Two-dimensional catalyst composite for methane dry reforming reaction and manufacturing method thereof

Abstract

The present invention relates to: a two-dimensional catalyst composite for a methane dry reforming reaction; and a manufacturing method thereof. The two-dimensional catalyst composite comprises: a two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) in which at least some of boron in an exfoliated MWW framework is substituted with nickel; and molybdenum particles supported on the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML).

Description

Two-dimensional catalyst composite for methane dry reforming reaction and method for preparing the same

[0001] The present invention relates to a two-dimensional catalyst composite for methane dry reforming reaction and a method for producing the same.

[0002] Dry reforming of methane (DRM) is a reaction (Reaction Formula 1) that converts greenhouse gases CH4 and CO2 into synthesis gas (a mixture of H2 and CO). The dry reforming of methane is attracting attention from the environmental and industrial fields because it is one of the key technologies for building a circular carbon economy that recycles CO2 into value-added chemicals such as synthetic fuels, methanol, and dimethyl ether, and mitigates emissions into the environment.

[0003] <Reaction Scheme 1>

[0004] CH4+ CO2→ 2H2△H° 298 = 247 kJ / mol -1

[0005] However, regardless of its high impact on the environment and industry, the successful commercialization of methane dry reforming is difficult due to the complexity and endothermic nature of the reaction. In fact, the dry reforming of methane is performed by the Boudouard reaction (2CO ↔ CO2, △H° 298 = -190 kJ mol -1 ) and methane cracking (CH4→ 2H2, △H° 298 = 75 kJ mol -1 ) to produce carbon deposits and reverse water-gas shift reaction (RWGS, CO2+ H2↔ H2O, △H°) 298 = 41 kJ mol -1 ) is accompanied by side reactions that reduce the H2 / CO ratio of the synthesis gas.

[0006] Therefore, to successfully commercialize the dry reforming reaction of methane, the development of highly active and stable catalysts is necessary.

[0007] In this dry reforming reaction of methane, much research has been conducted mainly on the catalytic potential of various types of transition metals, and in particular, catalyst development is being carried out including Group VIII (VIII) metals such as platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), nickel (Ni), and cobalt (Co). However, among these, Pt, Ru, Rh, and Pd are noble metals and, although they have good catalytic activity, selectivity, and stability, they are expensive and thus not economically efficient for industrial use.

[0008] Therefore, studies have been conducted on the possibility of using transition metals such as tungsten (W), titanium (Ti), vanadium (V), nickel (Ni), iron (Fe), copper (Cu), molybdenum (Mo), and cobalt (Co), which are less expensive than noble metals, as dry reforming catalysts for methane. Among these, nickel is widely used as a dry reforming catalyst for methane because it is relatively inexpensive compared to other transition metals and has relatively high selectivity and conversion rate for CO2 reforming of methane.

[0009] However, in the case of these Ni catalysts, it is difficult to maintain long catalytic activity for a relatively long time due to deactivation caused by coke deposition and active metal sintering during the dry reforming reaction of methane.

[0010] Therefore, in the dry reforming reaction of methane, it is necessary to develop a catalyst that can maintain long catalytic activity and minimize coke production.

[0011] [Prior Art Literature]

[0012] [Patent Document]

[0013] (Patent Document 1) Republic of Korea Patent Publication No. 10-2408100

[0014] The present invention aims to provide a catalyst complex and a method for producing the same that realizes a high conversion rate of methane and carbon dioxide and a low amount of coke production in a dry reforming reaction of methane.

[0015] One embodiment of the present invention provides a two-dimensional catalyst composite for a methane dry reforming reaction, comprising: a two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) in which at least a portion of boron in an exfoliated MWW skeleton structure is substituted with nickel; and molybdenum particles supported on the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML).

[0016] Another embodiment of the present invention provides a method for producing a two-dimensional catalyst composite for methane dry reforming. Specifically, the method comprises the steps of: (A) preparing a layered MWW skeletal borosilicate (B-MWW); (B) replacing at least a portion of boron in the MWW skeletal structure with nickel and delaminating the layered MWW skeleton to form a two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML); and (C) supporting molybdenum particles on the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML).

