KR20030066340A - Continuous method for preparing aromatic carbonate and reaction equipment for the same - Google Patents

Abstract

PURPOSE: Provided are a method for continuously and economically producing an aromatic carbonate, which is suitable for commercial production, and a reaction device for the method. CONSTITUTION: The method for continuously producing an aromatic carbonate by using a heterogeneous catalyst, comprises the steps of (i) injecting a dialkyl carbonate or alkyl aryl carbonate and an aromatic hydroxy compound into the reactor(1) injected with a heterogeneous catalyst; (ii) filtrating the reaction liquid obtained in the step(i) to isolate the heterogeneous catalyst; (iii) cycling the filtrated reaction liquid while applying the heat from the outside of the reactor; (iv) distilling a reaction byproduct vaporized with the heat of the step(iii) and ingredients with low boiling point, and condensing effective ingredients having relatively high boiling point to recover the reactor; and (v) extracting the high boiling ingredients which are final reactants, from the reaction liquid at intermediate time of the cycling step.

Description

Aromatic carbonate continuous manufacturing method and a reaction apparatus therefor {CONTINUOUS METHOD FOR PREPARING AROMATIC CARBONATE AND REACTION EQUIPMENT FOR THE SAME}

The present invention relates to a reaction apparatus for producing an aromatic carbonate and a manufacturing method using the same, and more particularly to a continuous method for producing an aromatic carbonate using a heterogeneous catalyst and a reaction apparatus for the same.

Aromatic carbonates are used as raw materials for the production of aromatic polycarbonates and various types of isocyanates that do not use toxic phosgene gas, mainly by transesterification of dialkyl carbonates and aromatic hydroxy compounds. Are synthesized. At this time, examples of the reaction raw material mainly used include dimethyl carbonate and phenol.

However, the transester reaction is a reversible reaction, so the equilibrium constant of the reaction is very small, the conversion after the reaction is very low, and the reaction rate is also very slow, there are many difficulties to be used in commercial production.

In order to solve these problems, various efforts have been made. Among them, efforts have been made to increase the reaction rate by improving the performance of the reaction catalyst. U.S. Patent No. 4,182,726 discloses discloses a process using a catalyst of _{AlX 3, UX 3, TiX 3} , VOX 3, VX 3, ZnX 2, FeX 3 and SnX ₃ series, such as AlCl _3. In the above, X means halogen group elements.

In addition, US Patent No. 4,045,464 discloses a Ti-based compound such as Lewis acids or titanium tetraphenate as a reaction catalyst. In addition, US Patent No. 4,552,704 discloses a Ti and Sn-based reaction catalyst such as butyltin oxide hydroxide, US Patent No. 4,554,110 is a reaction catalyst, the polymer tin (polymeric tin) compound US Patent No. 4,609,501 discloses a reaction catalyst in which at least one Lewis acid and one protic acid are mixed.

The conventional techniques can be seen that the effort was made to improve the reaction rate by the reaction catalyst rather than improving the reactivity by the reaction process in order to increase the efficiency of producing diphenyl carbonate (DPC) from dimethyl carbonate (DMC). However, all of the catalysts proposed in the above patents should be used as a homogeneous catalyst by mixing the reactants in a certain ratio, even though a process of continuously removing reaction by-products such as methanol generated during the reaction from the reaction system is applied. The reaction rate shown in the field was not high.

On the other hand, there have been attempts to use heterogeneous catalysts as reaction catalysts. U.S. Patent No. 5,354,923 uses a stirred reactor using a catalyst on powder having a surface area of 20 m 2 / g or more, and U.S. Patent No. 5,565,605 uses heterogeneous catalysts such as titanoalumino phosphate in the reaction.

However, until now, heterogeneous catalysts have been reacted and separated together with reactants in powder form, causing them to stick to the inner wall of equipment and pipes, causing problems. There is a problem.

