METHOD FOR PRODUCING TWO-DIMENSIONAL NICKEL SILICATE MOLECULAR SIEVE CATALYST FOR DRY REFORMING OF METHANE AND TWO-DIMENSIONAL NICKEL SILICATE MOLECULAR SIEVE CATALYST FOR DRY REFORMING OF METHANE PRODUCED BY SAME METHOD

Abstract

The present invention relates to a method for producing a two-dimensional nickel silicate molecular sieve catalyst for dry reforming of methane, wherein a catalyst containing a two-dimensional wide external surface area and nickel bonded to the surface area and having structural stability and activity is produced through hydrothermal treatment in one step.

Claims

1. A method of preparing a two-dimensional nickel silicate molecular sieve catalyst for dry reforming of methane (DRM), the method comprising: (a) synthesizing a layered borosilicate precursor having an MWW zeolite framework type; and (b) adding a nickel precursor to the B-MWW(P) and performing hydrothermal treatment.

2. The method of claim 1, wherein step (a) includes synthesizing a B-MWW(P) having an Si/B molar ratio of 5.0 to 20.0.

3. The method of claim 1, wherein a concentration of the nickel precursor in step (b) is 0.1 to 5.0 M.

4. The method of claim 1, wherein a hydrothermal treatment temperature in step (b) is to 200? C.

5. a two-dimensional nickel silicate molecular sieve catalyst for dry reforming of methane (DRM), prepared by the method of claim 1.

6. The two-dimensional nickel silicate molecular sieve catalyst of claim 5, wherein an Si/Ni molar ratio of the catalyst is 1.5 to 30.

7. The two-dimensional nickel silicate molecular sieve catalyst of claim 5, wherein the catalyst has a catalyst deactivation rate of less than 5% for methane and carbon dioxide in DRM at 700? C.

Description

DESCRIPTION OF DRAWINGS

[0025] FIG. 1 is a schematic diagram of a method of preparing a nickel silicate molecular sieve catalyst and dry reforming of methane (DRM) according to an example of the present invention.

[0026] FIG. 2 illustrates (A) nickel content measured using ICP elemental analysis, (B) N.sub.2 adsorption isotherms, and (C) BET surface area according to examples of the present invention.

[0027] FIG. 3 illustrates (A) CH.sub.4 conversion, (B) CO.sub.2 conversion, and (C) H.sub.2/CO ratios of Examples 1 to 4 and Comparative Examples 1 and 2 in DRM at 700? C., and (D) CH.sub.4 conversion, (E) CO.sub.2 conversion, and (F) H.sub.2/CO ratios of Examples 1 to 4 and Comparative Examples 1 and 2 in DRM at 750? ? C., and (G) a CH.sub.4 conversion, a CO.sub.2 conversion, and an H.sub.2/CO ratio and (H) Raman spectra of Example 3 for 10-day use, 12-hour use, and the fresh in DRM at 750? C., according an example of the present invention.

[0028] FIG. 4 illustrates (A) CH.sub.4 conversion, (B) CO.sub.2 conversion, and (C) H.sub.2/CO ratios of Examples 4 to 7 according to a hydrothermal treatment time in DRM at 750? C., and (D) CH.sub.4 conversion, (E) CO.sub.2 conversion, and (F) H.sub.2/CO ratios of Examples 4, 8, and 9 (Ni-DML-160-4-Z) according to a concentration of nickel precursor in DRM at 750? C., according to an example of the present invention.

MODES OF THE INVENTION

[0029] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as they are commonly understood by those skilled in the art. Generally, the nomenclature used herein is well known and commonly used in the art.

[0030] In this specification, when a part includes a certain component, it means that a part may further include other components rather than excluding other components, unless specifically stated to the contrary.

[0031] Hereinafter, the present invention will be described in detail.

[0032] In one aspect, the present invention provides a method of preparing a two-dimensional nickel silicate molecular sieve catalyst for dry reforming of methane (DRM), which includes: (a) synthesizing a layered borosilicate precursor having an MWW zeolite framework type [B-MWW(P)]; and (b) adding a nickel precursor to the B-MWW(P) and performing hydrothermal treatment.

[0033] FIG. 1 is a schematic diagram of a method of preparing a two-dimensional nickel silicate molecular sieve catalyst for dry reforming of methane (DRM) according to the present invention, and the present invention will be described in detail with reference to the schematic diagram.

