KR100353412B1 - Process for Preparing Metal Containing Bi-functional Catalyst for Dewaxing - Google Patents

Abstract

The present invention relates to a method for producing a metal-containing binary catalyst for dewaxing process. In the present invention, an aqueous alkali metal silicate solution obtained by reacting silica with an aqueous alkali metal solution is added dropwise to the template material and hydrothermally synthesized to obtain an MCM-41 carrier, an Al precursor is added and stirred to obtain an Al-MCM-41. Provided are a method of preparing a metal-containing binary catalyst by supporting and firing a metal, and a metal-containing binary catalyst prepared therefrom. The metal-containing binary catalyst of the present invention promotes the isomerization reaction rather than the cracking reaction in the conversion process of n-hexadecane. Therefore, the binary catalyst of the present invention can be widely used as a catalyst for dewaxing processes such as lubricating base oil and diesel oil.

Description

Process for Preparing Metal Containing Bi-functional Catalyst for Dewaxing

The present invention relates to a method for producing a metal-containing binary catalyst for dewaxing process and to a metal-containing binary catalyst prepared therefrom. More specifically, an aqueous alkali metal silicate solution obtained by reacting silica with an aqueous alkali metal solution is added dropwise to the template material and hydrothermally synthesized to obtain an MCM-41 carrier, and an Al-precursor is added and stirred to obtain an Al-MCM-41. Then, the present invention relates to a method for preparing a metal-containing binary catalyst by supporting and firing a metal and a metal-containing binary catalyst prepared therefrom.

Generally, wax refers to a straight chain hydrocarbon having 30 to 40 carbon atoms. When wax is contained in lubricating base oil or diesel oil, since the low-temperature performance is reduced, it removes through a dewaxing process in a manufacturing process. At this time, the wax removal process for removing the wax can be classified into two types, a solvent dewaxing process using a solvent and a contact dewaxing process using a catalyst. Of these, the solvent dewaxing process is a widely used conventional process to remove and remove the wax by using a solvent such as methyl ethyl ketone (MEK), liquid propane and the like. However, this process has disadvantages in terms of time and cost. Recently, a catalytic dewaxing process using a catalyst has been developed, and there are advantages in that it does not incur environmental costs such as waste solvent treatment problems. It's going on.

The contact dewaxing process was first applied to oils such as kerosene and diesel oil by Mobil in the late 1970s, and was named as a MDB (Mobil middle distillate dewaxing) process. The MLDW (Mobil lube dewaxing) process applied to the lubricating oil was developed in the early 1980s. The catalyst used was a synthetic zeolite-based ZSM-5, which was removed by cracking the wax component with a lower hydrocarbon by a strong acid point. In addition, in 1992, in order to improve the yield and viscosity index of lubricating oil, Chevron developed SAPO-11 catalyst in which elemental phosphorus (P) was added to the zeolite catalyst. However, the above catalysts are catalysts for cracking waxes with lower hydrocarbons, and in the actual wax removal process, isomerization of the wax is preferable to cracking, and thus the performance improvement of the lubricating oil has been limited.

Accordingly, studies on catalysts that promote isomerization rather than cracking in the wax removal process have been continued. Beck et al. Developed an MCM-41 carrier having mesopores, Al-MCM-41 was prepared by adding aluminum to the carrier mother liquor and hydrothermally synthesized (see US Pat. No. 5,057,296). However, this method has difficulty in commercialization due to the low hydrothermal stability of Al-MCM-41. . In addition, Ryoo Ryong et al. Obtained a high hydrothermal stability MCM-41 by adjusting the pH of the solution in the hydrothermal synthesis process (see US Patent No. 5,942,208), and Al-MCM was introduced into the carrier. -41 was prepared and this method was named post-synthetic metal implantation (Chem. Commun., 1997, 2225). In addition, D. Rossi et al. Developed a metal / Al-MCM-41 binary catalyst prepared by adding a metal to Al-MCM-41 prepared by adding Al to a mother liquor when preparing a carrier (see US Patent 5,256,277). However, the above technique has been applied only to the isomerization of the lower fraction of C ₄ -C ₈ , and there is a limit to the isomerization of the carbonaceous wax.

