KR20010049636A - Method of producing aromatic carbonates by gas phase reaction using heterogeneous catalyst - Google Patents

Abstract

PURPOSE: A method for preparing methyl phenyl carbonate by using an inhomogeneous solid catalyst in gas phase is provided, which provides the methyl phenyl carbonate having excellent activity. CONSTITUTION: The method comprises steps of: (i) preparing a liquid mixture solution by mixing dimethyl carbonate with phenol in a molar ratio of 1:1-10:1; (ii) vaporizing the liquid phase mixture solution; and (iii) gas phase reacting the vaporized mixture solution under a catalyst selected from the group consisting of molybdenum dipped in catalyst, titanium dipped in catalyst, chromium dipped in catalyst, tungsten dipped in catalyst, vanadium dipped in catalyst and stannum dipped in catalyst at a temperature of 300-600 deg.C.

Description

METHODS OF PRODUCING AROMATIC CARBONATES BY GAS PHASE REACTION USING HETEROGENEOUS CATALYST}

[Industrial use]

The present invention relates to a process for producing aromatic carbonate in the gas phase using a solid catalyst. In particular, the present invention relates to a method for preparing methylphenyl carbonate in the gas phase using dimethyl carbonate and phenol.

[Prior art]

It is generally known that a method of preparing methylphenyl carbonate using dimethyl carbonate and phenol as a starting material is carried out by a liquid phase reaction. The catalysts used are Lewis acids, salts of transition metals or esters, organic and inorganic borate.

Document (Ind. Eng. Chem. Res., 31, pp 1167-1170, 1992) reported the use of homogeneous catalysts such as tin and titanium compounds in the liquid phase reaction. 125617 describes a method of using a physical mixture such as silica-titania as a heterogeneous catalyst and another document (Pure and Applied Chemistry, 68, Iss. 2, pp. 367-375, 1996). It has been reported that the molybdenum oxide is excellent in activity.

A series of patents is also known to use titanium or tin compounds as catalysts. U.S. Patent No. 5,380,908 describes a method of extending diphenyl carbonate synthesis in a continuous process to employ distillation to remove alcohols by-products, using dibutyl tin oxide as a catalyst and reacting at atmospheric pressure, reduced pressure and vacuum. It is described that the reaction is carried out at a temperature of 100 to 200 ℃, US Patent No. 5,426,207 was divided into three reaction zones using an organic titanate catalyst, it was possible to improve the yield by employing a multi-stage reactor By using a multi-stage reactor, the heat of vaporization of the product can be used to separate the mixture, reducing the cost of the reboiler.

In addition, US Pat. No. 5,210,268 states that diphenyl carbonate has a high reaction rate, yield and high selectivity by using two multistage distillation columns using lead compounds as catalysts.

As described above, the prior arts are performed only in the liquid phase reaction in the preparation of the aromatic carbonate, and the present invention is methylphenyl which exhibits high activity by reacting dimethyl carbonate and phenol using a solid catalyst in a gas phase reaction not reported to date. It is an object to provide a method for producing a carbonate.

[Means for solving the problem]

In the present invention to achieve the above object

a) Mixing dimethyl carbonate and phenol in a molar ratio of 1: 1 to 10: 1

Preparing a mixed liquid;

b) vaporizing the liquid mixture; And

c) supporting the vaporized mixed solution with a molybdenum (Mo) supported catalyst, a titanium (Ti) supported catalyst,

Chromium (Cr) supported catalyst, tungsten (W) supported catalyst, vanadium (V) supported catalyst, and

300 to 600 under a catalyst selected from the group consisting of tin (Sn) supported catalysts

Gas phase reaction at a temperature of

It provides a method for producing methylphenyl carbonate comprising a.

Molybdenum (Mo) supported catalyst is a molybdenum (Mo) metal supported amount of 1 to 30% by weight, (NH ₄ ) ₆ Mo ₇ O ₂₄ 4H ₂ O molybdenum (Mo) oxide precursor aluminum oxide It is prepared by being supported on a carrier selected from the group consisting of (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), and activated carbon (C).