[0017] The two-dimensional catalyst composite for methane dry reforming according to the present invention has the advantage of maintaining high catalytic activity for a long period of time by realizing a high conversion rate of methane and carbon dioxide and a low amount of coke production.

[0018] Figure 1 is a graph showing the methane / carbon dioxide conversion rate and coke production amount of catalysts according to Comparative Example 1 and Examples 1 to 6.

[0019] Figure 2 shows the methane and carbon dioxide conversion rates over time of the catalyst according to Comparative Example 1.

[0020] Figure 3 shows the methane and carbon dioxide conversion rates over time of the catalyst according to Example 2.

[0021] In this specification, when a part is said to "include" a certain component, this does not mean that it excludes other components, but rather that it may include other components, unless specifically stated otherwise.

[0022] In this specification, when it is said that a member is located "on" another member, this includes not only cases where the member is in contact with the other member, but also cases where another member exists between the two members.

[0023] Hereinafter, the present invention will be described in detail.

[0024] One embodiment of the present invention provides a two-dimensional catalyst composite for a methane dry reforming reaction, comprising: a two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) in which at least a portion of boron in an exfoliated MWW skeleton structure is substituted with nickel; and molybdenum particles supported on the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML).

[0025] According to one embodiment of the present invention, the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML; Ni / B - delaminated MWW layers) may be one in which at least a portion of boron within the skeletal structure of an exfoliated MWW skeletal borosilicate (B-MWW) is replaced with nickel.

[0026] The above MWW framework is one of the zeolite framework topologies existing in a lamellar form, and the MWW framework structure is a three-dimensional structure including two independent pore systems, one of a pore system of two-dimensional sinusoidal 10-membered ring (10-MR) channels having an elliptical ring cross-section of 4.1 Å × 5.1 Å and a pore system including a large 12-MR giant cage connected to the 10-MR window.

[0027] According to one embodiment of the present invention, the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) may be a layered MWW skeleton-type borosilicate bonded in the form of Si-OB within the MWW skeleton, in which at least a portion of boron within the MWW skeleton structure is replaced with nickel.

[0028] According to one embodiment of the present invention, the molybdenum particles may be dispersed and provided on the surface of the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML). The molybdenum particles may serve as a cocatalyst that assists the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) in the dry reforming reaction of methane.

[0029] Specifically, the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) may include all of the contents disclosed in Korean Patent Publication No. 10-2408100. Specifically, the present invention can improve the molecular sieve catalyst according to the invention of No. 10-2408100, thereby realizing an improved conversion rate and a low coke production rate in the dry reforming reaction of methane.

[0030] According to one embodiment of the present invention, the content of molybdenum particles in the two-dimensional catalyst composite may be 0.3 wt% to 7 wt%. Specifically, the content of molybdenum particles in the two-dimensional catalyst composite may be 0.3 wt% to 6.5 wt%, 0.3 wt% to 6 wt%, 0.3 wt% to 5 wt%, 0.3 wt% to 3 wt%, 0.3 wt% to 1.5 wt%, or 0.3 wt% to 1 wt%. Within the content range of the molybdenum particles, the two-dimensional catalyst composite has a high conversion rate of both methane and carbon dioxide of 90% or more, and further has the advantage of reducing coke production, thereby extending the catalyst use time.

[0031] According to one embodiment of the present invention, the two-dimensional catalyst composite may further include nickel particles on the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML). Specifically, the nickel particles may be formed in a process of substituting nickel for boron positions (e.g., hydrothermal synthesis) during the formation of the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML), and these, together with the molybdenum particles, may serve as catalytic active sites in the dry reforming reaction of methane.