Along with the development of reaction catalysts, efforts have been made to increase the efficiency of DPC manufacturing by designing unique reaction processes. U.S. Patent No. 5,210,268 uses a multi-stage distillation column as a reactor to inject a high-boiling reactant with a homogeneous catalyst in the upper layer of the tower, and the low-boiling reactant is heat vaporized at the bottom of the column to countercurrently contact the two reactants with different boiling points. To synthesize an aromatic carbonate. U. S. Patent No. 5,426, 207 also discloses a reaction process using three reactors connected in series, and U. S. Patent No. 5,523, 451 discloses a process in which a plurality of bubble columns connected in series are applied to the reactor. U. S. Patent No. 6,057, 470 also discloses a reaction process using a reaction distillation technique.

However, these processes have a lot of difficulties in separating the catalyst using a homogeneous catalyst or a powdered catalyst, and there are economic problems in that a constant amount of catalyst must be continuously supplied to the reaction system during continuous operation.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and aims to provide a continuous production method of an aromatic carbonate which is capable of solving all the above-mentioned conventional problems and is suitable for commercial production, and a reaction apparatus therefor.

Another object of the present invention is to prepare an aromatic carbonate by reacting a dialkyl carbonate with an aromatic hydroxy compound under a heterogeneous catalyst, and does not undergo a reaction and separation process so that the catalyst and reactants do not cause problems due to sticking to the inner wall of the device and the pipe. To provide a continuous method for producing an aromatic carbonate in which a high boiling point reaction product and a catalyst do not exist, and a reaction apparatus therefor.

Another object of the present invention is to produce an aromatic carbonate by reacting a dialkyl carbonate with an aromatic hydroxy compound using a heterogeneous catalyst, thereby incurring costs in the process of using a homogeneous catalyst that requires continuous injection of new catalyst into the reactor. And to provide a continuous method of producing an economical aromatic carbonate that can minimize the catalyst separation process and a reaction apparatus for the same.

1 is a block diagram showing a reaction apparatus according to the present invention.

In order to achieve the above object, the present invention provides a continuous production process comprising a mixing step of injecting a dialkyl carbonate or an alkyl aryl carbonate and an aromatic hydroxy compound into the reactor while the heterogeneous catalyst is added to the reactor; A filtering step of filtering only the heterogeneous catalyst by filtering the reaction solution generated in the mixing step; A circulation step of circulating the reaction liquid filtered in the filtering step, while circulating while applying heat from the outside of the reactor; A distillation step of distilling the reaction by-products and the low boiling point component vaporized by the heat applied in the circulation step and condensing the active ingredients having a relatively high boiling point upon distillation and recovering them to the reactor; And a extraction step of extracting the high boiling point component, which is the final reactant, from the reaction solution in the middle of the circulation step.

In addition, the reactor according to the present invention is located in the reactor itself is equipped with a filter for preventing the heterogeneous catalyst outflow and only the reaction liquid outflow; A circulation pump connected to the side of the reactor in which the filter is installed; A heat exchanger connected between the circulating pump and the reactor, the heat exchanger configured to receive a reaction liquid from the reaction liquid circulation pump to raise and vaporize the reaction liquid to a desired reaction temperature; And a high boiling point component and a low boiling point component which are connected to an upper portion of the reactor and are supplied with vaporized reactants generated in the reactor and the heat exchanger to condense and recover the high boiling point component to the reactor, and the low boiling point component is vaporized. A distillation column for effluent.

Hereinafter, preferred embodiments of the present invention will be described in detail.

The present invention is a continuous production of an aromatic carbonate using a heterogeneous catalyst for producing an aromatic carbonate or a mixture thereof using an aromatic hydroxy compound such as dialkyl carbonate and phenol as a raw material. The present invention relates to a method and a reactor therefor, wherein a loop-type circulating reactor equipped with a distillation column is used to remove reaction by-products generated during a reaction, and a heterogeneous catalyst supported on silica is used as a reaction catalyst. have.

