KR100846333B1 - Process for industrial production of an aromatic carbonate - Google Patents

Abstract

The problem to be solved by the present invention is an industrial scale of at least 1 ton per hour from the dialkyl carbonate and the aromatic monohydroxy compound using two groups of continuous multi-stage distillation column, high selectivity, high productivity and stable for a long time It is providing the specific method which can be manufactured. Although many proposals have been made on the production of aromatic carbonates by reactive distillation, they are all on a small scale and in a short time at the laboratory level, and there is no disclosure of any specific method or apparatus for enabling industrial scale mass production. In the present invention, two specific continuous multi-stage distillation columns are provided, and using an apparatus connected thereto, an industrial scale of at least 1 ton / hour, high selectivity, high productivity, and aromatic carbonate from dialkyl carbonate and aromatic monohydroxy compound is used. There is provided a specific method which can be manufactured stably for a long time.

Description

Method for industrially producing aromatic carbonates {PROCESS FOR INDUSTRIAL PRODUCTION OF AN AROMATIC CARBONATE}

This invention relates to the industrial manufacturing method of aromatic carbonates. More specifically, the dialkyl carbonate and the aromatic monohydroxy compound are transesterified in a two-stage continuous multi-stage distillation column in which a catalyst is present, and the aromatic carbonate containing, as a main product, a diaryl carbonate useful as a raw material of the transesterification polycarbonate. The present invention relates to a method for mass production of industrial products.

Aromatic carbonate is important as a raw material for producing aromatic polycarbonate, which is the most in demand engineering plastic, without using toxic phosgene. As a manufacturing method of an aromatic carbonate, the method by reaction of an aromatic monohydroxy compound and phosgene has been known for a long time, and it is variously examined in recent years. However, this method, in addition to the problem of using phosgene, contains an chlorine-based impurity that is difficult to separate in the aromatic carbonate produced according to this method and cannot be used as a raw material of an aromatic polycarbonate as it is. This chlorine-based impurity significantly inhibits the polymerization reaction of the transesterification polycarbonate which is carried out in the presence of a trace amount of basic catalyst. For example, even at 1 ppm, the chlorine-based impurity hardly proceeds polymerization. Therefore, in order to use as a raw material for the transesterification polycarbonate, sufficient washing and washing with oil of an aqueous alkali solution and hot water are required in a multi-step cumbersome separation and purification process such as distillation, distillation, and the like. There are many problems to carry out this method on an economically suitable industrial scale, such as a decrease in yield due to loss or distillation loss.

On the other hand, the manufacturing method of aromatic carbonate by the transesterification reaction of a dialkyl carbonate and an aromatic monohydroxy compound is also known. However, all of these transesterification reactions are equilibrium reactions, and since the equilibrium is not only extremely skewed to the origin, but also the reaction rate is slow, industrially mass production of aromatic carbonates by this method is It was accompanied by great difficulties. In order to improve this, some proposals are made, but most of them are related to the development of a catalyst for increasing the reaction rate. Numerous metal compounds have been proposed as catalysts for this type of transesterification reaction. For example, compounds which generate Lewis acids or Lewis acids, such as transition metal halides (patent document 1: Unexamined-Japanese-Patent No. 51-105032, Unexamined-Japanese-Patent No. 56-123948, Japan Unexamined-Japanese-Patent No. 56). -123949 (West German Patent Publication No. 2524812, British Patent No. 1495530, US Patent No. 4,418,26), Japanese Patent Application Publication No. 51-75044 (West German Publication No. 2552907, US Patent No. 4045464) Specification)), tin compounds, such as organic tin alkoxide and organic tin oxides (patent document 2: Unexamined-Japanese-Patent No. 54-48733 (West Germany Unexamined-Japanese-Patent No. 2736062), Unexamined-Japanese-Patent No. 54-63023). Japanese Patent Application Laid-Open No. 60-169444 (US Patent No. 4452110), Japanese Patent Application Laid-Open No. 60-169445 (US Patent No. 4452704), Japanese Patent Laid-Open No. 62-277345, Japanese Patent Laid-Open Publication No. 1-265063 Crude), salts and alkoxides of alkali metals or alkaline earth metals (see Patent Document 3: JP-A-57-176932), Lead Compounds (Patent Document 4: JP-A-57-176932, JP) Patent publication No. Hei 1-93560), complexes of metals such as copper, iron and zirconium (Patent Document 5: Japanese Laid-Open Patent Publication No. 57-183745), titanate esters (Patent Document 6: Japanese Laid-Open Patent Publication) No. 58-185536 (US Pat. No. 4410464), Japanese Unexamined Patent Publication No. Hei 1-265062, A mixture of Lewis acid and protonic acid (Patent Document 7: Japanese Laid-Open Patent Publication No. 60-173016 (US Patent No. 4609501 specification), compounds such as Sc, Mo, Mn, Bi, Te (see Patent Document 8: Japanese Unexamined Patent Application Publication No. Hei 1-265064), ferric acetate (Patent Document 9: Japanese Unexamined Patent Publication) 61-172852) have been proposed. However, since the development of a catalyst alone cannot solve the problem of disadvantageous equilibrium, there are many problems to be studied, including the examination of the reaction system, in order to obtain an industrial production method for mass production.

In addition, attempts have been made to improve the yield of aromatic carbonates by leaving the equilibrium to the measurement measurement as possible by studying the reaction system. For example, in the reaction of dimethyl carbonate and phenol, a by-product distillation of methanol by-produced with an azeotropic forming agent is carried out by azeotropy (Patent Document 10: Japanese Patent Application Laid-Open No. 54-48732 (West German Patent Application Publication No. 736063). (US Pat. No. 4,425,337)), a method of adsorbing and removing by-product methanol with a molecular sieve (Patent Document 11: Japanese Unexamined Patent Publication No. 58-185536 (US Pat. No. 410464)) It is proposed. Moreover, by the apparatus provided with the distillation column in the upper part of a reactor, the method of distilling separation with the unreacted raw material which evaporates simultaneously while separating the by-product alcohols from a reaction mixture is also proposed (patent document 12: Unexamined-Japanese-Patent). Examples of Patent Publication No. 56-123948 (Specification of U.S. Patent No. 4,418,26), Examples of Japanese Patent Application Laid-Open No. 56-25138, Implementation of Japanese Patent Application Laid-Open No. 60-169444 (Specification of U.S. Patent 4455110) For example, the Example of Unexamined-Japanese-Patent No. 60-169445 (The specification of US Pat. No. 4452704), The Example of Unexamined-Japanese-Patent No. 60-173016 (The specification of U.S. Patent No. 4,460,501) (Examples of -172852, Examples of JP-A-61-291545, Examples of JP-A-62-277345).