[0032] According to one embodiment of the present invention, the two-dimensional catalyst composite has a methane conversion rate and a carbon dioxide conversion rate of at least 90% and a coke production amount of 0.9 mg / g in a dry reforming reaction of methane in the temperature range of 700 to 900 ℃. cat *h may be less. Specifically, the two-dimensional catalyst composite has a methane conversion rate and carbon dioxide conversion rate of at least 95% and a coke production amount of 0.5 mg / g in a dry reforming reaction of methane at a temperature of 800°C. cat *may be less than h.

[0033] Another embodiment of the present invention provides a method for producing a two-dimensional catalyst composite for methane dry reforming. Specifically, another embodiment of the present invention provides a method for producing a two-dimensional catalyst composite for methane dry reforming, comprising the steps of: (A) preparing a layered MWW framework-type borosilicate (B-MWW); (B) replacing at least a portion of boron in the MWW framework structure with nickel and delaminating the layered MWW framework to form a two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML); and (C) supporting molybdenum particles on the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML).

[0034] According to one embodiment of the present invention, step (A) may be to use a previously manufactured layered MWW skeletal borosilicate (B-MWW), or to synthesize it. When synthesizing the layered MWW skeletal borosilicate (B-MWW), it may be synthesized using an organic structural derivative (SDA), and during the synthesis process, a three-dimensional layered MWW skeleton may be formed by removal and condensation of the organic structural derivative by calcination. However, the present invention is not limited thereto, and since it may be synthesized by a generally known method, a detailed description thereof is omitted herein.

[0035] According to one embodiment of the present invention, boron in the layered MWW skeleton type borosilicate (B-MWW) can be combined in the form of Si-OB within the MWW skeleton, and at this time, the molar ratio of Si / B can be 5.0 to 20.0, preferably 10 to 15. When the molar ratio of Si / B is less than 5, B is excessively included in the B-MWW (P), so that the Si content is relatively insufficient, making it difficult to form a three-dimensional layered MWW skeleton type borosilicate (B-MWW), and when it is greater than 20, the relative content of B to Si in the B-MWW decreases, so that the sites that can be substituted with nickel metal during the subsequent hydrothermal treatment decrease, which may cause a decrease in catalytic activity.

[0036] According to one embodiment of the present invention, the step (B) may substitute at least a portion of boron in the MWW skeletal structure with nickel through hydrothermal treatment, and simultaneously delaminate the layered MWW. Specifically, the step (B) may include performing a hydrothermal treatment by adding an acidic nickel precursor solution having a pH of 4.0 or lower. More specifically, according to one embodiment of the present invention, the step (B) may include performing a hydrothermal treatment at a temperature range of 100°C to 200°C by adding the layered MWW skeletal borosilicate (B-MWW) to the nickel precursor solution.

[0037] The above nickel precursor solution may contain an acid component, for example, nitric acid, and may have a pH of 4.0 or lower. By the nickel precursor solution having a pH of 4.0 or lower, boron may be removed from the B-MWW by the acidic nickel precursor solution during the hydrothermal treatment in step (B) and replaced with nickel, which is an active metal. In this process, the interlayer bonding of the MWW may be destroyed and exfoliated, and the three-dimensional B-MWW may be transformed into a two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML). The two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) may have an increased catalytic activity due to an increase in a large external surface area having active nickel, as the layered MWW structure is exfoliated to form a two-dimensional framework in which nickel bonds are exposed to the outside.

[0038] In addition, the amount of the nickel precursor solution added can be controlled depending on the hydrothermal treatment temperature, and the nickel precursor solution concentration can have a concentration of 0.1 M to 5.0 M. When the nickel precursor solution concentration is less than 0.1 M, the pH of the pretreatment aqueous solution increases, which may reduce the desorption of boron within the MWW skeletal structure and the exfoliation of the MWW layered structure, and may make it difficult to replace nickel metal. When it exceeds 5.0 M, the MWW skeletal structure may collapse due to excessively low pH.

