KR102142686B1 - Bilayered catalytic reactor and system for producing the synthesis gas using the same - Google Patents

Abstract

The present invention is a reactor containing a catalyst for preparing a synthesis gas for producing a synthesis gas from a reactant containing natural gas, wherein the reactor is a first reaction unit provided on the side where the reactant is introduced and the synthesis gas produced from the reactant is discharged It includes a second reaction unit provided on the side, the first reaction unit is a first catalyst, which is an alkali-treated catalyst for syngas production, is accommodated, and the second reaction unit is a synthesis gas, which is a catalyst for synthesis gas production. Reactor for gas production and a synthesis gas production system using the same, by providing a reactor having a double catalyst layer, reactants containing natural gas are first passed through an alkali-treated first catalyst to deactivate catalysts due to carbon deposition. At the same time, the conversion rate can be increased by preventing the second catalyst to pass through the alkali-free treatment.

Description

Bilayered catalytic reactor and system for producing the synthesis gas using the same}

The present invention relates to a syngas production system for producing syngas by simultaneously reforming natural gas into water vapor and carbon dioxide using a reactor containing a catalyst for syngas production.

Here, background arts related to the present disclosure are provided, and they do not necessarily mean known technologies.

Syngas produced in the reforming process is a mixture of hydrogen and carbon monoxide, and can be mainly used as a reactant for the synthesis of expensive chemical products such as ammonia and methanol. In addition, since it is used as a reactant of the next-generation fuel DME (Dimethylesther) synthesis and FT (Fischer-Tropsch) synthesis process, the reforming process can be regarded as an essential technology for manufacturing synthetic fuels.

As a method for producing synthetic gas using natural gas, steam reforming of methane (SRM), partial oxidation of methane (POM) using oxygen, and carbon dioxide reforming of methane (carbon dioxide reforming of methane; CDR), and the carbon monoxide and hydrogen (H ₂ /CO) ratios generated from each reforming reaction can be used differently depending on the optimum ratio required in the subsequent process.

For example, in the case of the SRM reaction, which is a strong endothermic reaction, the H ₂ /CO ratio can be obtained by 3 or more, so it is a reforming reaction suitable for hydrogen production and ammonia synthesis, and in the case of the POM reaction, the H ₂ /CO ratio is obtained to about 2 It is known as a reforming reaction that is advantageous for hydrocarbon synthesis by methanol synthesis reaction and Fischer-Tropsch reaction.

The individual reforming processes are also referred to as auto-thermal reforming (ATR) and tri-reforming in which POM and SRM are mixed to increase energy and carbon efficiency and maintain an appropriate H ₂ /CO ratio. A method in which three modified reactions of POM, SRM, and CDR are called is well known. In addition, according to the type and catalyst of the reforming reaction, H ₂ /CO ratio can be prepared for different synthesis gases, and patents using differentiation in which the subsequent synthesis process using it is changed are currently being applied [Korea Patent] Publication 2006-0132293; Korean Patent Publication No. 2005-0051820].

On the other hand, when nickel is used as a catalytically active material, CO generated during the reaction is adsorbed on the nickel surface, causing a Boudouard reaction in which carbon is deposited as in the reaction formula.

2CO ↔ CO ₂ + C(coke)

In order to prevent such a coke formation reaction, basic steam metal oxides (BaO, MgO, etc.) or various materials are supplied while maintaining the ratio of steam (H ₂ O) and Methane (CH ₄ ) to 3 or more by supplying excess water vapor. Metals are also added. In the case of a catalyst used in a reformer for small hydrogen production, precious metals, which are catalytically active substances, are supported or impregnated in alumina (Al ₂ O ₃ , Alumina) having a large surface area.

That is, a precious metal such as ruthenium (Ru), rhodium (Rh), platinum (Pt), iridium (Ir), osmium (Os) or the like, is used as an alumina support or impregnated catalyst as a support (for example, Ru /Alumina, Rh/Alumina, etc.) When it is used by supporting or impregnating a noble metal on a support, it is known that most of the initial catalyst performance or activity is maintained even with a reformer of about 10,000 hours or more.

In the case of a nickel-based catalyst, since the performance decrease due to carbon deposition inevitably occurs for a long time, it is necessary to prevent carbon deposition through the introduction of precious metals, but the international price of such precious metals is international Since it is about 100 to 1000 times more expensive than the price, when using a precious metal to prevent carbon deposition while using nickel as the main catalytic active material, it is inevitable to use a precious metal in a small amount of about 0.5 wt% or less.