The titanium (Ti) supported catalyst is a titanium (Ti) metal supported amount of 1 to 30% by weight, titanium (IV) butoxide (Ti (IV) -butoxide), titanium (IV) ethoxide (Ti (IV)- titanium oxide (Ti) oxide precursor selected from the group consisting of ethoxide, titanium (IV) isopropoxide (Ti (IV) -isopropoxide), and titanium (IV) chloride Al ₂ O ₃ ), magnesium oxide (MgO), silicon oxide (SiO ₂ ), and activated carbon (C) to be supported on a carrier selected from the group consisting of.

The chromium (Cr) supported catalyst is prepared by supporting a chromium (Cr) metal supported amount of 1 to 30% by weight and supporting a chromium oxide precursor of Cr (NO ₃ ) ₃ .9H ₂ O on a silica (SiO ₂ ) carrier. .

The tungsten (W) supported catalyst has a tungsten (W) metal loading of 1 to 30% by weight, and a (NH ₄ ) ₆ W ₁₂ O ₃₉ .xH ₂ O tungsten oxide precursor is supported on a silica (SiO ₂ ) carrier. To be manufactured.

The vanadium (V) supported catalyst is prepared by supporting a vanadium oxide precursor having a vanadium (V) metal content of 1 to 30% by weight, and a (NH ₄ ) VO ₃ vanadium oxide precursor on a silica (SiO ₂ ) carrier.

The tin (Sn) supported catalyst is a tin (Sn) metal supported amount of 1 to 30% by weight, and the tin oxide precursor, which is SnCl ₂ , is prepared by a silica (SiO ₂ ) support.

The reaction system used in the present invention uses a glass tube made of Pyrex or quartz as a continuous flow gas phase reactor, and the reactant is reacted in the gas phase by vaporizing a liquid mixture of dimethyl carbonate and phenol through heating before reaching the reactor.

The reaction of the present invention uses a catalyst in which a metal oxide is supported on various supports. The metal precursor solution is supported by 1 to 30% by weight on each carrier by incipient wetness, and is then heated in an oven at 110 ° C. It is a heterogeneous solid catalyst produced by heat-treating for 4 hours at 500-800 degreeC in air or helium gas atmosphere after drying for more than time.

All catalysts are present in the form of fully oxidized metal oxides, unless otherwise indicated.

Hereinafter, the preparation examples and examples of the solid catalysts used in the reaction of the present invention will be described in detail, and these examples are provided to illustrate the present invention, but the present invention is not limited thereto.

EXAMPLE

Production Examples 1-15

Aluminum oxide (Al ₂ O ₃ ) by incipient the metal precursor solution of molybdenum (Mo), chromium (Cr), tungsten (W), vanadium (V), tin (Sn), titanium (Ti) ), Supported on a carrier selected from titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), and activated carbon (C), and then heat-treated at 500 ° C. for 4 hours while flowing air or helium gas to prepare a heterogeneous solid catalyst. Table 1 shows each preparation example such as the solvent at this time, the kind of precursor solution, and the kind of gas at the time of heat treatment.

These catalysts were prepared by reacting dimethyl carbonate and phenol to prepare methylphenyl carbonate, followed by heat treatment while flowing nitrogen gas for 1 hour at a temperature higher than 50 ° C. before the reaction, and then used as catalysts.

Preparation Example 16

The Mo (IV) -C catalyst of Preparation Example 4 was heat-treated at 700 ° C. for 1 hour while flowing ammonia gas to prepare a MoN-C catalyst.