[0034] In the present invention, step (a) is a step of (a) synthesizing a layered borosilicate precursor having an MWW zeolite framework type [B-MWW(P)].

[0035] The MWW is one of the zeolite framework topologies, which has a lamellar structure, and is a three-dimensional zeolite including two independent pore systems composed of a pore system of two-dimensional sinusoidal 10-membered ring (10-MR) channels with an elliptical ring cross-section of 4.1 ??5.1 ? and a pore system including a 12-MR supercage connected to 10-MR windows.

[0036] In step (a), a layered borosilicate precursor having an MWW zeolite framework type B-MWW(P), which having a structural specificity, is synthesized by including boron into a three-dimensional MWW zeolite framework type, wherein boron is bonded in the MWW framework in a form of SiOB, and an Si/B molar ratio may be 5.0 to 20.0, preferably 10 to 15. When the Si/B molar ratio is less than 5, Si content is relatively insufficient as an excess amount of B is included in the B-MWW(P), which may make it difficult to form a three-dimensional MWW zeolite framework type. When the Si/B molar ratio is greater than 20, a relative amount of B compared to Si is reduced in the B-MWW(P), and sites that can be substituted with nickel are reduced during hydrothermal treatment, which may cause a decrease in catalytic activity.

[0037] For example, in step (a), an organic structure-directing agent (SDA) may be used to synthesize a layered B-MWW(P), and a three-dimensional MWW zeolite may be formed through removal of the organic SDA by calcination and condensation during the synthesis process, but step (a) is not limited thereto and any commonly known method may be used for the synthesis, so a detailed description thereof is omitted herein.

[0038] In the present invention, step (b) is a step of performing hydrothermal treatment by adding an aqueous acidic nickel precursor solution of pH 4.0 or less to the B-MWW(P). Specifically, in step (b), an aqueous acidic nickel precursor solution is added to the synthesized B-MWW(P), and the mixture solution is hydrothermally treated at 100 to 200? ? C. Therefore, the B-MWW(P) is delaminated under one-step while boron is substituted with nickel to prepare a two-dimensional multilayered nickel silicate molecular sieve.

[0039] An amount of the aqueous nickel precursor solution may be adjusted according to a hydrothermal treatment temperature, and the aqueous nickel precursor solution may have a concentration of 0.1 to 5.0 M. When the concentration of the aqueous nickel precursor solution is less than 0.1 M, an increase in pH of the aqueous pretreatment solution causes a decrease in boron release and delamination of the MWW framework, and substitution of nickel becomes difficult. When the concentration of the aqueous nickel precursor solution exceeds 5.0 M, the MWW framework may collapse due to excessively low pH.

[0040] The aqueous nickel precursor solution includes an acid component, preferable nitric acid, and has a pH of 4.0 or lower. Under this condition, boron is removed from the B-MWW(P) and is substituted with nickel by the acidic nickel precursor solution during hydrothermal treatment in step (b), and during the process, the MWW zeolite is delaminated as interlayer bonds are broken, and the three-dimensional B-MWW may be transformed into a two-dimensional nickel silicate molecular sieve.

[0041] A temperature during the hydrothermal treatment is 100 to 200? C. When the temperature is lower than 100? C., the three-dimensional B-MWW(P) may not be sufficiently delaminated, and the substitution of nickel is reduced at sites where deboronation occurs, which may make it difficult to form a two-dimensional nickel silicate molecular sieve. In addition, while the number of defect sites in the molecular sieve is increased, an amount of nickel bonded to the framework is reduced, and therefore, the number of catalytically active sites may be reduced. On the other hand, when the temperature is higher than 200? ? C., an amount of nickel clusters formed by agglomeration of the nickel precursor increases rather than that of nickel bonded to the delaminated MWW zeolite due to the high temperature, and therefore, it may be difficult to obtain a uniform composition. Therefore, the hydrothermal treatment may be performed at 100 to 200? ? C., preferably at 140 to 160? C.

[0042] The hydrothermal treatment time is not limited as the hydrothermal treatment time may be adjusted according to a processing speed and reaction environment, and for example, may be 1 to 4 days.