1. U.S. Patent No. 6,136,279 2. US Patent No. 6,525,104 3. European Patent No. 0450872 4. Japanese Patent Publication No. 2000-104078 5. Republic of Korea Patent Publication No. 10-2004-00651953

The present invention is to solve the problems as described above, and it is easy to control the composition of the synthetic gas produced at an excellent conversion rate, and at the same time, the reactor containing the double catalyst layer capable of suppressing the carbon deposition phenomenon of the catalyst and syngas production using the same It is to provide a system.

However, the objects of the present invention are not limited to those mentioned above, and other objects not mentioned will be clearly understood by those skilled in the art from the following description.

The present invention is a reactor containing a catalyst for preparing a synthesis gas for producing a synthesis gas from a reactant containing natural gas, wherein the reactor is a first reaction unit provided on the side where the reactant is introduced and the synthesis gas produced from the reactant is discharged It includes a second reaction unit provided on the side, the first reaction unit is a first catalyst, which is an alkali-treated catalyst for syngas production, is accommodated, and the second reaction unit is a synthesis gas, which is a catalyst for synthesis gas production. A gas production reactor is provided.

In addition, the reactor is characterized in that the volume of the first reaction portion is 1/2 to 1.5 times the volume of the second reaction portion.

In addition, the second catalyst includes a support material containing at least magnesium (Mg) and aluminum (Al), an active accelerator containing at least cerium (Ce), and an active material containing at least nickel (Ni), and the catalyst It is characterized in that the O ₂ storage amount of the active material exposed on the surface of the metal and the oxide of the active accelerator is 60 to 70 μmol O ₂ /g _cat .

In addition, the first catalyst is characterized in that the catalyst is alkali-treated on the surface of the molding catalyst.

In addition, the present invention is a reactant supply unit for supplying a reactant containing natural gas, water vapor and carbon dioxide to the reactor through a supply line; And a reactor containing a catalyst for syngas production for receiving the reactant and preparing syngas, wherein the reactor includes a first reaction unit provided at the reactant inlet side and a synthetic gas prepared from the reactant outlet. It includes a second reaction unit provided in, the second reaction unit is a second catalyst, which is a catalyst for syngas production, is accommodated, and the first reaction unit is a reactor, which is a first catalyst, which is an alkali-treated catalyst for synthesis gas production. Provide a gas production system.

In addition, a fuel supply unit for supplying fuel including gas for fuel and air for ignition through a fuel line distinct from the supply line; further comprising, a heat exchange unit for heat exchange with the reactant and the fuel in front of the reactor; It is characterized by further including.

In addition, the heat exchange unit is characterized in that the temperature of the reactant is raised to 700 to 800 ℃.

In addition, the heat exchange unit is characterized in that the temperature of the fuel is raised to 300 to 400 ℃.

The present invention provides a reactor having a double catalyst layer so that a reactant containing natural gas first passes through an alkali-treated first catalyst to prevent deactivation of the catalyst due to carbon deposition, and reduce endothermic reaction at the top of the reactor. The conversion can be increased by preventing the reforming reaction from occurring intensively and at the same time passing the second catalyst that is not alkali-treated.

1 is a block diagram of a syngas production system according to an embodiment of the present invention.
Figure 2 shows the configuration of a bench-scale synthesis gas production system used in the experimental example of the present invention.

Before describing the present invention in detail below, it is understood that the terms used herein are only for describing specific embodiments and are not intended to limit the scope of the present invention, which is limited only by the scope of the appended claims. shall. All technical and scientific terms used in this specification have the same meaning as commonly understood by those skilled in the art unless otherwise stated.

Throughout this specification and claims, the term "comprise, comprises, comprising," unless otherwise stated, means including the recited article, step or group of articles, and steps, and any any other article. It is not meant to exclude a step or group of things or a group of steps.

On the other hand, various embodiments of the present invention can be combined with any other embodiments, unless otherwise indicated. Any feature indicated as particularly preferred or advantageous may be combined with any other feature or features indicated as preferred or advantageous. Hereinafter, embodiments and effects according to the present invention will be described with reference to the accompanying drawings.

The reactor 20 for syngas production according to an embodiment of the present invention is a reactor containing a catalyst for syngas production for producing syngas from reactants containing natural gas, and is produced by providing a reactor containing a double catalyst layer. It is easy to control the composition and at the same time provides an effect that can suppress the carbon deposition phenomenon of the catalyst.

The reactant containing natural gas is converted into synthetic gas while passing through the double catalyst layer filled in the reactor 20 for syngas production according to the present invention. The reactor 20 includes a first reaction unit 21 provided at a side where the reactants are introduced and a second reaction unit 22 provided at a side where the synthetic gas prepared from the reactants is discharged.