Preparation Example 17

The MoN-C catalyst of Preparation Example 16 was heat-treated at 700 ° C. for 1 hour while flowing methane and hydrogen at a ratio of 1: 4 to prepare a Mo ₂ CC catalyst.

division Catalyst type (metal-carrier) Metal precursor Metal loading in the carrier (% by weight) Supported solvent Heat treatment gas Preparation Example 1 Mo-SiO _{2 (NH 4) 6 Mo 7 O} 24 · 4H 2 O 10 Distilled water air Preparation Example 2 Mo-Al ₂ O _{3 (NH 4) 6 Mo 7 O} 24 · 4H 2 O 10 Distilled water air Preparation Example 3 Mo-TiO _{2 (NH 4) 6 Mo 7 O} 24 · 4H 2 O 10 Distilled water air Preparation Example 4 Mo (Ⅳ) -C _{(NH 4) 6 Mo 7 O} 24 · 4H 2 O 20 Distilled water helium Preparation Example 5 Cr-SiO ₂ Cr (NO ₃ ) ₃ 9H ₂ O 10 Distilled water air Preparation Example 6 W-SiO _{2 (NH 4) 6 W 12 O} 39 · xH 2 O 10 Distilled water air Preparation Example 7 V-SiO ₂ NH ₄ VO ₃ 10 Distilled water air Preparation Example 8 Sn-SiO ₂ SnCl ₂ 10 Methanol air Preparation Example 9 Ti-MgO Ti (Ⅳ) -butoxide 10 toluene air Preparation Example 10 Ti-C Ti (Ⅳ) -butoxide 10 toluene helium Preparation Example 11 Ti-Al ₂ O ₃ Ti (Ⅳ) -butoxide 10 toluene air Preparation Example 12 Ti-SiO ₂ Ti (Ⅳ) -butoxide 10 toluene air Preparation Example 13 Ti-SiO ₂ Ti (Ⅳ) -ethoxide 10 toluene air Preparation Example 14 Ti-SiO ₂ Ti (Ⅳ) -isopropoxide 10 toluene air Preparation Example 15 Ti-SiO ₂ Ti (Ⅳ) -chloride 10 toluene air Preparation Example 16 Mo ₂ NC _{(NH 4) 6 Mo 7 O} 24 · 4H 2 O ammonia injection 700 ℃ heat treatment 20 Distilled water helium Preparation Example 17 Mo ₂ CC _{(NH 4) 6 Mo 7 O} 24 · 4H 2 O methane, hydrogen injection 700 ℃ heat treatment 20 Distilled water helium

Examples 1-6

The reaction using the catalyst Mo-SiO ₂ of Preparation Example 1 as a reaction catalyst in a continuous flow reactor and injecting a mixture of dimethyl carbonate and phenol in a molar ratio of 5: 1 as a reactant at an injection rate of 1 ml / hr The reaction was carried out while changing the temperature to 300 to 600 ° C. At this time, the carrier gas was nitrogen, and the injection rate was 20 ml / min, and all the reactants were vaporized by heating before reaching the reactor in order to reach the catalyst layer smoothly.

Table 2 shows the degree of formation of phenol conversion, phenyl carbonate selectivity, yield, and the like in the reaction time of 500 minutes for each catalyst.

Phenol conversion was determined based on the weight of phenol added, and selectivity and yield of methylphenylcarbonate were determined from the mass concentration in the product resulting from conversion of phenol.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 catalyst Mo-SiO ₂ Mo-SiO ₂ Mo-SiO ₂ Mo-SiO ₂ Mo-SiO ₂ Mo-SiO ₂ Catalyst amount (g) 0.48 0.48 0.48 0.48 0.48 0.48 Metal supported amount of catalyst (wt%) 10 10 10 10 10 10 Molar ratio (DMC: Ph) 5: 1 5: 1 5: 1 5: 1 5: 1 5: 1 Reactant Flow Rate (ml / hr) One One One One One One Nitrogen Flow Rate (ml / min) 20 20 20 20 20 20 Reaction temperature (℃) 300 350 400 450 500 600 Phenolic Conversion Rate (%) 2.5 4.0 9.9 20.5 30.2 36.7 DMC selectivity (%) 20.5 26.3 47.1 40.8 35.3 30.2 DMC yield (%) 0.5 1.1 4.7 8.4 10.7 11.1

Examples 7-11

The amount of the catalyst Mo-SiO ₂ used in Preparation Example 1 was changed to 1 g, and the preparation was carried out as in Example 1, but the reaction temperature was fixed at 450 ° C., and the reaction molar ratio and the injection flow rate of the reactant were changed to prepare methylphenyl carbonate.