[0039] The temperature range of the above thermal treatment may be 100°C to 200°C. If the temperature of the thermal treatment is less than 100°C, the layered MWW skeletal borosilicate (B-MWW) may not be properly exfoliated, and further, the degree of nickel substitution into the deboronation site may decrease, so that the formation of a two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) may not proceed smoothly, and while the defect sites within the molecular sieve may increase, the nickel content bonded to the skeleton may decrease, so that the catalytically active sites may decrease. On the other hand, if the temperature of the thermal treatment exceeds 200°C, the nickel clusters due to the agglomeration of the nickel precursor may increase rather than the nickel substituted within the exfoliated MWW skeletal structure due to the high temperature, making it difficult to obtain a uniform composition. Therefore, the thermal treatment may be performed at 100°C to 200°C, preferably 140°C to 160°C.

[0040] According to one embodiment of the present invention, step (B) may further include, after the hydrothermal treatment, steps of filtration, drying, and calcination thereof. Since this can be performed by generally known methods, it will not be described in detail herein. Through the calcination step, the occluded organic structural derivative present within the framework of the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) can be removed.

[0041] The molar ratio of Si / B of the above two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) may be 11 to 130, and the molar ratio of Si / Ni may be 1.5 to 30. The two-dimensional nickel silicate molecular sieve catalyst may include B in addition to Si and Ni in the framework, but when the boron is included in the Si / B ratio of less than 11, the active Ni may not sufficiently substitute for the boron of the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML), resulting in low catalytic activity.

[0042] On the other hand, when nickel in the framework of a two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) is included in a ratio of Si / Ni of less than 1.5, Ni in the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) is included in excess, and Ni exists in the form of agglomeration within the molecular sieve or on the surface in addition to the Si-O-Ni bonds within the molecular sieve, which may rather inhibit the catalytic activity, and when it exceeds 30, the content of Ni having activity within the molecular sieve may be insufficient, which may reduce the catalytic activity.

[0043] Therefore, the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) may have Si and Ni within its framework, with the molar ratio of Si / Ni being 1.5 to 30, preferably 4 to 25, and the molar ratio of Si / B being 11 or more.

[0044] According to one embodiment of the present invention, step (C) may be forming molybdenum particles on the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) using a molybdenum precursor solution. Specifically, step (C) may form molybdenum particles on the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) by impregnating the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) with the molybdenum precursor solution, drying the same, and then heat-treating the same.

[0045] According to one embodiment of the present invention, step (C) may include a step (C1) of mixing a molybdenum precursor solution and the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) and then drying the same; and a step (C2) of heat-treating the dried two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) at a temperature range of 400°C to 800°C.

[0046] According to one embodiment of the present invention, the concentration of the molybdenum precursor in the molybdenum precursor solution may be 0.1 M to 7 M. Within the above concentration range, the content range of molybdenum in the final two-dimensional catalyst composite for methane dry reforming reaction is optimized, thereby improving the catalytic activity of nickel as a cocatalyst in the methane dry reforming reaction.

[0047] According to one embodiment of the present invention, drying in step (C1) can be performed at a temperature ranging from 70°C to 150°C. Through the drying process, the molybdenum precursor in the molybdenum precursor solution can be maintained in a state of being adsorbed to the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML), and molybdenum particles can be formed through a subsequent heat treatment process.

[0048] According to one embodiment of the present invention, the heat treatment temperature in step (C2) may be performed in a temperature range of 400°C to 800°C, 400°C to 700°C, or 500°C to 600°C. There is an advantage in that molybdenum particles can be formed uniformly without agglomeration within the above temperature range.

[0049] Hereinafter, the present invention will be described in detail using examples. However, the examples according to the present invention may be modified in various ways, and the scope of the present invention is not limited to the examples described below. The examples in this specification are provided to more fully explain the present invention to those of ordinary skill in the art.

[0050] [Comparative Example 1]

[0051] Hexamethyleneimine and sodium hydroxide were dissolved in deionized water, and then boric acid was added at approximately 50°C. After the boric acid was completely decomposed, fumed silica was slowly added and the solution was homogenized. The homogenized final solution was transferred to a Teflon-lined stainless steel autoclave and heated at approximately 175°C for approximately 7 days while stirring at approximately 100 rpm. Thereafter, the white solid was recovered by filtration with distilled water, and this was dried at room temperature to produce a layered MWW framework borosilicate (B-MWW).

