus and the synthesis gas production method using the composition control of the composition of the synthesis gas of the present invention, the synthesis gas of the composition required for the next step in the production of the synthesis gas using a low temperature barrier discharge plasma easily as desired It is possible to design a very economical process for raw material costs because it can be synthesized directly from natural gas methane and carbon dioxide instead of purchasing hydrogen and carbon monoxide separately in using syngas in another process using syngas. Could be.

Claims (11)

Apparatus for producing a synthesis gas capable of controlling the composition of the synthesis gas, each inlet pipe (1) for introducing any one oxygen compound selected from the group containing reactants methane and carbon dioxide, water and air (1) And 2) each of the flow control valves 7a and 7b for controlling the flow rate of the reactants introduced into the reactor through the inlet pipes 1 and 2 and adjusting the ratio thereof, and connected to the inlet pipe 2. Position control valve (8a to 8f) for controlling the position where the reactants are introduced in the middle of the reactor, the reaction tube (5) forming the body of the reactor and acts as a dielectric, the internal electrode (3) of the reactor, A power supply 6 for generating a plasma by supplying current to the external electrode 4, the internal electrode 3 and the external electrode 4, wires 10 and 11 through which the current passes, and a ground portion 12 of the current. ), And Synthetic gas production apparatus capable of controlling the composition of the synthesis gas, characterized in that it comprises a discharge port (9) for discharging the product (synthetic gas) produced by the reaction is completed. The composition control of the synthesis gas according to claim 1, wherein the reactant introduced into the inlet pipe (2) is introduced into the reactor by using any one selected from the group consisting of the position control valves (8a to 8f). Syngas production apparatus possible. delete 2. The syngas production apparatus of claim 1, wherein the external electrode (4) is coated with a thin metal plate or coated with a metal paste. The syngas production apparatus according to claim 1, wherein the reaction tube (5) is any one selected from the group consisting of quartz tubes, aluminum tubes, zirconia tubes, and mullite tubes. The syngas production apparatus of claim 1, wherein the position control valves (8a to 8f) are open / close valves. A method for producing a synthesis gas capable of controlling the composition of the synthesis gas, the reactor containing one of the oxygen compounds selected from the group containing reactant methane and carbon dioxide, water and air through the inlet pipe (1 and 2), respectively A first step of controlling the flow rate by controlling the flow rate using the flow rate control valves 7a and 7b while being introduced into; A second step of introducing a reactant introduced into the inlet pipe (2) in the first step into the reactor at a position selected by the position control valves (8a to 8f); Simultaneously with the first and second steps, a high voltage power supply 6 is applied to the inner electrode 3 of the reactor and the outer electrode 4 of the reactor to generate a plasma inside the reaction tube 5 to synthesize the same. A third step of producing a gas; And And a fourth step of discharging the syngas obtained in the third step to the outside through the outlet (9) of the reactor. delete 8. A method according to claim 7, wherein the external electrode (4) is coated with a thin metal plate or coated with a metal paste. 8. The method according to claim 7, wherein the reaction tube (5) is any one selected from the group consisting of quartz tubes, aluminum tubes, zirconia tubes, and mullite tubes. 8. Method according to claim 7, wherein said position control valves (8a to 8f) are open / close valves.

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