[0043] After step (b), filtration, drying, and sintering may be further included. As these processes may be carried out according to commonly known methods in the art, a detailed description will be omitted herein, and through the calcination step, an occluded organic structure-directing agent in the framework may be removed from the two-dimensional nickel silicate molecular sieve.

[0044] According to the preparation method of the present invention, boron is substituted with nickel in the MWW framework, and an SiONi bond may be formed in the MWW framework, and therefore, controlling nickel bonding sites may become easy and an interaction with a zeolite may be improved. In particular, as the three-dimensional layered MWW zeolite is delaminated to form a two-dimensional framework with nickel being exposed to the outside, an external surface area, where the active nickel is bonded, is increased so that catalytic activity may be significantly increased.

[0045] Therefore, a two-dimensional nickel silicate molecular sieve catalyst for dry reforming of methane (DRM) prepared according to the preparation method exhibits improved reactivity in DRM, that is, improved CH.sub.4 and CO.sub.2 conversion, depending on framework properties and nickel content.

[0046] Specifically, a Si/B molar ratio of the two-dimensional nickel silicate molecular sieve catalyst may be 11 to 130, and an Si/Ni molar ratio thereof may be 1.5 to 30. The two-dimensional nickel silicate molecular sieve catalyst may include not only Si and Ni, but also B in the framework, but when a relative amount of B in the Si/B molar ratio is less than 11, active Ni is not sufficient to replace B in the two-dimensional nickel silicate molecular sieve, which may cause a decrease in catalytic activity.

[0047] On the other hand, when a relative amount of Ni in the Si/Ni molar ratio of the two-dimensional nickel silicate molecular sieve catalyst framework is less than 1.5, an excess amount of Ni is included in the molecular sieve catalyst, and not only an SiONi bond, but also a nickel cluster is formed in the molecular sieve or on a surface of the molecular sieve, which may cause a decrease in catalytic activity.

[0048] When a relative amount of Ni exceeds 30, active Ni content in the molecular sieve is insufficient, which may cause a decrease in catalytic activity.

[0049] Therefore, the two-dimensional nickel silicate molecular sieve catalyst has Si and Ni in the framework, and the Si/Ni molar ratio may be 1.5 to 30, preferably 4 to 25, and the Si/B molar ratio may be 11 or more.

[0050] A deactivation rate of the two-dimensional nickel silicate molecular sieve catalyst having such composition and framework characteristics for methane and carbon dioxide in DRM at 700? C. may be less than 5%.

[0051] Hereinafter, examples of the present invention will be described in detail.

[0052] However, the following examples are merely preferred examples of the present invention, and the present invention is not limited to the following examples.

Examples

1. Materials

[0053] Hexamethyleneimine (99%) and sodium hydroxide (99%) used in synthesis of a B-MWW precursor were purchased from Sigma-Aldrich (USA), and boric acid (99.5%) was purchased from Junsei Chemical (Japan), and fumed silica was purchased from Evonik (Japan). As a nickel precursor, nickel(II) nitrate hexahydrate (Ni(NO.sub.3).sub.2.Math.6H.sub.2O) (98%) was purchased from Samchun Chemicals (South Korea).

2. Preparation of Nickel Silicate Catalyst for Dry Reforming of Methane

[0054] (1) Preparation of Examples 1 to 9 [0055] Ni-delaminated MWW layer (Ni-DML)-X-Y-Z catalyst

a) Preparation of B-MWW Precursor [B-MWW(P)]

[0056] Hexamethyleneimine and sodium hydroxide were dissolved in deionized water, and then boric acid was added at 50? C. After the boric acid was completely decomposed, fumed silica was slowly added, and the solution was homogenized.

[0057] The homogenized final solution was poured into a Teflon-lined stainless steel autoclave and heated at 175? C. for 7 days while stirring at 100 rpm.

[0058] After heating, a white solid was recovered by filtration with distilled water and then dried at room temperature to prepare a B-MWW precursor [B-MWW(P)].

b) Preparation of Ni-Delaminated MWW Layers (Ni-DML)

[0059] The prepared B-MWW(P) was added to a 0.25 to 1 M aqueous nickel (II) nitrate hexahydrate solution at 0.02 g/mL and mixed. The mixed solution was poured into a hydrothermal synthesis device (Teflon-lined stainless autoclave commercially available from PARR Instrument Company) and heated to 100 to 160? C. for 1 to 4 days while stirring at 0 to 100 rpm.