Therefore, there is a constant need to overcome the disadvantages of the foregoing prior arts and to develop a method capable of producing a catalyst capable of effectively isomerizing hydrocarbons having more carbon atoms such as wax.

Accordingly, the present inventors earnestly endeavored to develop a method for producing a catalyst having excellent isomerization performance, and as a result, a high hydrothermal stability MCM-41 carrier was obtained during the preparation process of the metal / Al-MCM-41 catalyst. When Al and metal were supported by the post-treatment method, it was confirmed that a binary catalyst having a high conversion rate of wax was produced, and thus, the present invention was completed.

After all, the main object of the present invention is to provide a method for producing a metal-containing binary catalyst for dewaxing process.

Another object of the present invention is to provide a binary catalyst prepared from the electric method.

1 is a graph showing the conversion rate of n-hexadecane over time of Pt / Al-MCM-41 catalyst having a different Si / Al ratio.

2 is a graph showing the conversion rate (cracking + isomerization) of n-hexadecane over time for the Pt / Al-MCM-41 catalyst prepared in the present invention and other catalysts.

Figure 3 is a graph showing the ratio of isomerization according to the conversion rate for the Pt / Al-MCM-41 catalyst and the other catalysts prepared in the present invention.

The method for producing a metal-containing binary catalyst of the present invention comprises the steps of reacting silica with an aqueous alkali metal solution to obtain an alkali metal silicate aqueous solution; Adding an aqueous alkali metal silicate solution previously obtained to the template material and hydrothermally synthesizing to obtain an MCM-41 carrier; Adding an Al precursor dissolved in an organic solvent to the carrier thus obtained, followed by stirring and firing the resulting precipitate to obtain Al-MCM-41; And a step of impregnating the obtained Al-MCM-41 in the precursor solution of the Group VIII metal on the chemical periodic table to support the metal, and then firing the metal.

Hereinafter, the method for preparing a metal-containing binary catalyst of the present invention will be described in more detail by dividing the process.

First Step : Obtaining Alkali Metal Silicates

The silica is reacted with an aqueous alkali metal solution to obtain an aqueous alkali metal silicate solution, wherein silica is one or more materials selected from fumed silica, aerosil, tetraorthosilicate and the like. Preferably, silica or the like manufactured by DuPont may be used under the trade names Ludox HS-40 or Ludox AS-30. In addition, an alkali metal means an element belonging to group IA in the chemical periodic table, preferably a lithium (Li), sodium (Na) or potassium (K) element, more preferably sodium.

Second Step : Obtaining an MCM-41 Carrier

An aqueous solution of the alkali metal silicate thus obtained was added dropwise to the template material and hydrothermally synthesized to obtain an MCM-41 carrier. At this time, the template material formed a uniform pore form by helping to form a chemically stable intermediate (micelle) in the synthesis of the carrier. Means a chemical that causes Template materials include octadecyltrimethylammonium bromide (C ₁₈ TMABR), cetyltrimethylammonium chloride (C ₁₆ TMACL), myristyltrimethylammonium chloride (C ₁₄ TMACL), dodecyltrimethylammonium bromide (dodecyltrimethylammonium bromide: C ₁₂ TMABR), decyltrimethylammonium bromide (C ₁₀ TMABR), octyltrimethylammonium bromide (C ₈ TMABR), hexyltrimethylammonium bromide (hexyltrimethylammonium compound, such as TMABR: ₆ bromide) Or mixtures thereof. In addition, hydrothermal synthesis is used to accelerate the growth of crystals by applying heat to a mixture containing water. The hydrothermal synthesis is performed by placing the mixture in a sealed container and raising the temperature to react under pressure generated. At this time, MCM-41 has a disadvantage in that the structure is broken when the temperature is high in the moisture condition, as a means to solve the addition of conventional acids such as hydrochloric acid (HCl), acetic acid (acetic acd) or diluent thereof It is preferable to maintain the pH of the reaction solution to 9 to 11, this operation may be carried out repeatedly.