However, these reaction methods are basically batch methods or conversion methods. The improvement of the reaction rate by the catalyst development is also limited to these transesterification reactions, and because the reaction rate is slow, it is considered that the batch method is preferable to the continuous method. Among them, a continuous stirred tank reactor (CSTR) method having a distillation column at the top of the reactor as a continuous method is also proposed, but the reaction rate cannot be increased because the reaction rate is slow or the gas-liquid interface of the reactor is small with respect to the liquid capacity. There is a problem. Therefore, it is difficult to attain the objective of continuously producing a large amount of aromatic carbonates in a long time and stably with these methods, and there are many problems to be solved in order to achieve economically suitable industrial practice.

The present inventors continuously supply a dialkyl carbonate and an aromatic hydroxy compound to a multi-stage distillation column, continuously react in a column in which a catalyst is present, and continuously extract a low boiling point component containing alcohol by-produced by distillation. In addition, the reaction distillation method which extracts the component containing the produced | generated alkylaryl carbonate from the bottom of a column (refer patent document 13: Unexamined-Japanese-Patent No. 3-291257), and supplies alkylaryl carbonate continuously to a multistage distillation column, The catalyst was continuously reacted in the column in which the catalyst was present to continuously extract the low-boiling component containing the by-product dialkyl carbonate by distillation, and the component containing the produced diaryl carbonate was extracted from the bottom of the column. Reactive distillation (see Patent Document 14: Japanese Patent Application Laid-open No. Hei 4-9358). A reaction distillation method (see Patent Document 15: Japanese Patent Application Laid-Open No. 4-211038) for continuously producing a diaryl carbonate while using a multi-stage distillation column and efficiently recycling by-product dialkyl carbonates, dialkyl carbonates and aromatics After supplying a hydroxy compound and the like continuously to the multi-stage distillation column, the liquid flowing down the column is extracted from the side outlet formed at the middle and / or bottom of the distillation column, introduced into a reactor installed outside the distillation column, and reacted. A reaction distillation method which reacts in both the reactor and the distillation column by introducing into a circulation inlet formed at an upper stage than the stage having the outlet port (Patent Document 16: Japanese Unexamined Patent Publication No. 4-224547, Japan). Transesterification reactions thereof), and the like (see Japanese Patent Application Laid-open No. Hei 4-230242 and Japanese Patent Laid-Open No. Hei 4-235951)) Developed a reaction distillation method in which a reaction and distillation were performed simultaneously in a continuous multi-stage distillation column, and the world first disclosed that a reaction distillation method is useful for these transesterification reactions.

These reaction distillation methods proposed by the present inventors are the first to enable efficient and continuous production of aromatic carbonates, and since then, many of the same reactive distillation methods based on these disclosures have been proposed. Reference Documents 17 to 32; Patent Document 17: International Publication No. 00/18720 (U.S. Patent No. 5362901); Patent Document 18: Italian Patent Publication No. 01255746; Patent Document 19: Japanese Patent Application Laid-Open No. 6-9506 (European Patent 0560159, U.S. Patent No. 5528965); Patent Document 20: Japanese Patent Application Laid-Open No. 6-41022 (European Patent 0572870 Specification, US Patent No. 5362901 Specification); Patent Document 21: Japanese Publication Japanese Patent Application Laid-open No. Hei 6-157424 (European Patent 0582931, US Patent No. 5334742), Japanese Patent Application Laid-Open No. 6-184058 (European Patent 0582930, Japanese Patent Laid-Open No. 5344954); Patent Document 22: Japanese Patent Application Laid-Open No. 7-304713; Patent Document 23: Japanese Patent Application Laid-Open No. 9-40616; Patent Document 24: Japanese Patent Laid-Open No. 9-59225; Patent Document 25: Japanese Patent Application Laid-Open No. 9-110805; Patent Document 26: Japanese Patent Application Laid-Open No. 9-165357; Patent Document 27: Japanese Patent Application Laid-Open No. 9-173819; Patent Document 28: Japanese Patent Application Laid-Open Japanese Patent Application Laid-Open No. 9-176094, Japanese Patent Application Laid-Open No. 2000-191596, Japanese Patent Application Laid-Open No. 2000-191597; Patent Document 29: Japanese Patent Application Laid-Open No. 9-194436 (European Patent 0785184, US Patent No. 5705673) Patent Document 30: International Publication No. 00/18720 (US Pat. No. 6,038,42); Patent Document 31: Japanese Patent Application Laid-Open No. 2001-64234, Japanese Patent Application Laid-Open No. 2001-64235; Patent Document 32: International Publication No. 02/40439 (U.S. Pat. U.S. Patent 665995, U.S. Patent 666061).

In addition, in the reaction distillation method, the present applicant does not require a large amount of catalyst and can stably produce a high-purity aromatic carbonate for a long time. After reacting a high-boiling substance containing a catalyst component with a working substance, Separation and recycling of the catalyst component (see Patent Document 31: JP-A-2001-64234; JP-A-2001-64235), or a polyvalent aromatic hydroxy compound in the reaction system in a mass ratio of 2.0 to the catalyst metal. A method (see Patent Document 32: International Publication No. 02/40439 (US Pat. No. 6,684,94, US Pat. No. 6,684,95, US Pat. No. 6,600,611 specifications)) was proposed. Moreover, the present inventors also proposed the method of making diphenyl carbonate by the reaction distillation method using 70-99 mass% of the phenol by-produced in a superposition | polymerization process as a raw material, and making this the polymerization raw material of aromatic polycarbonate (patent Document 33: See International Publication No. 97/11049 (European Patent 0855384 specification, US Pat. No. 5872275 specification).

However, all prior documents suggesting the production of aromatic carbonates by these reactive distillation methods do not disclose any specific methods or apparatuses that enable industrial scale mass production (e.g., more than 1 ton per hour). There is no description to suggest them. For example, the height (H ₁ and H ₂ : cm), diameter (D ₁ and D ₂ : cm), number of stages of the two-group reaction distillation column disclosed for producing mainly diphenyl carbonate (DPC) from dimethyl carbonate and phenol (Iii) (n ₁ and n ₂ ) and the amount of reaction raw material introduced (Q ₁ and Q ₂ : Kg / hr) is described in the following table.