The method for continuously preparing the aromatic carbonate according to the present invention includes a mixing step of continuously injecting dialkyl carbonate or alkyl aryl carbonate and an aromatic hydroxy compound into the reactor while the heterogeneous catalyst is added to the reactor, A filtering step for filtering only the heterogeneous catalyst by filtering the reaction solution generated in the mixing step, and a circulation step for circulating the filtered reaction solution in the filtering step, while circulating while applying heat from the outside of the reactor, in this circulation step The distillation step of distilling the reaction by-product and the low boiling point component evaporated by the applied heat and condensing the active ingredients having a relatively high boiling point during distillation, and extracting the high boiling point component as the final reactant from the reaction solution It includes.

Here, a transition metal oxide is used as the heterogeneous catalyst used in the mixing step.

The heterogeneous catalyst uses a carrier such as silica, and the carrier is formed in a spherical, cylindrical, ring, or the like shape having a size of 1 to 20 mm. At this time, the specific surface area of the silica is 20 to 500 m 2 / g, more preferably 100 to 300 m 2 / g, and the porosity is 0.25 to 0.8 cm 3 / g, more preferably 0.4 to 0.75 cm 3 / g.

Transition metal oxides are supported on such a carrier, for example, MoO ₃ , Ga ₂ O ₃ , V ₂ O ₅ , PbO, ZrO ₂ , TiO ₂ , CdO, Fe ₂ O ₃ , CuO, MgO, Y ₂ O It is preferable to select and support ₃ , Mn ₃ NiO, ZnO, Nd ₂ O ₃ , Co ₂ O ₃ , RuO ₂ , Nb ₂ O ₅ , Cr ₂ O ₃ , and the like.

The catalyst is added to adjust the amount of aromatic carbonate to be produced. That is, the amount of heterogeneous catalyst required for production is determined after experimentally determining the amount of aromatic carbonate prepared for a predetermined residence time by a certain amount of catalyst.

The reaction solution generated in the mixing step is separated from the catalyst through the filtering step.

In the circulation step, when the amount of the reaction solution generated in the mixing step is a predetermined amount or more, the reaction solution separated from the catalyst is reintroduced into the above mixing step and circulated. In particular, in this circulation step, heat is applied to the reaction liquid which is circulated outside the reactor, and reaction by-products and low boiling point components generated by such heating are subjected to a distillation step. At this time, the temperature of the reaction solution by heating may vary depending on the pressure of the reactor, preferably 100 ° C to 300 ° C, more preferably 150 ° C to 250 ° C.

In addition, during the distillation step, the reaction products of the alkyl alcohol and the relatively low boiling alkyl carbonates are not condensed, but are condensed through the condensation step.

The condensation step is a step of condensing the alkyl alcohol carbonate as a reaction by-product and alkyl carbonates having a relatively low boiling point to pass through the cooling heat exchanger. The condensation temperature is about 10 ° C. to 50 ° C. The condensate generated at this time is refluxed or taken out to the distillation step in whole or in part.

On the other hand, in the extraction step is a step of taking out a part of the circulating reaction solution, it is taken out of the reactor by controlling the reactor level.

At this time, the final reactant taken out is an aromatic carbonate reactant having a high boiling point component, which is subjected to a conventional purification process such as distillation or crystallization.

The reaction apparatus according to the present invention for realizing the above production method is a reactor suitable for the production of aromatic carbonate using a heterogeneous catalyst having a catalyst size of about 1 to 20 mm, and is equipped with a filter filled with a catalyst. The reactor and the heat exchanger section for supplying the necessary heat during the reaction are connected, and the reaction liquid during the reaction is circulated by the circulation pump with the catalyst charge part and the heat exchanger, the by-products, etc. are removed through a distillation tower connected to the reactor Device.