After the above hydrothermal synthesis is completed, the precipitate is filtered, washed and dried in a conventional manner to obtain an MCM-41 carrier. At this time, the pore size of the carrier can be adjusted by varying the mold material, the pore size of the carrier obtained is preferred that the average diameter is 1.5 to 20nm. If the average diameter does not reach 1.5nm, it is difficult for the surfactant to form colloidal particles in a liquid mixture, and thus the pore structure is difficult to develop and grow. If the average diameter exceeds 20nm, the pores of MCM-41 are difficult to synthesize. However, it is not preferable because of the problem that the lattice stability is poor and the structure easily collapses.

Third Step : Obtaining Al-MCM-41

Al-MCM-41 was obtained by adding Al precursor dissolved in an organic solvent to the previously obtained MCM-41 carrier and stirring to calcinate the resulting precipitate: wherein the organic solvent was ethanol, methanol, propanol, acetone or a mixture thereof. Solutions may be used, but it is preferable to use ethanol having a relatively low toxicity and high solubility in metal precursors. In addition, AlCl ₃ , Al (OH) ₃ , Al (OCH ₃ ) ₃ or a mixture thereof is used as the Al precursor, and in particular, AlCl ₃ is preferable because of its excellent reactivity. The addition amount of the Al precursor is preferably added so that the molar ratio of Si / Al of Al-MCM-41 to be finally prepared is 1 to 200, and when the molar ratio of Si / Al does not reach 1, that is, the amount of aluminum introduced When there is a large amount of Al is not introduced into the lattice of MCM-41, but the oxide state of alumina, there is a problem that the structure does not increase the reaction activity and breakage occurs, the acid point introduced when the molar ratio of Si / Al exceeds 200 Since the amount of is small and the reaction activity is low, it is not preferable for the purpose of the present invention. In addition, the resulting precipitate is filtered, washed and dried in a conventional manner, and then calcined at 350 to 600 ° C. for 2 to 24 hours. If the temperature of calcination does not reach 350 ° C, Al may not be enough to enter the lattice, and if it exceeds 600 ° C, the lattice of MCM-41 may collapse at a higher temperature than necessary. If the firing time does not reach 2 hours, Al is not sufficient time for the introduction of Al into the lattice, and if it exceeds 48 hours, the structure may be collapsed for a longer time than necessary, which is undesirable. .

Fourth Step : Preparation of Metal / Al-MCM-41 Binary Catalyst

The Al-MCM-41 obtained above is impregnated with a precursor solution of Group VIII metal on the chemical periodic table to be supported on a metal, and then calcined to prepare a metal / Al-MCM-41 binary catalyst: by Group VIII metal hydrogen. It is reduced and serves to cause hydrogenation and dehydrogenation reaction in the metal state, and it is preferable because platinum (Pt), palladium (Pd) or nickel (Ni) has less side reactions to break the carbon-carbon bond. On the other hand, elements such as platinum (Pt), palladium (Pd) or nickel (Ni) cannot be supported in a solid phase and should be added to Al-MCM-41 in the form of a precursor. As a precursor of these metals, Pt (NH _{3 ) 5 · Cl · H 2 0} , Pt (NH 3) 4 · Cl 2 · H 2 0, Pt (NH 3) 3 · Cl 3 · H 2 0 ,, Pt (NH 3) 2 · Cl 4 · H 2 _{0, Pt (NH 3) ·} Cl 5 · H 2 0, PtCl 6, PtCl 4, PtCl 2, PtS 2, PtSO 4, Pd (NH 3) 5 · Cl · H 2 0, Pd (NH 3) 4 · _{Cl 2 · H 2 0, Pd} (NH 3) 3 · Cl 3 · H 2 0 ,, Pd (NH 3) 2 · Cl 4 · H 2 0, Pd (NH 3) · Cl 5 · H 2 0, PdCl _{6, PdCl 4, PdCl 2,} PdS 2, PdSO 4, Ni (NH 3) 5 · Cl · H 2 0, Ni (NH 3) 4 · Cl 2 · H 2 0, Ni (NH 3) 3 · Cl 3 _{· H 2 0 ,, Ni (NH} 3) 2 · Cl 4 · H 2 0, Ni (NH 3) · Cl 5 · H 2 0, NiCl 6, NiCl 4, NiCl 2, NiS 2 , and the group consisting of NiSO ₄ One or more materials selected from are used. The supported amount of metal is such that the metal / (metal + Al-MCM-41) ratio is 0.0001 to 0.15 by weight. When the metal / (metal + Al-MCM-41) ratio does not reach 0.0001, there is a problem in that a cracking reaction occurs mainly due to a low hydrogenation-dehydrogenation ability due to a small metal point formed, and in case of exceeding 0.15, the degree of dispersion of the metal Even if a large amount of metal is dropped, the amount of metal points exposed on the surface does not increase, which is undesirable. And Al-MCM-41 impregnated in the precursor solution of the metal is filtered and dried by a conventional method known in the art, and calcined under the same conditions as in the third process.