The generation degree at this time is shown in Table 3.

division Example 7 Example 8 Example 9 Example 10 Example 11 catalyst Mo-SiO ₂ Mo-SiO ₂ Mo-SiO ₂ Mo-SiO ₂ Mo-SiO ₂ Catalyst amount (g) One One One One One Metal supported amount of catalyst (wt%) 10 10 10 10 10 Molar ratio (DMC: Ph) 1: 1 2.5: 1 5: 1 7.5: 1 10: 1 Reactant Flow Rate (ml / hr) 0.20 0.49 One 1.5 2 Nitrogen Flow Rate (ml / min) 20 20 20 20 20 Reaction temperature (℃) 450 450 450 450 450 Phenolic Conversion Rate (%) 6.8 11.3 20.6 29.6 35.7 DMC selectivity (%) 19.2 34.9 40.6 31.8 22.5 DMC yield (%) 1.3 3.9 8.4 9.4 8.0

Examples 12-16, Comparative Example 1

The methylphenyl carbonate was prepared in the same manner as in Example 1 while changing the nitrogen flow rate to 30 ml / min at a reaction temperature of 450 ° C. and changing the metal loading of the catalyst Mo-SiO ₂ of Preparation Example 1.

The production degree at this time is shown in Table 4.

division Comparative Example 1 Example 12 Example 13 Example 14 Example 15 Example 16 catalyst Mo-SiO ₂ Mo-SiO ₂ Mo-SiO ₂ Mo-SiO ₂ Mo-SiO ₂ Mo-SiO ₂ Catalyst amount (g) 0.48 0.48 0.48 0.48 0.48 0.48 Metal supported amount of catalyst (wt%) 0 One 5 10 20 30 Molar ratio (DMC: Ph) 5: 1 5: 1 5: 1 5: 1 5: 1 5: 1 Reactant Flow Rate (ml / hr) One One One One One One Nitrogen Flow Rate (ml / min) 30 30 30 30 30 30 Reaction temperature (℃) 450 450 450 450 450 450 Phenolic Conversion Rate (%) 39.0 30.1 19.6 11.5 9.3 3.5 DMC selectivity (%) 40.7 51.7 50.3 37.9 34.7 35.0 DMC yield (%) 15.9 15.6 9.9 4.4 3.2 1.2

Examples 17-21, Comparative Example 2

The reaction temperature was 450 deg. C, and methylphenyl carbonate was prepared in the same manner as in Example 1 while changing the amount of metal supported by the catalyst Mo (IV) -C in Preparation Example 4.

The generation degree at this time is shown in Table 5.

division Comparative Example 2 Example 17 Example 18 Example 19 Example 20 Example 21 catalyst Mo (Ⅳ) -C Mo (Ⅳ) -C Mo (Ⅳ) -C Mo (Ⅳ) -C Mo (Ⅳ) -C Mo (Ⅳ) -C Catalyst amount (g) 0.48 0.48 0.48 0.48 0.48 0.48 Metal supported amount of catalyst (wt%) 0 One 5 10 20 30 Molar ratio (DMC: Ph) 5: 1 5: 1 5: 1 5: 1 5: 1 5: 1 Reactant Flow Rate (ml / hr) One One One One One One Nitrogen Flow Rate (ml / min) 20 20 20 20 20 20 Reaction temperature (℃) 450 450 450 450 450 450 Phenolic Conversion Rate (%) 57.1 27.9 30.3 24.6 28.6 20.7 DMC selectivity (%) 7.2 29.4 32.5 38.6 47.4 50.3 DMC yield (%) 4.1 8.2 9.8 9.5 13.6 10.4

Examples 22-26, Comparative Example 3

Using the catalyst Mo (IV) -C of Preparation Example 4 as a catalyst, the reaction temperature was fixed at 450 ℃, methylphenyl carbonate was prepared in the same manner as in Example 1 while changing the flow rate of nitrogen as a carrier gas.