The first reaction unit 21 accommodates a first catalyst, which is an alkali-treated synthesis gas production catalyst, and the second reaction unit 22 accommodates a second catalyst, which is a synthesis gas production catalyst. By providing a reactor with a double catalyst layer, the reactant first passes through the alkali-treated first catalyst to prevent deactivation of the catalyst due to carbon deposition, and by reducing the endothermic reaction, the reforming reaction is intensively generated at the top of the reactor. At the same time, the conversion rate can be increased by allowing the second catalyst to pass through the alkali-free treatment.

More specifically, in the reactor 20, the volume of the first reaction unit 21 is 1/2 to 1.5 times the volume of the second reaction unit 22. When the volume of the first reaction unit 21 is less than 1/2 times the volume of the second reaction unit 22, there is a problem in that it is difficult to control a strong endothermic reaction due to a small number of low-active reaction parts, and when it exceeds 1.5 times There is a problem in that the activity of the reactor 20 is lowered because the portion of the low-activity reaction becomes longer.

The second catalyst includes steam reforming of methane (SRM) of natural gas containing methane (CH ₄ ) represented by the following Reaction Schemes 1 and 2, and carbon dioxide (CO ₂ ) reformation of methane (CH ₄ ). It is a nickel-based catalyst used to prepare a synthesis gas containing carbon monoxide (CO) and hydrogen (H ₂ ) by performing a mixed reforming reaction that simultaneously performs a reaction (Carbon dioxide reforming of methane; CDR).

[Scheme 1]

CH ₄ + H ₂ O = 3H ₂ + CO

[Scheme 2]

CH ₄ + CO ₂ = 2H ₂ + 2CO

The second catalyst is a catalyst in which 1.3 to 5.6% of the active material is exposed on the surface. In other aspects, the theoretical value when measuring the number of hydrogen atoms (H) adsorbed per one reduced metal active point exposed on the catalyst surface It is a catalyst with a hydrogen adsorption amount of 1.3 to 5.6% compared to (H/Ni=1). Nickel oxide in the molding catalyst is converted to nickel metal or nickel-alumina, etc. in the catalyst pretreatment (reduction) process, and nickel contained in 14.3 to 100% of the catalyst is converted to nickel metal, which is dependent on the interaction of each component. .

The second catalyst includes at least a part of an oxide of an active material, an oxide of an active accelerator, and an oxide of a support material. More specifically, in preparing a molding catalyst by impregnating a supporting material with the precursor of the active material and the precursor of the active accelerator, drying and firing, the active material and the active accelerator are partially reduced and oxidized, thereby oxidizing the active material on the catalyst surface. At least a part of the phosphorus metal (M ₁ ), the oxide of the active material (M ₁ O), the metal of the active accelerator (M ₂ ) and the oxide of the active accelerator (M ₂ O) is exposed. Depending on the interaction of the catalytic component, the active material-active accelerator (M ₁ -M ₂ ), active material-supporting material (M ₁ -S), and active accelerator-supporting material (M ₂ -S) mixed oxides Can be generated.

The second catalyst is characterized in that at least a portion of the metal, which is the active material, is exposed to 1.3 to 5.6% of the surface of the catalyst to contact the oxide of at least a part of the active accelerator exposed on the surface. When the metal, which is the active material, is exposed to less than 1.3% on the surface of the catalyst, there is a problem that the catalytic activity is too low, and when it is exposed to more than 5.6%, the catalytic activity is so high that the catalyst life is reduced due to carbon deposition and sintering have.

Wherein the second catalyst is that the metal (M ₁₎ and the molar ratio (M ₁ / M ₁ O) is 0.1 to 1.3 of the oxide of the active material (M ₁ O) active material in one aspect. When the molar ratio is less than 0.1, there is a problem that the catalyst activity is too low, and when it exceeds 1.3, the catalyst activity is too high, resulting in a decrease in catalyst life due to carbon deposition and sintering. More preferably, the molar ratio (M ₁ /M ₁ O) of the active material metal (M ₁ ) and the active material oxide (M ₁ O) is preferably 0.8 to 1.0.

The second catalyst is characterized in that the molar ratio of one (M ₁ / M ₂₎ of the active material of a metal (M ₁₎ and activity promoting material is a metal (M ₂₎ exposed at the surface it is 0.2 to 2. When the molar ratio (M ₁ /M ₂ ) is less than 0.2, there is a problem in that it is difficult to supply oxygen to the active metal during the reaction, and thus the activity is lowered. There is this. When the molar ratio (M ₁ /M ₂ ) is within the above range, it is thought that the resistance of the catalyst material to the poisoning material that may be included in the reactant is high, and the stability is also high, so that the life of the catalyst is good.