The step (four steps) of adding the precursor of the Group VIII metal on the chemical periodic table described above to support the metal may be changed within a range not departing from the essence of the present invention. After addition to the template, dropping of the Group VIII metal precursor solution is carried out (pretreatment synthesis of metals).

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention. .

Example 1 Preparation of Pt / Al-MCM-41 Catalyst Introduced by Metal by Post Treatment Synthesis

First, 14.3 g of colloidal silica Ludox HS-40 (Ludox HS-40, DuPont, USA) was mixed with 51.5 ml of 1 M NaOH aqueous solution, and then heated at 80 ° C. for 2 hours to obtain an aqueous sodium silicate solution. Next, the aqueous sodium silicate solution was added dropwise dropwise to 25% by weight aqueous solution of cetyltrimethylammonium chloride with a dropper for 1 hour, and then the mixture was placed in an oven at 100 ° C. for 2 days under hydrothermal synthesis to form silica-based MCM- 41 carriers were crystallized. Subsequently, after cooling to room temperature, the pH was adjusted to 10 with 1M aqueous HCl solution, followed by repeated hydrothermal synthesis, and then the precipitate was filtered, washed several times with tertiary distilled water at 80 ° C, and dried at 110 ° C to obtain an MCM-41 carrier. It was. The carrier thus obtained was kept at 140 ° C. for 10 hours and sufficiently dried. Then, 5 g of the carrier was added to 300 ml of anhydrous ethanol solution in which AlCl ₃ was dissolved, stirred well for 1 hour, filtered, washed with ethanol and dried at 110 ° C. The mixture was calcined at 550 ° C. for 10 hours to obtain Al-MCM-41 having a Si / Al ratio of 5, 20, 40 and 80, respectively. At this time, the ratio of Al / Si was adjusted by a method of varying the amount of AlCl ₃ dissolved in anhydrous ethanol. Finally, the _{Pt (NH 3) 4 · Cl} 2 · H 2 0 ( tetraamine platinum (Ⅱ) chloride hydrate (tetraamineplatinum (Ⅱ) chloride hydrate, 98% electrical to yield the Al-MCM-41 of platinum of the liquid precursor) Impregnated), and the platinum is supported so that the ratio of metal / (metal + Al-MCM-41) is 0.005 by weight, and then calcined at 350 ° C. for 10 hours to prepare a metal / Al-MCM-41 binary catalyst. It was.

As a result of measuring the BET surface area by the nitrogen adsorption method for the catalysts prepared above, all of them had a high surface area of more than 1100m ³ / g, the distance between the lattice (d-spacing) and pore size by X-ray diffraction analysis As a result, it was confirmed that it was 3.8 nm and 2.8 nm, respectively. In addition, in order to determine the acid characteristics of the catalyst, the ammonia elevated temperature desorption method was carried out to obtain a peak at about 260 ℃, which means a weak acid point. The chemical adsorption of carbon monoxide and the transmission electron microscope were used to confirm the state of the supported platinum. The dispersion of platinum was about 58% and the average size of platinum was measured at 3.3 nm.