H ₁ D ₁ n ₁ Q ₁ H ₂ D ₂ N ₂ Q ₂ Patent Literature 600 25 20 66 600 25 20 23 15 350 2.8 - 0.2 305 5-10 15 + fillers 0.6 21 500 5 50 0.6 400 8 50 0.6 23 100 4 - 1.4 200 4 - 0.8 24 300 5 40 1.5 - 5 25 0.7 28 1200 20 40 86 600 25 20 31 33 34 600 - 20 66 600 - 20 22 35

[Patent Document 34]: See Japanese Laid-Open Patent Publication No. Hei 11-92429 (European Patent No. 1016648, US Patent No.6262210))

[Patent Document 35]: Japanese Patent Application Laid-open No. Hei 9-255772 (see European Patent 0892001 Specification and US Patent No. 5747609 Specification)

That is, the largest of two continuous multistage distillation columns used in carrying out this reaction by the reaction distillation method is disclosed in Patent Documents 33 and 34 of the present applicant. In this way, the maximum value of each condition in the continuous multi-stage distillation column as disclosed for the reaction is, H ₁ = 1200 cm, H ₂ = 600 cm, D ₁ = 20 cm, D ₂ = 25 cm, n ₁ = n ₂ = 50 (Patent Document 23), Q ₁ = 86 kg / hr, Q ₂ = 31 kg / hr The yield of diphenyl carbonate was only about 6.7 kg / hr, which was not an industrial scale.

Disclosure of the Invention

Problems to be Solved by the Invention

The problem to be solved by the present invention is an industrial scale of at least 1 ton per hour of aromatic carbonates containing diaryl carbonate as the main product from two distillation columns of dialkyl carbonate and aromatic monohydroxy compound. In addition, the present invention provides a specific method for producing a high selectivity, high productivity, and long-term stability.

Means to solve the problem

Since the present inventors have disclosed a method for producing aromatic carbonates using a continuous multi-stage distillation column, there have been many proposals for a method for producing aromatic carbonates by reactive distillation, but these are all small and short-term laboratory levels. There is no disclosure of any specific methods or devices that enable mass production on a scale. Therefore, the present inventors have repeatedly studied to find a concrete method capable of stably producing aromatic carbonates having an industrial scale of 1 ton or more per hour, high selectivity, high productivity, and having a diaryl carbonate as a main product for a long time. As a result, the present invention was reached.

That is, in the first aspect of the present invention,

1. A method for producing aromatic carbonates using dialkyl carbonates and aromatic monohydroxy compounds as raw materials and having diaryl carbonates as a main product,

(i) continuously supplying the raw materials into the first continuous multistage distillation column in which the catalyst is present;

(ii) reacting the raw materials in the first column to produce alcohols and alkylaryl carbonates;

(iii) continuously extracting the first low boiling point reaction mixture containing the resulting alcohols from the top of the first column, and the first tower high boiling point reaction mixture containing the resulting alkylaryl carbonates in the first column. Continuous extraction from the lower portion into the liquid phase,

(iv) the first tower high boiling point reaction mixture is continuously fed into a second continuous multistage reaction distillation column in which a catalyst is connected to the first continuous multistage distillation column, and dialkyl carbonates and diaryl carbonates Reacting in the second column to produce

(v) The second tower high boiling point reaction mixture containing the produced dialkyl carbonates is continuously extracted in a gaseous form from the top of the second column, and the second tower high boiling point reaction containing the produced diaryl carbonates is produced. Continuously extracting the mixture from the lower part of the second column into the liquid phase,

(a) The dialkyl carbonate continuously supplied into the first continuous multistage distillation column is 0.1 to 10 in molar ratio with respect to the aromatic monohydroxy compound,

(b) The first continuous multi-stage distillation column has a hard plate portion above and below a cylindrical body portion having a length L ₁ (cm) and an inner diameter D ₁ (cm), and has an internal having a single stage n ₁ therein. The gas outlet of the inner diameter d ₁₁ (cm) in the tower | column part, or the upper part of a tower near it, the liquid outlet of inner diameter d ₁₂ (cm) in the tower bottom, or the lower part of a tower near it, The gas Having at least one inlet above the outlet and at the top and / or middle of the tower, at least one inlet above the liquid outlet and at the bottom of the tower,

(1) The length L ₁ (cm) satisfies the formula (1),

1500 ≤ L ₁ ≤ 8000 (1)

(2) The inner diameter D ₁ (cm) of the tower satisfies the formula (2),

100 ≤ D ₁ ≤ 2000 (2)

(3) The ratio between the length L ₁ (cm) and the inner diameter D ₁ (cm) of the tower satisfies the formula (3),

2 ≤ L ₁ / D ₁ ≤ 40 (3)

(4) The number n ₁ satisfies the formula (4),

20 ≤ n ₁ ≤ 120 (4)

(5) The ratio between the inner diameter D ₁ (cm) of the tower and the inner diameter d ₁₁ (cm) of the gas outlet port satisfies Expression (5),

5 ≤ D ₁ / d ₁₁ ≤ 30 (5)

(6) The ratio between the inner diameter D ₁ (cm) of the tower and the inner diameter d ₁₂ (cm) of the liquid outlet port satisfies Expression (6),

3 ≤ D ₁ / d ₁₂ ≤ 20 (6)

(c) The second continuous multi-stage distillation column has a structure having a hard plate portion above and below a cylindrical body portion having a length L ₂ (cm) and an inner diameter D ₂ (cm) and having an internal number having a single stage n ₂ therein. A gas outlet having an inner diameter d ₂₁ (cm) at the top of the tower, or near the top thereof, a liquid outlet having an inner diameter d ₂₂ (cm) at the bottom of the tower, or a lower portion of the tower close thereto; Having at least one inlet at the top and / or middle of the tower, at least one inlet above the liquid outlet and at the bottom of the tower,

(1) Length L ₂ (cm) satisfies formula (7),

1500 ≤ L ₂ ≤ 8000 (7)

(2) The inner diameter D ₂ (cm) of the tower satisfies the formula (8),

100 ≤ D ₂ ≤ 2000 (8)

(3) The ratio of the length L ₂ (cm) and the inner diameter D ₂ (cm) of the tower satisfies the formula (9),

2 ≤ L ₂ / D ₂ ≤ 40 (9)

(4) The singular n ₂ satisfies the formula (10),

10 ≤ n ₂ ≤ 80 (10)

(5) The ratio between the inner diameter D ₂ (cm) of the tower and the inner diameter d ₂₁ (cm) of the gas outlet port satisfies Expression (11),

2 ≤ D ₂ / d ₂₁ ≤ 15 (11)

(6) The ratio between the inner diameter D ₂ (cm) of the tower and the inner diameter d ₂₂ (cm) of the liquid outlet port satisfies Equation (12).