The active accelerator is a material that increases the oxygen storage capacity, and is included in the catalyst to primarily suppress the deactivation of the catalyst due to carbon deposition during the reforming reaction.

The second catalyst is characterized in that it comprises a mesopore (mesopore) having an average pore size of 18.6 to 33.5 nm and a micropore having a pore size of 1 nm or less. Preferably, the mesopore/micropore volume ratio is 92 to 115. If the mesopore/micropore volume ratio is too low, there is a problem that the particles of the active material metal are large and the dispersibility on the surface of the support is low. If the mesopore/micropore volume ratio is too high, the proximity of the oxide of the active material and the active accelerator is high. Can fall.

The second catalyst is a metal oxide containing a support material and includes a hydrotalcite crystal structure support. The support material includes at least magnesium (Mg) and aluminum (Al), and when formed as a support, the active material and activity in the form of a hydrotalcite crystal structure having a MgO/Al ₂ O ₃ weight ratio of 3/7 to 7/3 It provides a supporting structure that can promote chemical bonding.

The crystal size of the metal oxide containing the support material is 14.4 to 64.3nm. Depending on the crystal size of the metal oxide, the concentration of the acid point and the base point existing on the surface changes. When the crystal size is less than 14.4 nm, the concentration of the total base point/acid point increases, which adversely affects the catalytic reaction activity, 64.3 If it exceeds nm, the concentration of the total base point/acid point is lowered, which causes a problem of carbon deposition during the reaction.

The second catalyst is a catalyst formed in a form including at least two holes having a metal oxide oxygen storage amount of 60 to 70 μmol O ₂ /g _{cat as} an active material exposed to a surface and a metal. By providing a syngas production system for producing syngas by simultaneously reforming natural gas into water vapor and carbon dioxide using a reactor containing the catalyst for syngas production, it is resistant to carbon deposition and is stable even when compound reforming because it has good oxygen storage capacity. It can provide an effect that can maintain. It is preferably molded into a 4-hole shape.

The method of manufacturing the second catalyst is first, by supporting at least a precursor of an active accelerator containing cerium (Ce) on a support formed of a supporting material containing at least magnesium (Mg) and aluminum (Al), and at least simultaneously or sequentially A mixture carrying a precursor of an active material containing nickel (Ni) is prepared. After drying at 100 to 150 ℃ to obtain a catalyst in the form of a powder. The ball-milling process is performed for 9 to 12 hours by mixing the catalyst in the form of water and the powder, and the spray-drying process is performed using the ball-milled powder, followed by the use of a spherical spray-dried powder. Thus, a catalyst-like body having at least two holes is obtained. By firing the obtained molding catalyst at a temperature of 950 to 1050°C, a catalyst for preparing syngas having the above properties can be prepared.

More specifically, as a support for the second catalyst, MgO/Al ₂ O ₃ was used as a precursor of cerium by impregnation using an Mg-Al metal oxide having a hydrotalcite structure having a weight ratio of 3/7 to 7/3. The mixture is prepared so that the metal is 3 to 20% by weight based on the total weight of the prepared catalyst, and at the same time, 5 to 20% by weight based on the total weight of the catalyst prepared using a nickel precursor is prepared. After stirring for 10 to 15 hours at 50 to 100°C using a vacuum dryer, water as a solvent is removed and dried at 100 to 150°C for 24 hours or more to obtain a catalyst in powder form. The ball-milling process is performed for 9 to 12 hours by mixing the catalyst in the form of water and the powder, and the spray-drying process is performed using the ball-milled powder, followed by the use of a spherical spray-dried powder. Thus, a catalyst-like body having at least two holes is obtained. The obtained molding catalyst is calcined at a temperature of 950 to 1050° C. for 5 to 8 hours to prepare Ni-Ce/Mg-Al, a second catalyst.

The first catalyst is a catalyst treated with an alkali of the same composition (component and content) as the second catalyst, potassium (Potassium, K), sodium (Sodium, Na), magnesium (Magnasium, Mg) to the second catalyst ) Or calcium (calcium, Ca) is an alkali-treated catalyst.

The first catalyst contains 10 to 20 mol.% of an alkali metal material relative to the active material contained in the catalyst. When the alkali material is contained in less than 10 mol.%, the catalytic activity is maintained, and there is a problem that the endothermic amount cannot be controlled, and when it is included in excess of 20 mol.%, the catalytic activity is very low. Preferably, the alkali material is contained in 15 mol.% to 20 mol.%. More preferably, it is preferable that potassium is contained in 15 to 20 mol.% of potassium with respect to nickel contained in the alkali-treated nickel-based catalyst.