[0060] After heating, the solution was washed with deionized water, filtered, and dried at room temperature and then calcined at 550? C. for 8 hours.

[0061] Accordingly, Ni-DML-X-Y-Z was prepared, where X, Y, and Z refer to a hydrothermal synthesis temperature, a hydrothermal treatment time, and a molar concentration of nickel nitrate, respectively, and Examples 1 to 9 were prepared according to the X, Y, and Z.

(2) Preparation of Comparative Example 1: Ni/?-Al.SUB.2.O.SUB.3

[0062] Using ?-Al.sub.2O.sub.3 as a support and nickel(II) nitrate hexahydrate as a precursor of an active metal, Ni/?-Al.sub.2O.sub.3 impregnated with 5 wt % nickel was prepared using incipient wetness impregnation. The synthesized Ni/?-Al.sub.2O.sub.3 was dried at 100? C. overnight and calcined at 550? C. for 3 hours.

(3) Preparation of Comparative Example 2: Ni/B-MWW

[0063] The same method used for preparing Ni/?-Al.sub.2O.sub.3 was applied, except that a B-MWW precursor was used as a support to prepare Ni/B-MWW.

(4) Control Group: B-MWW

[0064] The B-MWW precursor prepared in the example described above was used as a control group.

[0065] Table 1 below shows nickel silicate catalysts for dry reforming of methane, prepared by each of the above-described methods.

TABLE-US-00001 TABLE 1 Hydrothermal synthesis Impregnation Temperature Time Concentration Concentration Catalyst precursor (? C.) (days) (M) Support (wt %) Example 1 Ni-DML- B-MWW(P) 100 4 1 100-4-1 Example 2 Ni-DML- B-MWW(P) 120 4 1 120-4-1 Example 3 Ni-DML- B-MWW(P) 140 4 1 140-4-1 Example 4 Ni-DML- B-MWW(P) 160 4 1 160-4-1 Example 5 Ni-DML- B-MWW(P) 160 1 1 160-1-1 Example 6 Ni-DML- B-MWW(P) 160 2 1 160-2-1 Example 7 Ni-DML- B-MWW(P) 160 3 1 160-3-1 Example 8 Ni-DML- B-MWW(P) 160 4 0.25 160-4-0.25 Example 9 Ni-DML- B-MWW(P) 160 4 0.5 160-4-0.5 Comparative Ni/?-Al.sub.2O.sub.3 ?-Al.sub.2O.sub.3 5 Example 1 Comparative Ni/B- B-MWW 5 Example 2 MWW

3. Analysis of Catalyst Properties

(1) ICP Analysis

[0066] FIG. 2A is a graph of nickel content measured by analyzing the composition of Examples 1 to 4 (Ni-DML-X-4-1) using ICP elemental analysis, and based on the elemental analysis, Table 2 below shows calculated values of the framework compositions of Examples 1 to 4 assuming 72 T-atoms in an MWW unit cell. The framework composition is based on a molar ratio. The symbol indicates a defect site.

TABLE-US-00002 TABLE 2 Framework Ni.sub.Cluster/ Catalyst composition.sup.b Si/B Si/Ni.sub.Total Si/Ni.sub.Framework Ni.sub.Framework Control Group B-MWW B.sub.6.8Si.sub.65.2O.sub.144 9.5 Example 1 Ni-DML- Ni.sub.2.7B.sub.3.4?.sub.0.7Si.sub.65.2O.sub.144 19.0 24.0 24.0 0 100-4-1 Example 2 Ni-DML- Ni.sub.3.7B.sub.3.1?.sub.1.6Si.sub.65.2O.sub.144 20.7 10.6 17.7 0.7 120-4-1 Example 3 Ni-DML- Ni.sub.4.2B.sub.2.6Si.sub.65.2O.sub.144 24.5 7.0 15.6 1.2 140-4-1 Example 4 Ni-DML- Ni.sub.6.3B.sub.0.5Si.sub.65.2O.sub.144 117.0 4.0 10.4 1.6 160-4-1

[0067] In FIG. 2A and Table 2, the Ni content of Examples 1 to 4 (Ni-DML-X-4-1) was increased in proportion to an increase in hydrothermal synthesis temperature during catalyst preparation.