5 ≤ D ₂ Of d ₂₂ ≤ 30 (12)

Characterized by

2. In the said process (ii) and (iv), distillation is also performed simultaneously, The method of the said claim | item 1 characterized by the above-mentioned.

3. The process according to item 1 or 2 above, wherein the production amount of diaryl carbonate is 1 ton or more per hour.

Moreover, in another aspect of the manufacturing method which concerns on this invention,

4. A dialkyl carbonate and an aromatic monohydroxy compound are used as raw materials, and the raw materials are continuously supplied into a first continuous multistage distillation column in which a catalyst is present, and the reaction and distillation are simultaneously performed in the first column to produce an alcohol. The first tower low boiling point reaction mixture containing the stream was continuously discharged in gaseous form from the top of the first column, and the first tower high boiling point reaction mixture containing the resulting alkylaryl carbonates was transferred from the bottom of the first column to the liquid phase. It extracts continuously, the 1st tower high boiling point reaction mixture is continuously supplied to the 2nd continuous multistage distillation column in which a catalyst exists, and reaction and distillation are simultaneously performed in the 2nd column, and contains dialkyl carbonates produced | generated. The second tower low boiling point reaction mixture was continuously extracted in a gaseous form from the top of the second tower, and the resulting diaryl carbo The second tower high boiling point reaction mixture containing yttres was continuously drawn out from the bottom of the second column in the liquid phase, while the second tower low boiling reaction mixture containing dialkyl carbonates was continuously in the first continuous multistage distillation column. In the continuous production of aromatic carbonates containing diaryl carbonates as a main product by supplying,

(a) The dialkyl carbonate continuously supplied into the first continuous multistage distillation column is 0.1 to 10 in molar ratio with respect to the aromatic monohydroxy compound,

(b) The first continuous multi-stage distillation column has a structure having a hard plate portion above and below a cylindrical body portion having a length L ₁ (cm) and an inner diameter D ₁ (cm) and having an internal number having a single stage n ₁ therein. Inner diameter at the top of the tower, or near the tower d ₁₁ (Cm) gas outlet, the bottom of the column or the bottom of the tower close to it, the liquid outlet of the inner diameter d ₁₂ (cm), lower than the gas outlet, at least one inlet at the top and / or middle of the tower At least one inlet at the bottom of the tower and above the liquid outlet,

(1) The length L ₁ (cm) satisfies the formula (1),

1500 ≤ L ₁ ≤ 8000 (1)

(2) The inner diameter D ₁ (cm) of the tower satisfies the formula (2),

100 ≤ D ₁ ≤ 2000 (2)

(3) The ratio between the length L ₁ (cm) and the inner diameter D ₁ (cm) of the tower satisfies the formula (3),

2 ≤ L ₁ / D ₁ ≤ 40 (3)

(4) The number n ₁ satisfies the formula (4),

20 ≤ n ₁ ≤ 120 (4)

(5) The ratio between the inner diameter D ₁ (cm) of the tower and the inner diameter d ₁₁ (cm) of the gas outlet port satisfies Expression (5),

5 ≤ D ₁ Of d ₁₁ ≤ 30 (5)

(6) The ratio between the inner diameter D ₁ (cm) of the tower and the inner diameter d ₁₂ (cm) of the liquid outlet port satisfies Expression (6),

3 ≤ D ₁ / d ₁₂ ≤ 20 (6)

(c) The second continuous multi-stage distillation column has a structure having a hard plate portion above and below a cylindrical body portion having a length L ₂ (cm) and an inner diameter D ₂ (cm) and having an internal number having a single stage n ₂ therein. A gas outlet having an inner diameter d ₂₁ (cm) at the top of the tower, or near the top thereof, a liquid outlet having an inner diameter d ₂₂ (cm) at the bottom of the tower, or a lower portion of the tower close thereto; Having at least one inlet at the top and / or middle of the tower, at least one inlet above the liquid outlet and at the bottom of the tower,

(1) Length L ₂ (cm) satisfies formula (7),

1500 ≤ L ₂ ≤ 8000 (7)

(2) The inner diameter D ₂ (cm) of the tower satisfies the formula (8),

100 ≤ D ₂ ≤ 2000 (8)

(3) The ratio of the length L ₂ (cm) and the inner diameter D ₂ (cm) of the tower satisfies the formula (9),

2 ≤ L ₂ / D ₂ ≤ 40 (9)

(4) The singular n ₂ satisfies the formula (10),

10 ≤ n ₂ ≤ 80 (10)

(5) The ratio between the inner diameter D ₂ (cm) of the tower and the inner diameter d ₂₁ (cm) of the gas outlet port satisfies Expression (11),

2 ≤ D ₂ / d ₂₁ ≤ 15 (11)

(6) The ratio between the inner diameter D ₂ (cm) of the tower and the inner diameter d ₂₂ (cm) of the liquid outlet port satisfies Equation (12).

5 ≤ D ₂ Of d ₂₂ ≤ 30 (12)

Industrial production method of aromatic carbonates containing a diaryl carbonate as a main product,

5. The method according to item 4, wherein the production amount of diaryl carbonate is at least 1 ton per hour,

6. d ₁₁ and d ₁₂ satisfy equation (13), and d ₂₁ and d ₂₂ satisfy equation (14),

1 ≤ d ₁₂ Of d ₁₁ ≤ 5 (13)

1 ≤ d ₂₁ / d ₂₂ ≤ 6 (14)

The method according to any one of items 1 to 5 above.