The first catalyst has an effect of reducing the conversion rate by partially reducing the active site of the active material while the alkali metal interacts with the active material, but it is suitable as a top catalyst because it reduces the endothermic reaction at the top of the reforming reactor. In addition, as the alkali metal is supported, the base point increases, so that the adsorption capacity and activation capacity with CO ₂ are increased, thereby reducing the amount of carbon deposition. However, if the base point becomes too large, it is preferable that the total base amount is 180 to 230 μmol CO ₂ /g _cat because the conversion rate decreases.

Alkali-treated catalysts have the effect of preventing the accumulation of coke on the surface of the catalyst and reducing the carbon deposition by the ability to gasify the coke, but the alkali metal interacts with the active material to partially reduce the activity point. Therefore, it was found that the conversion rate is lower than that of the catalyst that is not treated with alkali, and the conversion rate decreases as the amount of the alkali component treated in the catalyst increases. Therefore, the alkali-treated catalyst is accommodated in the first reaction unit 21 at the top of the reactor 20 according to the present invention to prevent carbon deposition while accommodating the catalyst that is not alkali-treated in the second reaction unit 22 at the bottom. By doing so, it was prevented that the conversion rate was lowered.

The first catalyst is a second catalyst, after preparing a molding catalyst, the prepared molding catalyst is initially impregnated with an aqueous alkaline precursor solution (incipient wetness impregnation), and after mixing for 2 hours to 4 hours at 100 to 120°C. It is prepared by drying and calcination at 500 to 700°C for 4 to 6 hours.

To describe a more specific alkali treatment method, the prepared second catalyst is supported and mixed in an aqueous alkali precursor solution through an incipient wetness impregnation. At this time, the alkali material is supported to be 4 to 16 mol.% with respect to the Ni metal of the molding catalyst. Even when supporting by mass production method, it is recommended to support at room temperature for more than 1 hour. Then, the supported and mixed composition is dried at 100 to 120°C for 2 hours or more (drying). When drying below 100 ℃, there is a problem that water is not dried in the aqueous alkali metal solution. When drying for less than 2 hours, there is a problem that water is not dried in the pores of the formed catalyst. Preferably, drying is performed at 105 to 115°C for 2 to 3 hours. Subsequently, the dried composition is calcined to obtain a final type of alkali-treated nickel-based catalyst, and calcined at 500 to 700° C. for 4 to 6 hours. When firing below 500°C, there is a problem that the nitrate contained in the alkali metal precursor does not decompose, and when firing above 700°C, there is a problem that the alkali metals may clump together. Preferably it is good to bake for 5 to 6 hours at 550 to 650 ℃.

Synthetic gas production system according to another embodiment of the present invention is a reactant supply unit 10 for supplying a reactant containing natural gas, water vapor and carbon dioxide to the reactor through a supply line and receiving the reactant to produce a synthesis gas And a reactor 20 containing a catalyst for syngas production. The reactor 20 uses the reactor according to the present invention described above. 1 is a block diagram of a syngas production system according to an embodiment of the present invention.

The reactant supply unit 10 supplies natural gas by adjusting the molar ratio of the components included in the reactant to obtain a synthesis gas containing a product having a desired composition. For example, the carbon dioxide is supplied at a molar ratio of 0.1 to 0.5 compared to natural gas supplied as a reactant.

In addition, the syngas production system according to the present invention further includes a fuel supply unit 30 for supplying fuel including gas for fuel and ignition air through a fuel line distinct from the supply line, and the reactor 20 is sheared. In addition, it further includes a heat exchange unit 40 in which heat exchange is made with reactants and fuel. In addition, it further includes a heating unit 50 that provides heat exchange in the heat exchange unit 40 and reaction heat required in the reactor 20.

The heat exchanger 40 is a heat exchanger indirectly heated with a heating medium heated in a boiler or the like, and the temperature of the reactant is raised to 700 to 800°C, and the temperature of the combustion air is raised to 300 to 400°C.

The heating unit 50 is a heater that is directly heated by heating such as combustion and resistance heat, and is heated to maintain a reaction temperature of 800 to 1000° C. for syngas production in the reactor 20.

The syngas produced through the syngas production system using the reactor 20 for syngas production according to the present invention has a molar ratio of H ₂ /(2CO+3CO ₂ ) of 0.8 to 1.2.