[0068] During preparation of Examples 1 to 4 (Ni-DML-X-4-1), when interlayer delamination and a nickel substitution mechanism were carried out in one-step, at a relatively low temperature of 100? C. or 120? C., some nickel atoms took up the framework space, where boron atoms were removed, but some of the framework space, where boron atoms were removed, remained as defect sites. On the other hand, at a relatively high temperature of 140? C. or 160? C., one or more nickel atoms may be present in an additional framework per substituted nickel atom in the framework.

[0069] Accordingly, the catalyst of Example 4 (Ni-DML-160-4-1) included the largest number of nickel atoms in the framework, whose Si/Ni.sub.Framework ratio was 10.4.

(2) Analysis of N.SUB.2 .Adsorption Isotherm

[0070] FIG. 2B illustrates a graph of N.sub.2 adsorption isotherms according to a hydrothermal treatment temperature when the catalysts of Examples 1 to 4 (Ni-DML-X-4-1) were prepared, and as the hydrothermal treatment temperature increases, properties changed from a Type I microporous structure to a Type IV mesoporous structure. The results show that a three-dimensional B-MWW precursor was successfully transformed into a two-dimensional layered structure.

[0071] In addition, the hysteresis in the adsorption-desorption isotherm of Example 4 (Ni-DML-160-4-1) shown in FIG. 2B is a typical characteristic of a parallel plate-like pore, indicating a characteristic of a delaminated substance.

(3) BET Analysis

[0072] FIG. 2C illustrates results of BET analysis of the catalysts of Examples 1 to 4 (Ni-DML-X-4-1), and it can be seen that an external surface area of Ni-DML was increased as the delamination of the B-MWW(P) was performed at a higher hydrothermal temperature.

4. Analysis of Catalyst for Dry Reforming of Methane (DRM)

[0073] An experiment was performed on a catalyst for dry reforming of methane (DRM) using a continuous flow device with a fixed-bed microreactor under atmospheric pressure, and the product was analyzed using a gas chromatograph (GC) equipped with a thermal conductivity detector (TCD). Before the experiment, the catalyst was activated under a flow of pure H.sub.2 (50 mL/min) at 700? C. for 3 hours and purged with N.sub.2 (60 mL/min) for 0.5 hours at the same temperature. (However, if necessary, the reaction proceeded without H.sub.2 pretreatment.)

[0074] DRM catalytic activity was measured by supplying a feed gas stream composed of 40 vol % CH.sub.4 and 40 vol % CO.sub.2 (balanced with N.sub.2) at a gas hourly space velocity (GHSV) of 30,000 mL/gcath (supplying a feed gas stream composed of CH.sub.4, CO.sub.2, and N.sub.2 at a rate of 20, 20, and 10 mL/min, respectively) to a reactor containing 0.1 g of the catalyst activated by the above process. An inert gas, N.sub.2, was used as an internal standard for GC-TCD analysis, and concentration changes due to an increase in gas volume after DRM were conducted.

[0075] In addition, a CH.sub.4 conversion, CO.sub.2 conversion, and H.sub.2/CO ratio were calculated using the following equations.

[00001]${\mathrm{CH}}_4\mathrm{conversion}\left(\%\right)=\left\{\left({\mathrm{CH}}_4\right)\mathrm{in}-\left({\mathrm{CH}}_4\right)\mathrm{out}\right\}/\left({\mathrm{CH}}_4\right)\mathrm{in}?100$${\mathrm{CO}}_2\mathrm{conversion}\left(\%\right)=\left\{\left({\mathrm{CO}}_2\right)\mathrm{in}-\left({\mathrm{CO}}_2\right)\mathrm{out}\right\}/\left({\mathrm{CO}}_2\right)\mathrm{in}?100$$H_2/\mathrm{CO}\mathrm{ratio}=[\left(H_2\right)\mathrm{out}/2\left({\mathrm{CH}}_4\right)\mathrm{in}]/\left[\left(\mathrm{CO}\right)\mathrm{out}/\left\{\left({\mathrm{CH}}_4\right)\mathrm{in}+\left({\mathrm{CO}}_2\right)\mathrm{in}\right\}\right]$$\mathrm{Deactivation}\mathrm{rate}=\left(10\mathrm{days}\mathrm{conversion}-12h\mathrm{conversion}\right)/10\mathrm{days}\mathrm{conversion}?100$

(1) Catalytic Activity According to Reaction Temperature

[0076] FIG. 3 illustrates the catalytic activity of Examples 1 to 4 (Ni-DML-X-4-1) and Comparative Example 1 (Ni/?-Al.sub.2O.sub.3) and Comparative Example 2 (Ni/B-MWW) according to a measured DRM temperature and a usage time, and the results are summarized in Table 3 below.