In more detail with reference to Figure 1, the loop type catalyst charging reactor of the present invention is a filter (1a) for filtering the catalyst and the reaction liquid installed in the reactor 1, the lower portion of the reactor (1) And a heat exchanger (3) connected to the lower and upper portions of the reactor (1) through a pipe (8), and a circulation pump (4) for circulating the reaction liquid from the reactor (1) to the heat exchanger (3); , A water level regulator installed between the heat exchanger 3 and the circulation pump 4 to discharge a part of the circulating reaction to the outside, a distillation tower 2 connected to the upper portion of the reactor 1, and a distillation tower ( 2) the cooling heat exchanger (5) connected to the upper side of the installation, and connected to the cooling heat exchanger (5) so that all or part of the condensate generated during cooling can be refluxed or taken out to the distillation column (2). It includes branch pipes (11, 12).

Here, a plurality of pipes 2a and 2b are connected to the upper portion of the reactor 1 so that raw materials can be continuously supplied into the reactor 1.

These plurality of pipes 2a, 2b continuously inject a calculated amount of dialkyl carbonate or alkyl aryl carbonate and aromatic hydroxy compound into the reactor, respectively or in combination.

The filter 1a installed in the inner lower part of the reactor 1 is a conventional filter used for fluid separation, so that only the reaction solution is allowed to flow out smoothly without flowing out the heterogeneous catalyst. Thus, the filter 1a has a mesh eye smaller than the size of the heterogeneous catalyst. The mesh eye of the filter 1a is about 0.1 to 15 mm.

The level controller keeps the level of the reaction liquid in the reactor 1 constant by taking out a part of the reaction liquid generated in the reactor 1 to the outside. At this time, the level controller used may be of any type commonly used in chemical processes.

Through this water level regulator, the high boiling point component (final reactant) containing the desired aromatic carbonate in the reactor 1 can be taken out through a pipe or directly from the reactor 1 on the side where the filter 1a is installed.

The distillation column (2) is connected to the reactor (1) and the upper tube (2a) and the lower tube (2b), the upper tube (2a) is a distillation column of the reaction by-products and low boiling point vaporized by the heat exchanger (3) Guided to (2), the lower tube (2b) allows the relatively high boiling point active ingredients in the distillation column (2) to be recovered to the reactor (1) after condensation.

The cooling heat exchanger 5 is connected to the upper side of the distillation column 2 and also to the branch pipes 11 and 12 so that the alkyl carbonate, which is a non-condensed reaction product in the distillation column 2, is relatively low in boiling point. After the inflow, condensation is carried out by cooling, and all or part of the condensate is refluxed through the pipe 11 to the distillation column 2 or the whole or part is taken out through the pipe 12.

The operation of the reactor according to the present invention configured as described above is as follows.

First, a heterogeneous catalyst is introduced into the reactor 1. The introduced heterogeneous catalyst is placed on top of the filter 1a. The amount of catalyst introduced is determined by the amount of aromatic carbonate to be produced. That is, the amount of heterogeneous catalyst required for production may be determined after experimentally determining the amount of aromatic carbonate prepared for a predetermined residence time by a certain amount of catalyst.

After the addition of the catalyst, dialkyl carbonate or alkyl aryl carbonate and aromatic hydroxy compound are introduced into the reactor 1. Then, a chemical reaction occurs inside the reactor 1, and the reaction liquid is accumulated in the reactor 1 while raising the water level.

When the amount of the reaction liquid in the reactor 1 exceeds a predetermined amount, the reaction liquid is circulated through the reactor 1, the pipe 8, and the heat exchanger 3 using the circulation pump 4.

A part of the circulating reaction liquid flows out of the reaction system through the pipe 9 by controlling the reactor level.

While the reaction solution is circulated, the heat exchanger 3 is used to raise the reaction temperature to a desired reaction temperature, and a boiling point of a relatively low boiling point component such as alkyl alcohol, which is a reaction byproduct, is provided to enable smooth extraction of the reaction byproduct.