Example 1-Preparation of catalyst for syngas production

(1) Preparation of molding catalyst (second catalyst)

First, PURAL MG30, a hydrotalcite-structure Mg-Al metal oxide having a weight ratio of 3/7 of MgO/Al ₂ O ₃ as a support for a catalyst for syngas production (manufactured by Sasol, has a specific surface area of at least 250 m ² /g or more, Hereinafter, by using the "Mg-Al") using the cerium acetate by impregnation method so that the Ce metal is 6% by weight compared to the total weight of the prepared catalyst and at the same time nickel nitrate as a nickel precursor (Ni(NO ₃ ) ₂ After supporting 15% by weight of the total catalyst weight prepared using 6H ₂ O) and stirring for 12 hours at 70°C using a vacuum dryer, the solvent water is removed and dried in an oven at 100°C for 24 hours or more, The ball-milling process is performed for 10 hours by mixing water and powder. Spray dry process is performed using ball-milled powder. A 4-hole catalyst was molded using a spherical spray-dried powder, and fired at 1000° C. for 6 hours to prepare a final catalyst, Ni-Ce/Mg-Al.

(2) Preparation of alkali treated catalyst (first catalyst)

H ₂ O 450 g and KNO ₃ 77.5 g aqueous solution was impregnated with 2000 g of the prepared NCMA catalyst, and after mixing, dried at 110° C. for 2 hours or more and calcined at 600° C. for 5 hours to obtain a potassium treated NCMA catalyst (K-NCMA). It was prepared.

Alkali-treated catalyst was prepared by changing the content and type of alkali as shown in Table 1 below.

As a comparative example, a catalyst (Production Example 10) as a commercial catalyst was purchased.

Treatment ingredients Alkali metal content (mol.%) catalyst Preparation Example 1 - - NCMA Preparation Example 2 K 5 5K-NCMA Preparation Example 3 K 10 10K-NCMA Preparation Example 4 K 15 15K-NCMA Preparation Example 5 K 20 20K-NCMA Preparation Example 6 K 30 30K-NCMA Preparation Example 7 Na 15 15Na-NCMA Preparation Example 8 Mg 15 15Mg-NCMA Preparation Example 9 Ca 15 15Ca-NCMA Preparation Example 10 - - SRM commercial catalyst

Example 2-Reactor configuration for syngas production

The catalyst configuration accommodated in the reactor is shown in Table 2 below. In addition, the volume ratio of the first reaction part and the second reaction part is shown in Table 2 below.

1st reaction part Second reaction part Volume ratio Example 1 Preparation Example 3 Preparation Example 1 1:1 Example 2 Preparation Example 4 Preparation Example 1 1:1 Example 3 Preparation Example 5 Preparation Example 1 1:1 Example 4 Preparation Example 7 Preparation Example 1 1:1 Example 5 Preparation Example 8 Preparation Example 1 1:1 Example 6 Preparation Example 9 Preparation Example 1 1:1 Example 7 Preparation Example 3 Preparation Example 1 1:2 Example 8 Preparation Example 3 Preparation Example 1 2:3 Example 9 Preparation Example 3 Preparation Example 1 3:2 Comparative Example 1 Preparation Example 1 Preparation Example 1 1:1 Comparative Example 2 Preparation Example 2 Preparation Example 1 1:1 Comparative Example 3 Preparation Example 6 Preparation Example 1 1:1 Comparative Example 4 Preparation Example 10 Preparation Example 1 1:1 Comparative Example 5 Preparation Example 3 Preparation Example 1 1:3 Comparative Example 6 Preparation Example 3 Preparation Example 1 2:1 Comparative Example 7 Preparation Example 3 Preparation Example 1 3:1

Experimental Example

(1) Measurement of conversion rate of methane (CH ₄ ) and carbon dioxide (CO ₂ )

As a reactant in the supply part, a molar ratio of CH ₄ : CO ₂ : H ₂ O: N ₂ was fixed at a ratio of 1: 0.4: 1.6: 1 and injected into the reactor to perform a reforming reaction. The bench reactor consists of three heaters, and the temperature of the heaters is set to 850°C. The reactor has an inner diameter of 32.52 mm and the total length of the reactor is 110 cm. In the reactor, a catalyst layer was installed with TC to indicate temperature. In the case of the formed catalyst, the size was 2 cm or more and pulverized to a size of 4.8 to 6.4 mm for a bench scale reactor experiment. As shown in Fig. 3, the actual catalyst layer reaction region was 66 cm, and five temperatures were indicated.

After loading the catalyst into the reforming reactor with the volume composition shown in Table 2 and reducing it for 3 hours under a hydrogen (5 vol% H ₂ /N ₂ ) atmosphere at 700° C., the three heater temperatures are 850° C., the reaction pressure is 0.5 MPa, and space The reaction was carried out for 24 hours at a condition of a rate of 5000 L (CH ₄ )/kgcat/hr, and the temperature of the catalyst layer was shown in Table 3 below while the reaction reached and maintained the equilibrium, and the conversion rate measurement results are shown in Table 4 below. Did.