Next, with respect to the catalyst prepared above, n-hexadecane having 16 carbon atoms was used as a model reactant of the wax to investigate the activity of the dewaxing reaction. First, 0.5 g of each catalyst was added to a 300 ml high-pressure reactor to reduce the metal to hydrogen at 320 ° C., 50 ml of linear hexadecane was injected under a hydrogen atmosphere, and the temperature of the reactor was increased to 350 ° C. and the pressure was 103 bar. Samples were taken over time while the n-hexadecane was subjected to the isomerization reaction, and analyzed by gas chromatography (gas chromatography of HP 6890, manufactured by Hewlett-Packard Co., Ltd. using a 50m HP-1 column) (see FIG. 1).

1 is a graph showing the conversion rate of n-hexadecane over time of Pt / Al-MCM-41 catalyst having a different Si / Al ratio. In Fig. 1, the conversion rate of n-hexadecane in the isomerization reaction of n-hexadecane is decreased as the ratio of Si / Al in the Pt / Al-MCM-41 catalyst system decreases, that is, the amount of Al added. This increase was confirmed.

Example 2 Preparation of Pt / Al-MCM-41 Catalyst Introduced by Metal by Pretreatment Synthesis

An aqueous sodium silicate solution was obtained in the same manner as in Example 1, and dropwise was added dropwise with dropper to an aqueous solution of cetyltrimethylammonium chloride (25% by weight), followed by Pt (NH ₃ ) ₄ .Cl as a platinum precursor. _2. H ₂ O was added dropwise by dropper so that the ratio of metal / (metal + Al-MCM-41) was 0.005 in weight ratio. Next, the process of adjusting the pH was prepared in the same process as in Example 1 (except step 4) metal / Al-MCM-41 binary catalyst.

About the catalyst prepared above, the conversion rate of n-hexadecane was evaluated by the same method as Example 1, and compared with the Pt / Al-MCM-41 (Si / Al = 5) catalyst of Example 1, We summarized in 1. As shown in Table 1, the Pt / Al-MCM-41 catalyst prepared by the pretreatment introduction method has a slightly higher conversion rate of n-hexadecane compared to the Pt / Al-MCM-41 catalyst prepared by the posttreatment introduction method. However, the selectivity for isomerization is slightly lower, but it can be seen that both catalysts have similar performance.

Table 1 : Conversion of n-hexadecane (350 ° C., 103 bar)

catalyst Pt / Al-MCM-41 Pt / Al-MCM-41 Catalyst manufacturing method Post Treatment of Metals Pretreatment of metals Conversion rate 37.9 40.0 Selectivity to Isohexadecane 98.2 95.5 Isohexadecane (methylpentadegan) with one branch 72.6 (61.1) 55.5 (47.8) Isohexadecane with two branches 21.0 27.7 Isohexadecane with three branches 4.6 12.3 Selectivity of Hydrocracking for C≤15 1.8 4.5

Example 3 Pt / Al-MCM-41 Isomerization Performance Evaluation

As described above, in the dewaxing process, the cracking reaction and the isomerization reaction of the wax occur simultaneously, but the isomerization reaction is more preferable for the yield and the physical properties than the cracking reaction in terms of the yield and the physical properties of the product. In this example, the isomerization performance of the Pt / Al-MCM-41 catalyst (Si / Al = 5) prepared in Example 1 and the catalyst for a conventional dewaxing process was evaluated.

First, as the conventional catalysts, Pt / ZSM-5, Pt / ZSM-22, Pt / SAPO-11, Pt / HY, and the like were evaluated, and ZSM-5, ZSM-22, and SAPO-11 were each US patents. 4,139,600, U.S. Patent No. 3,702,886, and U.S. Patent No. 4,310,440, HY was purchased from Strem Co., USA, and the same amount of platinum on all carriers was carried in 0.005 weight ratio catalyst. Was prepared.

The above catalyst was reacted with n-hexadecane in the same manner as in Example 1, followed by measuring the conversion rate at which n-hexadecane cracked or isomerized over time (see FIG. 2), The conversion to following isohexadecane was measured (see FIG. 3). FIG. 2 is a graph showing the conversion rate (cracking + isomerization) of n-hexadecane over time for each catalyst evaluated, and FIG. 3 is a graph showing the ratio of isomerization according to conversion rate for each catalyst evaluated. to be. In Figure 2, it was confirmed that the conversion rate of n-hexadecane including (cracking + isomerization) is excellent in the Pt / ZSM series of catalysts. However, as shown in FIG. 3, the yield of isomerization reaction is superior to other catalysts of Pt / Al-MCM-41 catalyst, and in case of Pt / ZSM-based catalysts, most of the conversion is due to cracking. Confirmed. Therefore, it can be concluded that the catalyst of the present invention has more suitable performance as a catalyst for dewaxing process.