The reaction by-products and the low boiling point components vaporized by the heat exchanger (3) enter the distillation column (2) through the upper side pipe, and the active ingredients having a relatively high boiling point in the distillation column (2) are condensed and passed through the lower side of the reactor (1). Is recovered.

Also, by-product alkyl alcohol and relatively low boiling alkyl carbonate are not condensed, but enter the cooling heat exchanger 5 through the pipe 10 in the gas phase without condensation and condensation by cooling. It is refluxed to the distillation column 2 through the pipe 11, or all or part is taken out through the pipe 12.

The extracted aromatic carbonate reactant is subjected to a conventional purification process such as distillation or crystallization.

The aromatic carbonate may be manufactured using a continuous production method of the aromatic carbonate using the heterogeneous catalyst as described above, and a reaction apparatus therefor.

The aromatic carbonate prepared by the present invention is used as a raw material for the production of various kinds of isocyanates and aromatic polycarbonates which do not use toxic phosgene gas, and is a transester between dialkyl carbonate and aromatic hydroxy compound. It is synthesized by transesterfication.

The transester reaction may be achieved in a balanced reaction by continuously removing by-products having a relatively low boiling point generated by the reaction. The reactor provided from the present invention is a device suitable for the removal of the continuous reaction by-products described above, and the reactivity such as conversion, selectivity, etc. is high through actual reaction experiments.

In addition, the reaction apparatus is an economic apparatus that minimizes the cost incurred in the process of using a homogeneous catalyst and a catalyst separation process by using a heterogeneous catalyst as a reaction catalyst, thereby continuously injecting a new catalyst into the reactor 1.

Aromatic carbonate is prepared from dialkyl carbonates, which can be represented by the following formula (1).

[Formula 1]

In the formula (1), R is an alkyl group. Examples of the alkyl group here are general alkyl groups such as methyl, ethyl, propyl, butyl and cyclohexyl.

These dialkyl carbonates are synthesized by alkyl aryl carbonates represented by the following formula (2) or (3) by transesterification with an aromatic hydroxy compound represented by ArOH (where Ar is an aromatic group). Reaction byproducts result in alkyl alcohols.

[Formula 2]

[Formula 3]

In the formulas (2) and (3), each Ar is an aromatic group having 5 to 30 carbon atoms.

Typical schemes related to the reaction process devised in the present invention can be represented as in the following schemes 1-3.

Scheme 1

Scheme 2

Scheme 3

In the formulas 1, 2, and 3, R is an alkyl group, and Ar is an aromatic group.

The above reactions are reversible reactions in which equilibrium exists and high reaction conversion can be obtained by extracting the reaction by-products generated during the reaction out of the reaction system, and since the reaction rate is fundamentally slow, the reaction rate is increased by using an efficient reaction catalyst. You can increase it.

The present invention will be described in more detail with reference to the following examples. However, an Example is for illustrating this invention and is not limited only to these.

EXAMPLE

The numerical values shown in the following examples were calculated by the following equations.

[Equation 1]

[Equation 2]

[Equation 3]

[Equation 4]

Example 1

Dialkyl carbonate (dimethyl carbonate, DMC) was used as a raw material dialkyl carbonate, and phenol was used as an aromatic hydroxy compound. The raw material dimethyl carbonate (DMC) and phenol were premixed so that the molar ratio was 3: 1 and continuously injected into the reactor at a flow rate of 33.3 g / min using a quantitative high pressure pump.

The reaction temperature was 160 ° C. and the reaction pressure was maintained at 4 atmospheres. At this time, the flow rate of the reaction liquid circulated by the circulation pump was maintained at 6.0 L / min. The reaction proceeded continuously under the same conditions for more than 12 hours, and the catalyst used was a heterogeneous catalyst in which titania (TiO ₂ ) was supported on silica having a diameter of 3 mm, and the amount of catalyst charged in the reactor was 1200 g.