[0052] The layered MWW skeletal borosilicate (B-MWW) was added to about 1 M nickel (II) nitrate hexahydrate aqueous solution at a ratio of about 0.02 g / mL and mixed. The mixed solution was placed in a hydrothermal synthesis device (Teflon-lined stainless autoclaves, PARR Instrument Company) and heated at about 140°C for about 4 days with stirring. Thereafter, the mixture was washed and filtered with deionized water, dried at room temperature (RT), and calcined at about 550°C for about 8 hours to obtain a two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) catalyst. The molecular sieve catalyst of Comparative Example 1 was prepared in the same manner as Example 3 of Korean Patent No. 10-2408100.

[0053] [Example 1]

[0054] The two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) catalyst obtained as in Comparative Example 1 was added to an ammonium molybdate solution so that the molybdenum content was 0.3 wt%, stirred for about 2 hours, and dried in a dry oven at about 105°C for about a day. Then, the particles were uniformly sieved through a 200-mesh sieve and calcined at about 550°C for about 6 hours, thereby obtaining a two-dimensional catalyst composite for methane dry reforming reaction having Mo particles on a two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML).

[0055] [Example 2]

[0056] A two-dimensional catalyst composite for methane dry reforming reaction was obtained in the same manner as in Example 1, except that an ammonium molybdate solution was applied so that the molybdenum content was 0.5 wt%.

[0057] [Example 3]

[0058] A two-dimensional catalyst composite for methane dry reforming reaction was obtained in the same manner as in Example 1, except that an ammonium molybdate solution was applied so that the molybdenum content was 1 wt%.

[0059] [Example 4]

[0060] A two-dimensional catalyst composite for methane dry reforming reaction was obtained in the same manner as in Example 1, except that an ammonium molybdate solution was applied so that the molybdenum content was 3 wt%.

[0061] [Example 5]

[0062] A two-dimensional catalyst composite for methane dry reforming reaction was obtained in the same manner as in Example 1, except that an ammonium molybdate solution was applied so that the molybdenum content was 5 wt%.

[0063] [Example 6]

[0064] A two-dimensional catalyst composite for methane dry reforming reaction was obtained in the same manner as in Example 1, except that an ammonium molybdate solution was applied so that the molybdenum content was 7 wt%.

[0065] [Comparative Example 2]

[0066] A two-dimensional catalyst composite for methane dry reforming reaction was obtained in the same manner as in Example 1, except that a cerium nitrate hexahydrate solution was applied so that the cerium content was 1 wt%.

[0067] [Comparative Example 3]

[0068] A two-dimensional catalyst composite for methane dry reforming reaction was obtained in the same manner as in Example 1, except that an iron nitrate nonahydrate solution was applied so that the iron content was 1 wt%.

[0069] [Comparative Example 4]

[0070] A two-dimensional catalyst composite for methane dry reforming reaction was obtained in the same manner as in Example 1, except that a cobalt nitrate hexahydrate solution was applied so that the cobalt content was 1 wt%.

[0071] To evaluate the activity of the catalyst for methane dry reforming reaction manufactured according to the above examples and comparative examples, the catalyst was charged into a fixed-bed reactor and the reaction was performed under atmospheric pressure, and the product was analyzed by gas chromatography (GC, TCD). Prior to the reaction, the catalyst was activated through reduction treatment (10 sccm of H2, 90 sccm of N2) at 750°C, and purged with N2 (100 sccm) at the same temperature.

[0072] At this time, the reaction gas supply was a mixed gas of CO2 (47.5 sccm), CH4 (47.5 sccm), and N2 (5 sccm), and 0.2 g of catalyst was charged and the space velocity was 30,000 mL / g. cat *The catalytic activity of the methane dry reforming reaction was measured by adjusting the reaction rate to hr. N2 was used as an internal standard during product analysis, and the concentration change due to the increase in gas volume after the reaction was corrected. The CH4 conversion rate and CO2 conversion rate were calculated by the following equations.