The production degree at this time is shown in Table 6.

division Comparative Example 3 Example 22 Example 23 Example 24 Example 25 Example 26 catalyst Mo (Ⅳ) -C Mo (Ⅳ) -C Mo (Ⅳ) -C Mo (Ⅳ) -C Mo (Ⅳ) -C Mo (Ⅳ) -C Catalyst amount (g) 0.48 0.48 0.48 0.48 0.48 0.48 Metal supported amount of catalyst (wt%) 20 20 20 20 20 20 Molar ratio (DMC: Ph) 5: 1 5: 1 5: 1 5: 1 5: 1 5: 1 Reactant Flow Rate (ml / hr) One One One One One One Nitrogen Flow Rate (ml / min) 0 10 20 30 50 70 Reaction temperature (℃) 450 450 450 450 450 450 Phenolic Conversion Rate (%) 51.7 26.8 21.2 17.9 16.0 14.7 DMC selectivity (%) 13.3 47.7 55.3 70.1 70.9 71.2 DMC yield (%) 6.9 12.8 11.7 12.5 11.3 10.5

Examples 27-31

Using the catalyst Mo (IV) -C of Preparation Example 4 as a catalyst, the reaction temperature was fixed at 450 ℃ nitrogen flow rate to 30 ml / min, and the injection flow rate of the reactants were changed to prepare methylphenyl carbonate as in Example 1 It was.

The activity at this time is shown in Table 7.

division Example 27 Example 28 Example 29 Example 24 Example 30 Example 31 catalyst Mo (Ⅳ) -C Mo (Ⅳ) -C Mo (Ⅳ) -C Mo (Ⅳ) -C Mo (Ⅳ) -C Mo (Ⅳ) -C Catalyst amount (g) 0.48 0.48 0.48 0.48 0.48 0.48 Metal supported amount of catalyst (wt%) 20 20 20 20 20 20 Molar ratio (DMC: Ph) 5: 1 5: 1 5: 1 5: 1 5: 1 5: 1 Reactant Flow Rate (ml / hr) 0.20 0.49 0.74 1.00 1.50 2.00 Nitrogen Flow Rate (ml / min) 30 30 30 30 30 30 Reaction temperature (℃) 450 450 450 450 450 450 Phenolic Conversion Rate (%) 25.4 23.9 22.3 17.9 12.3 10.1 DMC selectivity (%) 40.8 48.2 58.6 70.1 61.7 55.4 DMC yield (%) 10.4 11.5 13.1 12.5 7.6 5.6

Examples 32-38

Methylphenyl carbonate was prepared in the same manner as in Example 1, using the catalyst Ti-SiO ₂ of Preparation Example 12 and changing the reaction temperature.

The generation degree at this time is shown in Table 8.

division Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Example 38 catalyst Ti-SiO ₂ Ti-SiO ₂ Ti-SiO ₂ Ti-SiO ₂ Ti-SiO ₂ Ti-SiO ₂ Ti-SiO ₂ Catalyst amount (g) 0.48 0.48 0.48 0.48 0.48 0.48 0.48 Metal supported amount of catalyst (wt%) 10 10 10 10 10 10 10 Molar ratio (DMC: Ph) 5: 1 5: 1 5: 1 5: 1 5: 1 5: 1 5: 1 Reactant Flow Rate (ml / hr) One One One One One One One Nitrogen Flow Rate (ml / min) 20 20 20 20 20 20 20 Reaction temperature (℃) 300 370 400 430 450 480 600 Phenolic Conversion Rate (%) 12.7 20.3 29.5 36.4 37.2 38.2 45.9 DMC selectivity (%) 77.4 78.5 93.6 87.5 85.1 86.0 68.6 DMC yield (%) 9.8 15.9 27.6 31.8 31.7 32.9 31.5

Examples 39-42, Comparative Example 4

The reaction temperature was 430 ° C., and methylphenyl carbonate was prepared in the same manner as in Example 1 while varying the metal loading of the Ti-SiO ₂ catalyst of Preparation Example 12.