External control
(Heater 830 ^o C) Temperature 1
( ^o C) Temperature 2
( ^o C) Temperature 3
( ^o C) Temperature 4
( ^o C) Temperature 5
( ^o C) Example 1 720 746 784 799 812 Example 2 754 771 783 797 813 Example 3 759 774 788 799 812 Example 4 750 770 780 794 809 Example 5 748 768 783 793 809 Example 6 753 771 784 791 810 Example 7 748 759 781 793 813 Example 8 753 764 780 794 810 Example 9 754 766 781 793 811 Comparative Example 1 714 734 778 805 815 Comparative Example 2 717 740 781 803 815 Comparative Example 3 770 774 782 788 803 Comparative Example 4 721 739 779 804 813 Comparative Example 5 729 739 778 799 812 Comparative Example 6 753 767 782 789 805 Comparative Example 7 754 768 780 788 803

In the case of Comparative Example 1, only the NCMA catalyst is filled, so the reactivity is relatively high, so the temperature of temperature 1 is relatively low. The temperature distribution similar to that of Comparative Example 1 is shown. In the case of Comparative Example 4, since the activity of the commercial catalyst is shown as it is, it can be seen that the temperature of temperature 1 is low. In the case of Comparative Example 5, the volume ratio of the 15K-NCMA catalyst, which is the first catalyst, was relatively small, confirming that the temperature of Temperature 1 was low. In the case of Comparative Examples 1, 2, 4 and 5, it can be seen that the temperature of temperature 1 is relatively low, so that the temperature deviation is large. In the case of Comparative Example 3, when the low activity 30K-NCMA catalyst is filled with the first catalyst, the temperature distribution is advantageous due to the low activity, but when the low activity first catalyst is filled, the overall activity is lowered. . A catalyst having an activity capable of reaching an equilibrium conversion rate while maintaining a uniform temperature distribution should be utilized as the first catalyst. In the case of the embodiments according to the present invention, it can be confirmed that the temperature deviation is relatively small, which is advantageous for controlling the reaction heat. The composition of the first catalyst can control the heat of endothermic reaction at the entrance of the reaction and reduce the temperature distribution gap due to the controlled heat of reaction. This can greatly help reduce the stress of the actual reformer material.

External control
(Heater 830 ^o C) CH ₄ conversion rate (%) CO ₂ conversion (%) Example 1 90.7 14.8 Example 2 90.8 14.7 Example 3 90.7 14.6 Example 4 90.7 14.6 Example 5 90.8 14.7 Example 6 90.9 14.9 Example 7 90.7 14.4 Example 8 90.4 14.7 Example 9 90.6 14.9 Comparative Example 1 91.1 15.3 Comparative Example 2 90.9 14.8 Comparative Example 3 89.2 13.5 Comparative Example 4 90.7 14.7 Comparative Example 5 90.6 14.8 Comparative Example 6 89.3 13.7 Comparative Example 7 89.1 13.5

In the case of a reforming reaction, the conversion rate changes according to the temperature at the bottom as a temperature-dependent reaction. Examples 1 to 9 and Comparative Examples 1 to 5 can be confirmed that the temperature 5 is similar, as shown in Table 3, it can be confirmed that the CH ₄ conversion rate, CO ₂ conversion rate is similar, as shown in Table 4. In the case of Comparative Examples 6 and 7, it was confirmed that the volume ratio of the 15K-NCMA catalyst, which is the first catalyst, was relatively high and the temperature 5 was relatively low. Accordingly, it can be seen that the CH ₄ conversion rate and the CO ₂ conversion rate are also relatively lowest. When the volume of the first catalyst having a relatively low activity is excessively set, the temperature of the lower temperature 5 catalyst layer is lowered, and this has the disadvantage of lowering the conversion rate of the entire reforming reaction. Therefore, the volume of the first catalyst is preferably maintained at about 1/2 to 1.5 times the volume of the second catalyst.

(2) Carbon deposition measurement

The results of measuring carbon deposition of the first catalyst accommodated in the first reaction unit and the results of measuring carbon deposition of the second catalyst accommodated in the second reaction unit are shown in Table 5 below. The amount of carbon deposits of each catalyst was confirmed by thermo-Gravimetric Analysis (TGA) for the catalyst accommodated in each reaction unit.