[0073] - CH4Conversion (%) = (CH 4 in - CH 4 out ) / CH 4 in * 100

[0074] - CO2Conversion (%) = (CO 2 in - CO 2 out ) / CO 2 in * 100

[0075] In addition, the coke production amount was measured by performing a methane dry reforming reaction for 10 hours for each catalyst, recovering the used catalyst, and calculating it through TGA analysis. At this time, the TGA analysis conditions were to increase the temperature from room temperature to 900°C at 10°C / min, and since the peak appearing from 640 to 660°C is the peak where coke deposited on the catalyst is desorbed, the coke production amount was calculated through the weight decreased from the above temperature to 900°C.

[0076] The results of the property evaluation of the catalyst according to the above comparative examples and examples are as shown in Table 1 below.

[0077] Ni / B-DML(wt%)Mo(wt%)Ce(wt%)Fe(wt%)Co(wt%)Conversion rate(%)Coke production(mg / g) CAT*h)CH4CO2Comparative Example 11000---91.593.10.98Example 199.70.3---98.297.20.35Example 299.50.5---98.597.90.20Example 399.01---98.598.10.30Example 497.03---98.497.30.41Example 595.05---97.396.60.50Example 693.07---93.995.40.83Comparative Example 299.0-1--97.884.90.23Comparative Example 399.0--1-95.489.32.40Comparative Example 499.0---192.881.20.32

[0078] Figure 1 is a graph showing the methane / carbon dioxide conversion rate and coke production amount of the catalysts according to Comparative Example 1 and Examples 1 to 6. Furthermore, Figure 2 shows the methane and carbon dioxide conversion rate over time of the catalyst according to Comparative Example 1. And Figure 3 shows the methane and carbon dioxide conversion rate over time of the catalyst according to Example 2.

[0079] According to the above Table 1 and Figures 1 to 3, it was confirmed that the catalyst according to the example that additionally provided Mo particles, unlike Comparative Example 1, could secure an improved catalytic activity time due to a low coke production amount. Furthermore, it was confirmed that in the case of Comparative Examples 2 to 4 that additionally provided other metal particles other than Mo, the carbon dioxide conversion rate was low at less than 90%. Therefore, the catalyst according to the example secures both the methane and carbon dioxide conversion rates of 90% or more, and further, the coke production amount is 0.9 mg / g. CAT *Less than h, preferably 0.5 mg / g CAT *It has the advantage of being able to be implemented with less than h.

Claims

1. A two-dimensional catalyst composite for methane dry reforming, comprising: a two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML) in which at least a portion of boron in the exfoliated MWW framework structure is substituted with nickel; and molybdenum particles supported on the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML).

2. In claim 1, A two-dimensional catalyst composite for methane dry reforming reaction, wherein the content of molybdenum particles in the two-dimensional catalyst composite is 0.3 wt% to 7 wt%.

3. In claim 1, A two-dimensional catalyst composite for methane dry reforming reaction, wherein nickel particles are further provided on the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML).

4. In claim 1, In the dry reforming reaction of methane in the temperature range of 700 to 900 ℃, the methane conversion and carbon dioxide conversion are at least 90%, and the coke production amount is 0.9 mg / g. cat *A two-dimensional catalyst composite for methane dry reforming reaction having a melting point of less than h. 5.(A) Step of preparing a layered MWW skeletal borosilicate (B-MWW); (B) a step of replacing at least a portion of boron in the MWW skeleton structure with nickel and delaminating the layered MWW skeleton to form a two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML); and (C) a step of supporting molybdenum particles on the two-dimensional nickel / borosilicate molecular sieve (Ni / B-DML); Method for preparing a two-dimensional catalyst composite for methane dry reforming reaction.

6. In claim 5, A method for producing a two-dimensional catalyst composite for a methane dry reforming reaction, wherein the concentration of the molybdenum precursor in the above molybdenum precursor solution is 0.1 M to 7 M.

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