Table 9 shows the degree of generation at this time.

division Comparative Example 4 Example 39 Example 35 Example 40 Example 41 Example 42 catalyst Ti-SiO ₂ Ti-SiO ₂ Ti-SiO ₂ Ti-SiO ₂ Ti-SiO ₂ Ti-SiO ₂ Catalyst amount (g) 0.48 0.48 0.48 0.48 0.48 0.48 Metal supported amount of catalyst (wt%) 0 5 10 13 20 30 Molar ratio (DMC: Ph) 5: 1 5: 1 5: 1 5: 1 5: 1 5: 1 Reactant Flow Rate (ml / hr) One One One One One One Nitrogen Flow Rate (ml / min) 20 20 20 20 20 20 Reaction temperature (℃) 430 430 430 430 430 430 Phenolic Conversion Rate (%) 13.7 30.6 36.4 33.0 23.4 13.5 DMC selectivity (%) 52.1 65.2 87.5 85.7 85.3 85.0 DMC yield (%) 7.1 20.0 31.8 28.3 20.0 11.5

Examples 43-56

Using the catalysts of Preparation Examples 1 to 17, a solution containing dimethyl carbonate and phenol mixed at a molar ratio of 5: 1 was injected at an injection rate of 1 ml / hr, and reacted while flowing nitrogen at 20 ml / min as a carrier gas. The reaction of the catalyst layer is facilitated to vaporize the reactant through heating before reaching the reactor. Each catalyst was heat treated at 500 ° C. for 1 hour while flowing nitrogen gas, and the reaction temperature was fixed at 450 ° C. for 500 minutes.

Table 10 shows the activities of methylphenyl carbonate prepared by gas phase reaction between dimethyl carbonate and phenol.

division catalyst Catalyst amount (g) Phenol Conversion Rate (%) Methylphenylcarbonate selectivity (%) Methylphenylcarbonate yield (%) Example 4 Mo-SiO ₂ (Manufacturing Example 1) 0.48 20.6 40.6 8.4 Example 43 Mo-Al ₂ O ₃ (Preparation Example 2) 1.00 2.1 34.6 0.7 Example 44 Mo-TiO ₂ (Manufacturing Example 3) 1.00 0.9 57.6 0.5 Example 20 Mo (IV) -C (production example 4) 1.00 28.6 47.4 13.6 Example 45 Cr-SiO ₂ (Manufacturing Example 5) 0.48 29.9 16.8 5.0 Example 46 W-SiO ₂ (Manufacturing Example 6) 0.48 12.1 27.7 3.4 Example 47 V-SiO ₂ (Preparation Example 7) 0.48 6.0 47.7 2.9 Example 48 Sn-SiO ₂ (Manufacturing Example 8) 0.48 20.7 52.9 11.0 Example 49 Ti-MgO (Manufacturing Example 9) 0.48 24.3 37.1 9.0 Example 50 Ti-C (Production Example 10) 0.48 30.4 91.2 27.7 Example 51 Ti-Al ₂ O ₃ (Manufacturing Example 11) 0.48 37.0 80.8 29.9 Example 36 Ti-SiO ₂ (Manufacturing Example 12) 0.48 37.2 85.1 31.7 Example 52 Ti-SiO ₂ (Manufacturing Example 13) 0.48 30.4 84.9 25.8 Example 53 Ti-SiO ₂ (Manufacturing Example 14) 0.48 28.9 80.4 23.2 Example 54 Ti-SiO ₂ (Manufacturing Example 15) 0.48 32.4 87.9 28.5 Example 55 Mo ₂ NC (Production Example 16) 1.00 16.8 18.2 3.1 Example 56 Mo ₂ CC (Manufacturing Example 17) 1.00 17.5 24.5 4.3

The methylphenyl carbonate prepared by reacting dimethyl carbonate and phenol by the gas phase reaction process of the present invention exhibits an activity having better selectivity and yield of methyl phenyl carbonate than the conventional liquid phase reaction process. Therefore, methylphenyl carbonate can be manufactured by raising productivity more.