1st reaction part Second reaction part Volume ratio Example 1 - - 1:1 Example 2 - - 1:1 Example 3 - - 1:1 Example 4 - - 1:1 Example 5 - - 1:1 Example 6 - - 1:1 Example 7 - - 1:2 Example 8 - - 3:2 Example 9 - - 2:3 Comparative Example 1 - - 1:1 Comparative Example 2 - - 1:1 Comparative Example 3 - - 1:1 Comparative Example 4 3.2 wt% - 1:1 Comparative Example 5 - - 1:3 Comparative Example 6 - - 2:1 Comparative Example 7 - - 3:1

The features, structures, effects, and the like exemplified in each of the above-described embodiments may be combined or modified for other embodiments by a person having ordinary knowledge in the field to which the embodiments belong. Therefore, the contents related to such combinations and modifications should be interpreted as being included in the scope of the present invention.

10: reactant supply
20: reactor
21: first reaction unit 22: second reaction unit
30: fuel supply
40: heat exchanger
50: heating section

Claims (8)

As a reactor containing a synthesis gas production catalyst for producing a synthesis gas from a reactant containing natural gas,
The reactor includes a first reaction unit provided on the side where the reactants are introduced and a second reaction unit provided on the side where synthetic gas prepared from the reactants flows out,
In the first reaction unit, a first catalyst that is a catalyst for syngas production is accommodated, and in the second reaction unit, a second catalyst that is a catalyst for synthesis gas production is accommodated,
The first and second catalysts include a support material including magnesium (Mg) and aluminum (Al), an active accelerator material including cerium (Ce), and an active material including nickel (Ni),
The first catalyst contains alkali metal, magnesium (Mg) or calcium (Ca), which prevents carbon deposition on the surface, in an amount of 10 to 20 mol% with respect to the active material,
The alkali metal, magnesium (Mg) or calcium (Ca) interacts with the active material to reduce the active site of the active material,
The cerium (Ce) is included in 6 to 20 wt% of the total catalyst,
The second catalyst is a molar ratio of the active material of a metal (M ₁₎ and the oxide of the active material _{(M 1 O) (M 1} / M 1 O) is 0.1 to 1.3,
Reactor for syngas production in which the molar ratio (M ₁ /M ₂ ) of the active material metal (M ₁ ) and the active accelerator metal (M ₂ ) exposed to the surface is 0.2 to 2.
According to claim 1,
The reactor is a reactor for syngas production, characterized in that the volume of the first reaction unit is 1/2 to 1.5 times the volume of the second reaction unit.
According to claim 2,
Synthesis of a catalyst formed into a form containing at least two or more holes, with an O ₂ storage amount of an active material metal exposed on the surface of the second catalyst and an oxide of the active accelerator 60 to 70 μmol O ₂ /g _cat Reactor for gas production.
According to claim 3,
The reactor for syngas production wherein the temperature of the first reaction unit is maintained at 720 to 1000°C.
A reactant supply unit supplying a reactant containing natural gas, water vapor and carbon dioxide to the reactor through a supply line; And
Includes a reactor containing a catalyst for producing a synthesis gas to produce a synthesis gas receiving the reactant;
The reactor includes a first reaction portion provided on the reactant inlet side and a second reaction portion provided on the side from which the synthetic gas prepared from the reactant flows,
In the first reaction unit, a first catalyst that is a catalyst for syngas production is accommodated, and in the second reaction unit, a second catalyst that is a catalyst for synthesis gas production is accommodated,
The first and second catalysts include a support material including magnesium (Mg) and aluminum (Al), an active accelerator material including cerium (Ce), and an active material including nickel (Ni),
The first catalyst contains alkali metal, magnesium (Mg) or calcium (Ca), which prevents carbon deposition on the surface, in an amount of 10 to 20 mol% with respect to the active material,
The alkali metal, magnesium (Mg) or calcium (Ca) interacts with the active material to reduce the active site of the active material,
The cerium (Ce) is included in 6 to 20 wt% of the total catalyst,
The second catalyst is from 0.1 to 1.3 mole ratio (M1 / M ₁ O) of the active material of a metal (M ₁₎ and the oxide of the active material (M ₁ O),
The active material of a metal (M ₁₎ and activity promoting material is a metal (M ₂₎ the molar ratio (M ₁ / M ₂₎ is from 0.2 to 2 for preparing a synthesis gas reactor, the synthesis gas production system on the surface.
The method of claim 5,
It further includes a fuel supply unit for supplying fuel including gas for fuel and ignition air through a fuel line distinct from the supply line;
Synthesis gas production system further comprises a; heat exchange unit to heat exchange with the reactant and the fuel in front of the reactor.
The method of claim 6,
The heat exchange portion is heated to 700 to 800 ℃ temperature of the reactants,
The temperature of the first reaction unit is 720 ~ 1000 ℃ synthesis gas production system.
The method of claim 6,
The heat exchange unit syngas production system, characterized in that the temperature of the fuel is raised to 300 to 400 ℃.

Images