7. L ₁ , D ₁ , L ₁ of the first continuous multi-stage distillation column Of D ₁ , n ₁ , D ₁ Of d ₁₁ , D ₁ Of d ₁₂ is 2000 ≤ L ₁ ≤ 6000, 150 ≤ D ₁ ≤ 1000, 3 ≤ L ₁ Of D ₁ ≤ 30, 30 ≤ n ₁ ≤ 100, 8 ≤ D ₁ Of d ₁₁ ≤ 25, 5 ≤ D ₁ Of d ₁₂ ≤ 18, and L ₂ , D ₂ , L ₂ of the second continuous multi-stage distillation column Of D ₂ , n ₂ , D ₂ Of d _{21 ,} D ₂ Of d ₂₂ is 2000 ≤ L ₂ ≤ 6000, 150 ≤ D ₂ ≤ 1000, 3 ≤ L ₂ Of D ₂ ≤ 30, 15 ≤ n ₂ ≤ 60, 2.5 ≤ D ₂ Of d ₂₁ ≤ 12, 7 ≤ D ₂ Of d ₂₂ ? 25, wherein the method according to any one of items 1 to 6 above,

8. L ₁ , D ₁ , L ₁ of the first continuous multi-stage distillation column Of D ₁ , n ₁ , D ₁ Of d _{11 ,} D ₁ Of d ₁₂ is 2500 ≤ L ₁ ≤ 5000, 200 ≤ D ₁ ≤ 800, 5 ≤ L ₁ Of D ₁ ≤ 15, 40 ≤ n ₁ ≤ 90, 10 ≤ D ₁ / d ₁₁ ≤ 25, 7 ≤ D ₁ / d ₁₂ ≤ 15, and L ₂ , D ₂ , L ₂ of the second continuous multi-stage distillation column Of D ₂ , n ₂ , D ₂ Of d _{21 ,} D ₂ Of d ₂₂ is 2500 ≤ L ₂ ≤ 5000, 200 ≤ D ₂ ≤ 800, 5 ≤ L ₂ Of D ₂ ≤ 15, 20 ≤ n ₂ ≤ 50, 3 ≤ D ₂ Of d ₂₁ ≤ 10, 9 ≤ D ₂ Of d ₂₂ ? 20, wherein the method according to any one of items 1 to 7,

9. The method according to any one of the above items 1 to 8, wherein the first continuous multistage distillation column and the second continuous multistage distillation column are distillation columns each having a tray and / or a packing as its internal.

10. The first continuous multistage distillation column is a shelf single distillation column having a tray as its internal, and the second continuous multistage distillation column is a distillation column having both a packing and a tray as its internal. Method described,

11. The method according to item 9 or 10 above, wherein each of the trays of the first continuous multistage distillation column and the second continuous multistage distillation column is a porous plate tray having a porous plate portion and a downcomer portion.

12. The method according to item 11, wherein the porous plate tray has 100 to 1000 holes per 1 m 2 of the porous plate portion.

13. The method according to item 11 or 12 above, wherein the cross-sectional area per hole in the perforated plate tray is 0.5 to 5 cm 2.

14. The method according to item 9 or 10 above, wherein the second continuous multi-stage distillation column is a distillation column having a packing at the upper side and a tray at the bottom thereof as the internal.

15. The process according to any one of items 9 to 14 above, wherein the filling of the internal of the second continuous multi-stage distillation column is one or two or more regular fillings,

16. The regular fillings of the second continuous multi-stage distillation column are Melapak, Gempak, TECHNO-PAK, FLEXI-PAK, Sulzer packing, Good roll packing. Goodroll, at least one selected from Glitchgrid, the method according to item 15,

17. The method according to any one of items 1 to 16, wherein two or more distillation columns are used as the first continuous multistage distillation column.

18. As the second continuous multi-stage distillation column, there is provided the method according to any one of items 1 to 17, wherein two or more distillation columns are used.

Moreover, in the 2nd aspect of this invention,

19. Provided are aromatic carbonates produced by the method according to any one of items 1 to 18 and having a halogen content of 0.1 ppm or less.

Moreover, in the 3rd aspect of this invention,

20. A reactive distillation apparatus having a first continuous multistage distillation column for carrying out reaction and distillation, and a second continuous multistage distillation column for carrying out reaction and distillation, connected to the first continuous multistage distillation column, wherein (a) the 1 continuous multistage distillation column, length L ₁ (Cm), having a hard plate portion above and below a cylindrical body portion having an inner diameter D ₁ (cm), and having a internal structure having a singular number n ₁ therein, and having an inner diameter d _{11 at} the top of the tower or near the top thereof. (Cm) gas outlet, the bottom of the column or the bottom of the tower close to it, the liquid outlet of the inner diameter d ₁₂ (cm), lower than the gas outlet, at least one inlet at the top and / or middle of the tower At least one inlet at the bottom of the tower and above the liquid outlet,

(1) The length L ₁ (cm) satisfies the formula (1),

1500 ≤ L ₁ ≤ 8000 (1)

(2) The inner diameter D ₁ (cm) of the tower satisfies the formula (2),

100 ≤ D ₁ ≤ 2000 (2)

(3) The ratio between the length L ₁ (cm) and the inner diameter D ₁ (cm) of the tower satisfies the formula (3),

2 ≤ L ₁ / D ₁ ≤ 40 (3)

(4) The number n ₁ satisfies the formula (4),

20 ≤ n ₁ ≤ 120 (4)

(5) The ratio between the inner diameter D ₁ (cm) of the tower and the inner diameter d ₁₁ (cm) of the gas outlet port satisfies Expression (5),

5 ≤ D ₁ / d ₁₁ ≤ 30 Equation (5)

(6) The ratio between the inner diameter D ₁ (cm) of the tower and the inner diameter d ₁₂ (cm) of the liquid outlet port satisfies Expression (6),

3 ≤ D ₁ / d ₁₂ ≤ 20 (6)

(b) The second continuous multi-stage distillation column has a structure having a hard plate portion above and below a cylindrical body portion having a length L ₂ (cm) and an inner diameter D ₂ (cm), and having an internal having a single stage n ₂ therein. A gas outlet having an inner diameter d ₂₁ (cm) at the top of the tower, or near the top thereof, a liquid outlet having an inner diameter d ₂₂ (cm) at the bottom of the tower, or a lower portion of the tower close thereto; Having at least one inlet at the top and / or middle of the tower, at least one inlet above the liquid outlet and at the bottom of the tower,

(1) Length L ₂ (cm) satisfies formula (7),

1500 ≤ L ₂ ≤ 8000 (7)

(2) The inner diameter D ₂ (cm) of the tower satisfies the formula (8),

100 ≤ D ₂ ≤ 2000 Equation (8)

(3) The ratio of the length L ₂ (cm) and the inner diameter D ₂ (cm) of the tower satisfies the formula (9),

2 ≤ L ₂ / D ₂ ≤ 40 (9)

(4) The singular n ₂ satisfies the formula (10),

10 ≤ n ₂ ≤ 80 (10)

(5) The ratio between the inner diameter D ₂ (cm) of the tower and the inner diameter d ₂₁ (cm) of the gas outlet port satisfies Expression (11),

2 ≤ D ₂ / d ₂₁ ≤ 15 Equation (11)

(6) The ratio between the inner diameter D ₂ (cm) of the tower and the inner diameter d ₂₂ (cm) of the liquid outlet port satisfies Equation (12).