Claims (7)

In the manufacturing method of methylphenyl carbonate, a) Mixing dimethyl carbonate and phenol in a molar ratio of 1: 1 to 10: 1 Preparing a mixed liquid; b) vaporizing the liquid mixture; And c) supporting the vaporized mixed solution with a molybdenum (Mo) supported catalyst, a titanium (Ti) supported catalyst, Chromium (Cr) supported catalyst, tungsten (W) supported catalyst, vanadium (V) supported catalyst, and 300 to 600 under a catalyst selected from the group consisting of tin (Sn) supported catalysts Gas phase reaction at a temperature of ℃ to prepare methylphenyl carbonate Method for producing methylphenyl carbonate comprising a. The method of claim 1, The molybdenum (Mo) supported catalyst is a molybdenum (Mo) oxide precursor of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] aluminum oxide (Al ₂ O ₃ ), titanium oxide ( TiO ₂ ), supported by a carrier selected from the group consisting of silicon oxide (SiO ₂ ), and activated carbon (C) and dried, and then fired for 4 hours at 500 ~ 800 ℃ firing temperature under air or helium gas atmosphere, A method for producing methylphenyl carbonate having a molybdenum (Mo) metal loading of 1 to 30% by weight. The method of claim 1, The titanium (Ti) supported catalyst is titanium (IV) butoxide (Ti (IV)-butoxide), titanium (IV) ethoxide (Ti (IV)-ethoxide), titanium (IV) isopropoxide (Ti (IV) ) titanium oxide precursors selected from the group consisting of isopropoxide, and titanium (IV) chloride, such as aluminum oxide (Al ₂ O ₃ ), magnesium oxide (MgO), and silica (SiO). ₂ ) and dried on a carrier selected from the group consisting of activated carbon (C), and then calcined at 500 to 800 ° C. for 4 hours under an air or helium gas atmosphere, and the amount of titanium (Ti) metal supported is 1 The manufacturing method of methylphenyl carbonate which is-30 weight%. The method of claim 1, The chromium (Cr) supported catalyst is dried by supporting a chromium oxide precursor of chromium nitrate hydrate [Cr (NO ₃ ) ₃ .9H ₂ O] on a silica (SiO ₂ ) carrier, followed by drying in an air or helium gas atmosphere. It is produced by firing at 500 to 800 ° C. for 4 hours, and has a chromium (Cr) metal loading of 1 to 30% by weight. The method of claim 1, The tungsten (W) supported catalyst is formed by drying a tungsten oxide precursor of ammonium metatungstate hydrate [(NH ₄ ) ₆ W ₁₂ O ₃₉ .xH ₂ O] on a silica (SiO ₂ ) carrier, followed by air or helium gas. A method for producing methylphenyl carbonate, which is prepared by firing at a firing temperature of 500 to 800 ° C. for 4 hours in an atmosphere, and has a tungsten (W) metal loading of 1 to 30% by weight. The method of claim 1, The vanadium (V) supported catalyst is dried by supporting a vanadium oxide precursor of ammonium metavanadate (NH ₄ VO ₃ ) on a silica (SiO ₂ ) carrier and then drying at 500 to 800 ° C. under an air or helium gas atmosphere. It is produced by baking for a time, and the manufacturing method of methylphenyl carbonate whose vanadium (V) metal loading amount is 1-30 weight%. The method of claim 1, The tin (Sn) supported catalyst is prepared by drying a tin precursor of tin chloride (SnCl ₂ ) on a silica (SiO ₂ ) carrier, followed by drying at 500 to 800 ° C. under an air or helium gas atmosphere for 4 hours. The manufacturing method of methylphenyl carbonate whose tin (Sn) metal loading is 1-30 weight%.