As described in detail and demonstrated above, in the present invention, an aqueous alkali metal silicate solution obtained by reacting silica with an aqueous alkali metal solution is added dropwise to a template material and hydrothermally synthesized to obtain an MCM-41 carrier, and an Al precursor is added and stirred. After Al-MCM-41 is obtained, a method of preparing a metal-containing binary catalyst by supporting and firing the metal, and a metal-containing binary catalyst prepared therefrom are provided. The metal-containing binary catalyst of the present invention promotes the isomerization reaction rather than the cracking reaction in the conversion process of n-hexadecane. Therefore, the binary catalyst of the present invention may be widely used as a catalyst for dewaxing processes such as lubricating base oil and diesel oil.

Claims (23)

A first step of reacting silica with an aqueous alkali metal solution to obtain an aqueous alkali metal silicate solution; A second step of adding the previously obtained aqueous alkali metal silicate solution to the template material and hydrothermally synthesizing to obtain an MCM-41 carrier; A third step of adding Al precursor dissolved in an organic solvent to the carrier thus obtained and stirring to calcinate the resulting precipitate to obtain Al-MCM-41; And And a fourth step of impregnating the obtained Al-MCM-41 in the precursor solution of the Group VIII metal on the chemical periodic table to support the metal and then to fire it. Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 1, Characterized in that the silica is at least one material selected from the group consisting of fumed silica, aerosil, tetraorthosilicate Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 1, Silica is characterized in that Ludox HS-40 or Ludox AS-30 (Ludox AS-30) Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 1, The alkali metal is a material selected from the group consisting of lithium (Li), sodium (Na) and potassium (K). Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 1, Template materials include octadecyltrimethylammonium bromide (C ₁₈ TMABR), cetyltrimethylammonium chloride (C ₁₆ TMACL), myristyltrimethylammonium chloride (C ₁₄ TMACL), dodecyltrimethylammonium bromide (C ₁₄ TMACL) dodecyltrimethylammonium bromide: C ₁₂ TMABR), decyltrimethylammonium bromide (C ₁₀ TMABR), octyltrimethylammonium bromide (C ₈ TMABR) and hexyltrimethylammonium bromide (hexyltrimethylammonium bromide ₆ group consisting of CMA TMABR): At least one substance selected Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 1, Hydrothermal synthesis is characterized in that the pH is carried out at 9 to 11 Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 1, MCM-41 carrier is characterized in that the pore size is 1.5 to 20 nm in average diameter Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 1, Al precursor is characterized in that at least one material selected from the group consisting of AlCl ₃ , Al (OH) ₃ and Al (OCH ₃ ) ₃ Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 1, The molar ratio of Si / Al in the finally produced Al-MCM-41 is characterized in that 1 to 200 Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 1, The firing of the third and fourth processes is performed for 2 to 48 hours at 350 to 600 ° C., respectively. Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 1, Precursor of Ⅷ group metal is _{Pt (NH 3) 5 · Cl} · H 2 0, Pt (NH 3) 4 · Cl 2 · H 2 0, Pt (NH 3) 3 · Cl 3 · H 2 0 ,, Pt ( _{NH 3) 2 · Cl 4 ·} H 2 0, Pt (NH 3) · Cl 5 · H 2 0, PtCl 6, PtCl 4, PtCl 2, PtS 2, PtSO 4, Pd (NH 3) 5 · Cl · H _{2 0, Pd (NH 3)} 4 · Cl 2 · H 2 0, Pd (NH 3) 3 · Cl 3 · H 2 0 ,, Pd (NH 3) 2 · Cl 4 · H 2 0, Pd (NH 3 _{) · Cl 5 · H 2 0} , PdCl 6, PdCl 4, PdCl 2, PdS 2, PdSO 4, Ni (NH 3) 5 · Cl · H 2 0, Ni (NH 3) 4 · Cl 2 · H 2 0 _{, Ni (NH 3) 3 ·} Cl 3 · H 2 0, Ni (NH 3) 2 · Cl 4 · H 2 0, Ni (NH 3) · Cl 5 · H 2 0, NiCl 6, NiCl 4, NiCl 2 , At least one material selected from the group consisting of NiS ₂ and NiSO ₄ Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. A first step of reacting silica with an aqueous alkali metal solution to obtain an aqueous alkali metal silicate solution; A second step of adding the previously obtained aqueous alkali metal silicate solution to the mold material and mixing the alkali metal silicate and the mold material; A third step of dropwise adding a Group VIII metal precursor solution to the previously obtained mixture and hydrothermally synthesizing to obtain a metal-containing MCM-41 carrier; And And a fourth step of adding the Al precursor dissolved in the organic solvent to the previously obtained metal-containing MCM-41 carrier, stirring, and calcining the resulting precipitate. Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 12, Characterized in that the silica is at least one material selected from the group consisting of fumed silica, aerosil, tetraorthosilicate Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 12, Silica is characterized in that Ludox HS-40 or Ludox AS-30 (Ludox AS-30) Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 12, The alkali metal is a material selected from the group consisting of lithium (Li), sodium (Na) and potassium (K). Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 12, Template materials include octadecyltrimethylammonium bromide (C ₁₈ TMABR), cetyltrimethylammonium chloride (C ₁₆ TMACL), myristyltrimethylammonium chloride (C ₁₄ TMACL), dodecyltrimethylammonium bromide (C ₁₄ TMACL) dodecyltrimethylammonium bromide: C ₁₂ TMABR), decyltrimethylammonium bromide (C ₁₀ TMABR), octyltrimethylammonium bromide (C ₈ TMABR) and hexyltrimethylammonium bromide (hexyltrimethylammonium bromide ₆ group consisting of CMA TMABR): At least one substance selected Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 12, Hydrothermal synthesis, characterized in that carried out at pH 9 to 11 Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 12, Metal-containing MCM-41 carrier is characterized in that the pore size is 1.5 to 20 nm in average diameter Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 12, Al precursor is characterized in that at least one material selected from the group consisting of AlCl ₃ , Al (OH) ₃ and Al (OCH ₃ ) ₃ Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 12, The molar ratio of Si / Al in the finally produced Al-MCM-41 is characterized in that 1 to 200 Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 12, Firing of the fourth process is characterized in that it is carried out at 350 to 600 ℃ for 2 to 48 hours Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. The method of claim 12, Precursor of Ⅷ group metal is _{Pt (NH 3) 5 · Cl} · H 2 0, Pt (NH 3) 4 · Cl 2 · H 2 0, Pt (NH 3) 3 · Cl 3 · H 2 0 ,, Pt ( _{NH 3) 2 · Cl 4 ·} H 2 0, Pt (NH 3) · Cl 5 · H 2 0, PtCl 6, PtCl 4, PtCl 2, PtS 2, PtSO 4, Pd (NH 3) 5 · Cl · H _{2 0, Pd (NH 3)} 4 · Cl 2 · H 2 0, Pd (NH 3) 3 · Cl 3 · H 2 0 ,, Pd (NH 3) 2 · Cl 4 · H 2 0, Pd (NH 3 _{) · Cl 5 · H 2 0} , PdCl 6, PdCl 4, PdCl 2, PdS 2, PdSO 4, Ni (NH 3) 5 · Cl · H 2 0, Ni (NH 3) 4 · Cl 2 · H 2 0 _{, Ni (NH 3) 3 ·} Cl 3 · H 2 0, Ni (NH 3) 2 · Cl 4 · H 2 0, Ni (NH 3) · Cl 5 · H 2 0, NiCl 6, NiCl 4, NiCl 2 , At least one material selected from the group consisting of NiS ₂ and NiSO ₄ Method for preparing metal / Al-MCM-41 binary catalyst for dewaxing process. A metal / AL-MCM-41 binary catalyst for a dewaxing process prepared by the method of claim 1, wherein the weight ratio of metal / (metal + Al-MCM-41) is 0.0001 to 0.15.