5 ≤ D ₂ / d ₂₂ ≤ 30 Equation (12)

Reactive distillation apparatus, characterized in that

21. The d ₁₁ and the d ₁₂ satisfy Equation (13), and the d ₂₁ and the d ₂₂ satisfy Equation (14).

1 ≤ d ₁₂ / d ₁₁ ≤ 5 Equation (13)

1 ≤ d ₂₁ / d ₂₂ ≤ 6 Equation (14)

A reactive distillation apparatus according to item 20,

22. L ₁ , D ₁ , L ₁ of the first continuous multi-stage distillation column / D ₁ , n ₁ , D ₁ / d _{11 ,} D ₁ / d ₁₂ is 2000 ≤ L ₁ ≤ 6000, 150 ≤ D ₁ ≤ 1000, 3 ≤ L ₁ / D ₁ ≤ 30, 30 ≤ n ₁ ≤ 100, 8 ≤ D ₁ / d ₁₁ ≤ 25, 5 ≤ D ₁ / d ₁₂ ≤ 18, and L ₂ , D ₂ , L ₂ of the second continuous multi-stage distillation column / D ₂ , n ₂ , D ₂ / d ₂₁ , D ₂ / d ₂₂ is 2000 ≤ L ₂ ≤ 6000, 150 ≤ D ₂ ≤ 1000, 3 ≤ L ₂ / D ₂ ≤ 30, 15 ≤ n ₂ ≤ 60, 2.5 ≤ D ₂ / d ₂₁ ≤ 12, 7 ≤ D ₂ / d ₂₂ ≤ 25, wherein the reaction distillation apparatus according to item 20 or 21,

23. L ₁ , D ₁ , L ₁ of the first continuous multi-stage distillation column / D ₁ , n ₁ , D ₁ / d ₁₁ , D ₁ / d ₁₂ is 2500 ≤ L ₁ ≤ 5000, 200 ≤ D ₁ ≤ 800, 5 ≤ L ₁ / D ₁ ≤ 15, 40 ≤ n ₁ ≤ 90, 10 ≤ D ₁ / d ₁₁ ≤ 25, 7 ≤ D ₁ / d ₁₂ ≤ 15, and L ₂ , D ₂ , L ₂ of the second continuous multi-stage distillation column / D ₂ , n ₂ , D ₂ / d _{21 ,} D ₂ / d ₂₂ is 2500 ≤ L ₂ ≤ 5000, 200 ≤ D ₂ ≤ 800, 5 ≤ L ₂ / D ₂ ≤ 15, 20 ≤ n ₂ ≤ 50, 3 ≤ D ₂ / d ₂₁ ≤ 10, 9 ≤ D ₂ / d ₂₂ ≤ 20, the reaction distillation apparatus according to any one of items 20 to 22,

24. The reactive distillation apparatus according to any one of items 20 to 23, wherein the first continuous multistage distillation column and the second continuous multistage distillation column are distillation columns each having a tray and / or a packing as its internal.

25. The above item 24, wherein the first continuous multistage distillation column is a shelf single distillation column having a tray as its internal, and the second continuous multistage distillation column is a distillation column having both a packing and a tray as its internal. Described reactive distillation apparatus,

26. The reactive distillation apparatus according to item 24 or 25, wherein each of the trays of the first continuous multistage distillation column and the second continuous multistage distillation column is a porous plate tray having a porous plate portion and a downcomer portion.

27. The reactive distillation apparatus according to item 26, wherein the porous plate tray has 100 to 1000 holes per 1 m 2 of the porous plate portion.

28. The reactive distillation apparatus according to item 26 or 27, wherein the cross-sectional area per hole in the porous plate tray is 0.5 to 5 cm 2.

29. The reaction distillation apparatus according to item 24 or 25, wherein the second continuous multi-stage distillation column is a distillation column having a packing at a lower portion and a tray at a lower portion thereof as an internal.

30. The reactive distillation apparatus according to any one of items 24 to 29, wherein the packing of the internal of the second continuous multi-stage distillation column is a regular packing having one group or two or more groups,

31. The reactive distillation apparatus according to item 30, wherein the regular filler material of the second continuous multi-stage distillation column is at least one selected from melapack, gempack, technopack, flexipack, sulzer packing, good roll packing, and glitch grid. ,

32. A reactive distillation apparatus according to any one of items 20 to 31, wherein the first continuous multi-stage distillation column uses two or more distillation columns.

33. As the second continuous multi-stage distillation column, two or more distillation columns are used, and the reaction distillation apparatus according to any one of items 20 to 32 is provided.

Effects of the Invention

By carrying out the present invention, aromatic carbonates containing diaryl carbonate as the main product at a high selectivity of at least 95%, preferably at least 97%, more preferably at least 98%, from dialkyl carbonates and aromatic monohydroxy compounds. Long term at least 1 tonne per hour, preferably at least 2 tonnes per hour, more preferably at least 3 tonnes per hour, at least 2000 hours, preferably at least 3000 hours, more preferably at least 5000 hours, It was found that it can be manufactured stably. Diaryl carbonate obtained by isolating and purifying aromatic carbonates containing diaryl carbonate obtained as the main component by distillation or the like is of high purity. It is useful as a raw material such as urethane. Moreover, in this invention, since the raw material and catalyst which do not contain a halogen are normally used, the halogen content of the diaryl carbonate obtained is 0.1 ppm or less, Preferably it is 10 ppb or less, More preferably, it is 1 ppb or less.

Implement the invention  Best form for

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

Dialkyl carbonate used by this invention is represented by General formula (15).