[0077] FIGS. 3A to C illustrate the CH.sub.4 conversion, CO.sub.2 conversion, and H.sub.2/CO ratios of Examples 1 to 4 (Ni-DML-X-4-1) and Comparative Example 1 (Ni/y-Al.sub.2O.sub.3) and Comparative Example 2 (Ni/B-MWW) measured in DRM at 700? C., and through FIGS. 3A and B and Table 3, it can be seen that Examples 1 to 4 (Ni-DML-X-4-1), which have similar amounts of nickel compared to Comparative Example 1 (Ni/?-Al.sub.2O.sub.3) and Comparative Example 2 (Ni/B-MWW) showed higher and more stable CH.sub.4 and CO.sub.2 conversion at 700? ? C. This is because catalyst deactivation due to coke deposition proceeded is much faster in Comparative Examples 1 and 2 compared to Examples 1 to 4.

[0078] In general, in DRM, coke is formed much faster at a low temperature due to an increase in Boudouard reaction (2CO++>C+CO.sub.2).

[0079] The deactivation rate of CO.sub.2 conversion of Examples 1 to 4 (Ni-DML-X-4-1) for 12 hours was 0 to 1% while the deactivation rate of CO.sub.2 conversion of Comparative Example 1 (Ni/?-Al.sub.2O.sub.3) and Comparative Example 2 (Ni/B-MWW) was 10% and 45%, respectively. This is because, in Examples 1 to 4 (Ni-DML-X-4-1), high activity and excellent stability may be maintained due to highly dispersed nickel sites on an external surface area.

[0080] In Examples 1 to 4, as a hydrothermal treatment temperature increased, the number of active nickel sites increased, and therefore, CH.sub.4 and CO.sub.2 conversion was increased.

[0081] In FIG. 3C, the H.sub.2/CO ratio of Example 1 (Ni-DML100-4-1) to Example 3 (Ni-DML-140-4-1) was about 0.89, which is close to a thermodynamic equilibrium value at the experimental temperature. On the other hand, the CH.sub.4 conversion and H.sub.2/CO ratio of Example 4 (Ni-DML-160-4-1) were higher than the thermodynamic equilibrium value. This is because H.sub.2 and molecular carbon were generated by catalytic methane cracking under high temperature DRM conditions.

[0082] FIGS. 3D to F illustrate the CH.sub.4 conversion, CO.sub.2 conversion, and H.sub.2/CO ratios of Examples 1 to 4 (Ni-DML-X-4-1) and Comparative Example 1 (Ni/y-Al.sub.2O.sub.3) and Comparative Example 2 (Ni/B-MWW) measured in DRM at 750? C., and the catalytic activity of Examples 1 to 4 was 8 to 18% higher than that of Examples 1 to measured at 700? C.

[0083] In FIGS. 3A to F, the H.sub.2/CO ratios of Comparative Example 1 (Ni/?-Al.sub.2O.sub.3) and Comparative Example 2 (Ni/B-MWW) were lower than those of Examples 1 to 4 (Ni-DML-X-4-1), which may be explained by an effect of a reverse water gas shift (RWGS) in DRM. In other words, the RWGS reaction is a reaction in which CO.sub.2 and hydrogen react to produce CO and water, and a lower H.sub.2/CO ratio indicates that the RWGS reaction occurs actively, which may be further supported by a relatively high CO.sub.2 conversion caused by RWGS reaction compared to the CH.sub.4 conversion.

[0084] FIGS. 3G and H illustrate the CH.sub.4 and CO.sub.2 conversion and Raman spectra of Example 3 (Ni-DML-140-4-1) for 10-day use (marked with*in Table 3), 12-hour use, and (unused) fresh use in DRM at 750? C. It can be seen that the deactivation of the catalyst of Example 3 was not detected because Example 3 maintained remarkable catalytic stability and activity for 10 days, rather, the CH.sub.4 and CO.sub.2 conversion increased by 1% or 2% (FIG. 3G) during time on stream (TOS). This is because endothermic side reactions such as methane cracking or the RWGS reaction occur at a high temperature, and an effect of the methane cracking became more pronounced at high temperatures, and as a result, the H.sub.2/CO ratio gradually increased over time.