As a result of the reaction, the yield of methyl phenyl carbonate (MPC) was 21.7 wt%, and the yield of diphenyl carbonate (DPC) was 0.34 wt%. The productivity of the catalyst used at this time was 92.6 MPC (g) / catalyst (kg) hr.

Examples 2-7

A continuous reaction of the same type as in Example 1 was carried out, but the reaction conditions were changed as shown in Table 2 below. The reaction results are also shown in Table 1.

division Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Reaction condition Temperature (℃) 160 170 160 170 160 180 Pressure (kg) 4 5 4.5 5.5 4.5 4.5 Molar ratio 3 3 5 5 5 5 feed rate (g / min) 11.5 11.5 11.5 11.5 22.4 33.3 Response result phenol molar conversion (%) 18.46 20.59 24.95 26.64 18.82 11.79 MPC yield (% by weight) 21.08 32.29 39.30 41.98 29.65 18.55 DPC yield (wt%) 0.54 0.69 0.72 0.75 0.54 0.36 total feed amount (g / h) 690 690 690 690 1344 1998 Phenolic Feed Amount (g / h) 178.2 178.2 119.3 119.3 232.3 345.3 MPC yield (g / h) 53.2 59.3 48.1 51.3 70.6 65.8 Catalyst productivity (MPC g / catalyst kg · h) 44.3 49.4 40.1 42.8 58.9 54.8

Example 8

In order to synthesize diphenyl carbonate (DPC) using the reaction apparatus shown in Figure 1, after removing a considerable amount of dimethyl carbonate (DMC) by using a distillation apparatus for the reaction product prepared in Examples 1-7, 50 liters of the reaction was obtained in a constant composition. The composition of the reaction was trace amounts of methanol, 34.44 wt% dimethyl carbonate (DMC), 13.92 wt% methylphenyl carbonate, 51.64 wt% phenol and 0.01 wt% diphenyl carbonate (DPC).

The catalyst used in synthesizing diphenyl carbonate was a heterogeneous catalyst in which titania (TiO ₂ ) was supported on silica having a diameter of 3 mm. The catalyst amount charged in the reactor was 1200 g. The reactants of the above-mentioned composition were continuously injected into the reactor at a constant flow rate of 1592 g / hr using a metering pump. At this time, the reaction temperature was maintained at 173 ℃, the reaction pressure was maintained at 550 mbar.

Through the pipe 12 located at the top of the reactor during the reaction, 0.2 wt% methanol, 43.59 wt% dimethyl carbonate (DMC), 2.68 wt% methylphenyl carbonate (MPC), 53.52 wt% phenol and trace amounts of diphenyl Reaction by-products and unreacted products having a composition of carbonate (DPC) were discharged at a constant flow rate of 1274 g / hr, and a large amount of diphenyl carbonate (DPC) at a constant flow rate of 318 g / hr through a pipe (9) located at the bottom of the reactor. The reaction product was prepared.

The composition of the reaction product was 1.49% by weight of DMC, 26.52% by weight of MPC, 30.9% by weight of phenol, 41.09% by weight of DPC. In this reaction, the catalyst productivity was 111 DPC g / kg kg hr.

Example 9

The same reactor as in Example 1 was used, and reactants of the same composition were continuously injected into the reactor. In this example, the flow rate of reactant injected is increased to 2750 g / hr to improve the productivity of the catalyst.

The reaction temperature was maintained at 165 ℃, the reaction pressure was maintained at 550 mbar. During the continuous reaction, 0.23 wt% methanol, 47.95 wt% dimethyl carbonate (DMC), 1.09 wt% methylphenyl carbonate (MPC) and 50.73 wt% phenol were passed through a branch tube 12 located above the reactor 1. Reaction by-products and unreacted products having a composition of trace amounts of diphenyl carbonate (DPC) were discharged at a constant flow rate of 2094 g / hr, and a large amount of diphenyl at a constant flow rate of 656 g / hr through a pipe (9) located at the bottom of the reactor. Reaction products including carbonate (DPC) were prepared.