R ¹ OCOOR ¹ (15)

Here, R <^1> represents a C1-C10 alkyl group, a C3-C10 alicyclic group, and a C6-C10 aralkyl group. As such R ¹ , for example, methyl, ethyl, propyl (keratoisomer), allyl, butyl (keratoisomer), butenyl (keratoisomer), pentyl (keratoisomer), hexyl (keratoisomer), heptyl (keratoisomer) ), Alkyl groups such as octyl (isomer), nonyl (isomer), decyl (isomer), and cyclohexylmethyl; alicyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl; benzyl, phenethyl And aralkyl groups such as (isomers), phenylpropyl (isomers), phenylbutyl (isomers) and methylbenzyl (isomers). Moreover, in these alkyl groups, alicyclic groups, and aralkyl groups, they may be substituted by other substituents, for example, a lower alkyl group, a lower alkoxy group, a cyano group, a halogen, etc., and may have an unsaturated bond.

Examples of the dialkyl carbonate having R ¹ include dimethyl carbonate, diethyl carbonate, dipropyl carbonate (isomers), diallyl carbonate, dibutenyl carbonate (isomers), dibutyl carbonate (isomers) and diphene. Tylcarbonate (each isomer), dihexylcarbonate (each isomer), diheptylcarbonate (each isomer), dioctylcarbonate (each isomer), dinonylcarbonate (each isomer), didecylcarbonate (each isomer), dicyclopentyl Carbonate, dicyclohexylcarbonate, dicycloheptylcarbonate, dibenzylcarbonate, diphenethyl carbonate (isomer isomer), di (phenylpropyl) carbonate (isomer isomer), di (phenylbutyl) carbonate (isomer isomer), di (chlorobenzyl ) Carbonate (each isomer), di (methoxybenzyl) carbonate (each isomer), di (methoxymethyl) carbonate, Di (methoxyethyl) carbonate (each isomer), di (chloroethyl) carbonate (each isomer), di (cyanoethyl) carbonate (each isomer), and the like.

Among them, preferably used in the present invention is a dialkyl carbonate composed of an alkyl group having 4 or less carbon atoms, wherein R ¹ does not contain a halogen, and particularly preferred is dimethyl carbonate. Among the preferred dialkyl carbonates, more preferred are dialkyl carbonates prepared in a substantially free state of, for example, alkylene carbonates substantially free of halogen and alcohols substantially free of halogen. It is manufactured as.

The aromatic monohydroxy compound used in the present invention is represented by the following general formula (16), and may be any type as long as the hydroxyl group is directly bonded to the aromatic group.

Ar ¹ OH (16)

Where Ar ¹ Represents an aromatic group having 5 to 30 carbon atoms. As such an aromatic monohydroxy compound having Ar ¹ , for example, phenol; cresol (keratoisomers), xylenol (keratoisomers), trimethylphenol (keratoisomers), tetramethylphenol (keratoisomers), ethylphenol ( Each isomer), propylphenol (each isomer), butylphenol (each isomer), diethylphenol (each isomer), methylethylphenol (each isomer), methylpropylphenol (each isomer), dipropylphenol (each isomer), Various alkyl phenols such as methylbutyl phenol (isomer), pentyl phenol (isomer), hexyl phenol (isomer), cyclohexyl phenol (isomer), methoxy phenol (isomer), ethoxy phenol (isomer) Various alkoxyphenols such as arylpropylphenols such as phenylpropylphenol (isomers), naphthol (isomers) and various substituted naphthols; hydroxypyridine (isomers), hydroxycoumarin (isomers) Form), hydroxyquinoline (including a heteroaromatic monohydroxy compounds, such as individual isomers) is used.

Among these aromatic monohydroxy compounds, those which are preferably used in the present invention are Ar ¹ It is an aromatic monohydroxy compound which consists of this C6-C10 aromatic group, A phenol is especially preferable. Moreover, among these aromatic monohydroxy compounds, what is used preferably in this invention does not contain a halogen substantially.

The dialkyl carbonate used as a raw material in this invention needs to be 0.1-10 in molar ratio with respect to an aromatic monohydroxy compound. Outside this range, the amount of unreacted raw material remaining is large, and it is inefficient with respect to predetermined | prescribed production amount of the target aromatic carbonate, and requires a lot of energy in order to collect | recover them. In this sense, the molar ratio is preferably from 0.5 to 5, more preferably from 0.8 to 3, still more preferably from 1 to 2.

In the present invention, one ton or more of diaryl carbonate is continuously produced per hour, but the minimum amount of the aromatic monohydroxy compound continuously supplied for that is determined by the amount of aromatic carbonate (P ton / hr) to be produced. On the other hand, it is usually 15P ton / hr, preferably 13P ton / hr, more preferably 10P ton / hr. In more preferable cases, it can be made smaller than 8P ton / hr.

Further, the dialkyl carbonate and the aromatic monohydroxy compound used as raw materials in the present invention may each be of high purity, or may contain other compounds, for example, a first continuous multistage distillation column or / and a second. It may contain a compound produced in a continuous multi-stage distillation column or a reaction by-product. In the case of industrial implementation, dialkyl carbonate recovered from the first continuous multistage distillation column or the second continuous multistage distillation column in addition to the dialkyl carbonate and aromatic monohydroxy compound newly introduced into the reaction system as these raw materials; Preference is also given to using aromatic monohydroxy compounds. In the method of the present invention, the top component, which is a low boiling reaction mixture in the second continuous multistage distillation column, is supplied to the first continuous multistage distillation column. In this case, a 2nd tower low boiling point reaction mixture may be supplied as it is to a 1st continuous multistage distillation column, or may be supplied after isolate | separating a part of components. Therefore, in the present invention carried out industrially, it is preferable that the raw materials supplied to the first continuous multi-stage distillation column contain alcohols, alkylaryl carbonates, diaryl carbonates, alkylaryl ethers, and the like, and alkylaryl which is a product. Even if it contains a small amount of high boiling by-products, such as the fleece transition product of a carbonate and a diaryl carbonate, and its derivative (s), it is used preferably. In the present invention, for example, when methylphenyl carbonate and diphenyl carbonate are produced using dimethyl carbonate as a dialkyl carbonate and phenol as an aromatic monohydroxy compound, methyl alcohol or methyl phenyl as the reaction product in the raw material and It is preferable to contain diphenyl carbonate, and may further contain a small amount of anisole which is a reaction by-product, phenyl salicylate, methyl salicylate, and the high boiling point by-product derived from these.