[0085] The Raman spectra of FIG. 3H showed that, compared to the unused (fresh use) catalyst, when the catalyst of Example 3 was used for 12 hours and 10 days in DRM, signals corresponding to disordered crystalline graphite and ordered crystalline graphite were detected, and it can be seen that coke was formed.

TABLE-US-00003 TABLE 3 Reaction CH.sub.4 conv. (%) CO.sub.2 conv. (%) H.sub.2/CO Deactivation Temperature 10 12 10 12 10 12 Rate (%) Coke Catalyst (? C.) day h day h day h CH.sub.4 CO.sub.2 (wt %) Example 1 Ni-DML-100- 700 65 64 77 76 0.87 0.86 2 1 3 4-1 Example 2 Ni-DML-120- 68 66 79 78 0.88 0.87 3 1 2 4-1 Example 3 Ni-DML-140- 70 69 80 80 0.88 0.88 1 0 1 4-1 Example 4 Ni-DML-160- 77 78 80 80 0.93 0.93 0 2 4-1 Comparative Ni/?-Al.sub.2O.sub.3 65 57 69 62 0.82 0.80 12 10 3 Example 1 Comparative Ni/B-MWW 35 15 51 28 0.63 0.45 57 45 Example 2 Example 1 Ni-DML-100- 750 83 81 90 88 0.93 0.92 2 2 2 4-1 Example 2 Ni-DML-120- 81 80 90 90 0.91 0.91 1 0 1 4-1 Example 3 Ni-DML-140- 83 83 89 90 0.92 0.92 0 2 4-1 Example 3* Ni-DML-140- 83 84 89 91 0.80 0.84 6 4-1 (10 days) Example 4 Ni-DML-160- 87 87 92 93 0.94 0.94 0 2 4-1 Comparative Ni/?-Al.sub.2O.sub.3 81 80 84 82 0.92 0.91 1 2 2 Example 1 Comparative Ni/B-MWW 9 43 36 57 0.43 0.66 Example 2

(2) Catalytic Activity According to Hydrothermal Treatment Time and Nickel Precursor Concentration

[0086] FIG. 4 and Table 4 below illustrate catalytic activity according to a hydrothermal treatment time and nickel precursor concentration.

[0087] FIG. 4A to C illustrate the CH.sub.4 conversion, CO.sub.2 conversion, and H.sub.2/CO ratios according to the hydrothermal treatment time of Examples 4 to 7 (Ni-DML-160-Y-1) measured in DRM at 750? C., respectively. It was found that the difference in catalytic activity according to hydrothermal treatment time was not significant.

[0088] Meanwhile, FIGS. 4D to F illustrate the CH.sub.4 conversion, CO.sub.2 conversion, and H.sub.2/CO ratios according to the nickel precursor concentration of Examples 4, 8 and 9 (Ni-DML-160-4-Z) measured in DRM at 750? C. respectively, and it was found that catalytic activity was relatively low when the concentration of nickel precursor was low (0.25 to 0.5 M).

TABLE-US-00004 TABLE 4 Reaction CH.sub.4 conv. (%) CO.sub.2 conv. (%) H.sub.2/CO Deactivation Temperature 10 12 10 12 10 12 Rate (%) Coke Catalyst (? C.) day h day h day h CH.sub.4 CO.sub.2 (wt %) Example 4 Ni-DML- 750 87 87 92 93 0.94 0.94 0 2 160-4-1 Example 5 Ni-DML- 84 83 90 90 0.95 0.95 1 0 2 160-1-1 Example 6 Ni-DML- 84 84 91 91 0.94 0.94 0 0 2 160-2-1 Example 7 Ni-DML- 84 85 91 91 0.93 0.94 0 2 160-3-1 Example 8 Ni-DML- 87 88 91 89 0.86 0.86 2 6 160-4- 0.25 Example 9 Ni-DML- 87 84 86 86 0.86 0.85 3 0 4 160-4-0.5