At this time, the composition of the prepared reaction product was 2.74 wt% of DMC, 28.65 wt% of MPC, 40.57 wt% of phenol, and 28.04 wt% of DPC. In this reaction, the catalyst productivity was 142 DPC g / kg kg hr.

As described above, the production method and the reaction apparatus for the same according to the present invention do not undergo a reaction and separation process in the preparation of the aromatic carbonate by reacting the dialkyl carbonate and the aromatic hydroxy compound under a heterogeneous catalyst, so that the catalyst and the reactant are It is possible to economically and continuously produce aromatic carbonates in which high boiling point reaction products and catalysts do not exist without sticking to the device and the pipe inner wall and causing problems.

Claims (9)

A mixing step of injecting a dialkyl carbonate or an alkyl aryl carbonate and an aromatic hydroxy compound into the reactor while the heterogeneous catalyst is introduced into the reactor; A filtering step of filtering only the heterogeneous catalyst by filtering the reaction solution generated in the mixing step; A circulation step of circulating the reaction liquid filtered in the filtering step, while circulating while applying heat from the outside of the reactor; A distillation step of distilling the reaction by-products and the low boiling point component vaporized by the heat applied in the circulation step and condensing the active ingredients having a relatively high boiling point upon distillation and recovering them to the reactor; And Extraction step of extracting the high boiling point component of the final reactant in the reaction step in the middle of the circulation step Continuous production method of the aromatic carbonate using a heterogeneous catalyst comprising a. The method of claim 1, The distillation step further comprises a condensation step of condensing the alkyl alcohol carbonate and the relatively low boiling point alkyl carbonate by passing through the cooling heat exchanger in the distillation step, so that all or part of the reaction is refluxed or taken out to the outside Continuous process for preparing carbonates. The method of claim 2, Temperature range applied in the cooling heat exchanger is 10 ℃ to 50 ℃ a continuous manufacturing method of aromatic carbonate. The method of claim 1, The temperature range of the heat applied in the circulation step is 150 ℃ to 250 ℃ continuous manufacturing method of aromatic carbonate. The method of claim 1, The heterogeneous catalyst is a continuous method of producing an aromatic carbonate is a supported catalyst in which a transition metal oxide is supported on a carrier of 1 to 20 mm size. The method of claim 4, wherein The transition metal oxide is MoO ₃ , Ga ₂ O ₃ , V ₂ O ₅ , PbO, ZrO ₂ , TiO ₂ , CdO, Fe ₂ O ₃ , CuO, MgO, Y ₂ O ₃ , Mn ₃ NiO, ZnO, Nd ₂ A method for continuously preparing at least one aromatic carbonate selected from the group consisting of O ₃ , Co ₂ O ₃ , RuO ₂ , Nb ₂ O ₅ , and Cr ₂ O ₃ . The method of claim 1, Shape of the carrier is a continuous manufacturing method of aromatic carbonate is formed in any one of the shape, such as spherical, cylindrical, ring (ring). The method of claim 4, wherein The specific surface area of the carrier is 20 to 500 m 2 / g, the porosity is 0.25 to 0.8 cm 3 / g continuous method of producing an aromatic carbonate. A reactor located within itself and equipped with a filter for preventing the heterogeneous catalyst outflow and for discharging only the reaction liquid; A circulation pump connected to the side of the reactor in which the filter is installed; A heat exchanger connected between the circulating pump and the reactor, the heat exchanger configured to receive a reaction liquid from the reaction liquid circulation pump to raise and vaporize the reaction liquid to a desired reaction temperature; And It is connected to the upper part of the reactor and is supplied with vaporized reactants generated from the reactor and the heat exchanger to separate the high boiling point component and the low boiling point component to condense and recover the high boiling point component to the reactor, and the low boiling point component flows out into the gas phase. Distillation tower Reactor for the production of aromatic carbonate comprising a.