The aromatic carbonates produced in the present invention are alkylaryl carbonates, diaryl carbonates, and mixtures thereof obtained by transesterification of dialkyl carbonates and aromatic monohydroxy compounds. In this transesterification reaction, one or two alkoxy groups in the dialkyl carbonate are exchanged with the aryloxy group of the aromatic monohydroxy compound, leaving the alcohols, and the transesterification reaction between the resulting two alkylarylcarbonate molecules. The reaction which exchanges diaryl carbonate and dialkyl carbonate by phosphorus disproportionation reaction is included. In the present invention, alkylaryl carbonate is mainly obtained in the first continuous multistage distillation column, and in the second continuous multistage distillation column, aromatic carbonates containing diaryl carbonate as the main product are mainly produced by heterogeneous reaction of the alkylaryl carbonate. Obtained. In the present invention, it is particularly preferable to use a raw material and a catalyst containing no halogen. In this case, since the produced diaryl carbonate does not contain any halogen, when industrially producing a polycarbonate by a transesterification method, It is important as a raw material. This is because, if the amount of halogen is less than 1 ppm, for example, in the polymerization raw material, it inhibits the polymerization reaction, reduces the physical properties of the produced polycarbonate, or causes coloring.

As a catalyst used in the 1st continuous multistage distillation column and / or the 2nd continuous multistage distillation column of this invention, it selects from the following compounds, for example.

<Lead Compound> PbO, PbO ₂ , Pb ₃ O ₄ Lead oxides such as PbS and Pb ₂ S; lead hydroxides such as Pb (OH) ₂ and Pb ₂ O ₂ (OH) ₂ ; Na ₂ PbO ₂ , K ₂ PbO ₂ , NaHPbO ₂ , KHPbO ₂ Nitrite salts such as Na ₂ PbO ₃ , Na ₂ H ₂ PbO ₄ , K ₂ PbO ₃ , K ₂ [Pb (OH) ₆ ], K ₄ PbO ₄ , Ca ₂ PbO ₄ , CaPbO ₃ Lead carbonates such as PbCO ₃ , 2PbCO ₃ and Pb (OH) ₂ and basic salts thereof; Pb (OCOCH ₃ ) ₂ , Pb (OCOCH ₃ ) ₄ , Pb (OCOCH ₃ ) ₂ ㆍ PbO · 3H ₂ Lead salts of organic acids such as O, carbonates and basic salts thereof; organic such as Bu ₄ Pb, Ph ₄ Pb, Bu ₃ PbCl, Ph ₃ PbBr, Ph ₃ Pb (or Ph ₆ Pb ₂ ), Bu ₃ PbOH, Ph ₃ PbO Lead compounds (Bu represents a butyl group, Ph represents a phenyl group); alkoxy lead such as Pb (OCH ₃ ) ₂ , (CH ₃ O) Pb (OPh), Pb (OPh) ₂ , and aryloxy lead; Pb- Alloys of lead such as Na, Pb-Ca, Pb-Ba, Pb-Sn, and Pb-Sb, lead minerals such as galena and island zinc, and hydrates of lead compounds thereof;

<Compound of copper group metal> CuCl, CuCl ₂ , CuBr, CuBr ₂ , CuI, CuI ₂ , Cu (OAc) ₂ , Cu (acac) ₂ , copper oleate, Bu ₂ Cu, (CH ₃ O) ₂ Cu, AgNO ₃ , AgBr, picric acid are salts and complexes of copper group metals such as AgC ₆ H ₆ ClO ₄ , [AuC≡CC (CH ₃ ) ₃ ] _n , [Cu (C ₇ H ₈ ) Cl] ₄ , and acac is acetyl Acetone chelate ligand.);

<Complex of Alkali Metal> Complexes of alkali metals such as Li (acac) and LiN (C ₄ H ₉ ) ₂ ;

<Complex of zinc> Zinc complexes such as Zn (acac) ₂ ;

<Complex of cadmium> Complexes of cadmium such as Cd (acac) ₂ ;

<Compound of iron group metal> Fe (C ₁₀ H ₈ ) (CO) ₅ , Fe (CO) ₅ , Fe (C ₄ H ₆ ) (CO) ₃ , Co (mesitylene) ₂ (PEt ₂ Ph) ₂ , CoC Complexes of iron group metals such as ₅ F ₅ (CO) ₇ , Ni-π-C ₅ H ₅ NO, and ferrocene;

<Zirconium Complex> Zirconium complexes such as Zr (acac) ₄ and zirconocene;

<Lewis Acid Compounds> Lewis such as AlX ₃ , TiX ₃ , TiX ₄ , VOX ₃ , VX ₅ , ZnX ₂ , FeX ₃ , SnX ₄ (where X is a halogen, acetoxy group, alkoxy group or aryloxy group). Transition metal compounds for generating acids and Lewis acids;

<Organic Tin Compound> (CH ₃ ) ₃ SnOCOCH ₃ , (C ₂ H ₅ ) ₃ SnOCOC ₆ H ₅ , Bu ₃ SnOCOCH ₃ , Ph ₃ SnO

COCH ₃ , Bu ₂ Sn (OCOCH ₃ ) ₂ , Bu ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , Ph ₃ SnOCH ₃ , (C ₂ H ₅ ) ₃ SnOPh, Bu ₂ Sn (OCH ₃ ) ₂ , Bu ₂ Sn ( OC ₂ H ₅ ) ₂ , Bu ₂ Sn (OPh) ₂ , Ph ₂ Sn (OCH ₃ ) ₂ , (C ₂ H ₅ ) ₃ SnOH, Ph ₃ SnOH, Bu ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, Organic tin compounds such as Bu ₂ SnCl ₂ and BuSnO (OH);

Metal containing compounds, such as these, are used as a catalyst. These catalysts may be solid catalysts fixed in a multi-stage distillation column or soluble catalysts dissolved in the reaction system.

Of course, these catalyst components may be reacted with organic compounds existing in the reaction system, for example, aliphatic alcohols, aromatic monohydroxy compounds, alkylaryl carbonates, diaryl carbonates, dialkyl carbonates, and the like, It may be heat-treated with a raw material or a product before reaction.

When implementing this invention with the soluble catalyst melt | dissolved in a reaction system, it is preferable that these catalysts have high solubility to a reaction liquid in reaction conditions. As a preferable catalyst in this sense, For example, PbO, Pb (OH) ₂ , Pb (OPh) ₂ ; TiCl ₄ , Ti (OMe) ₄ , (MeO) Ti (OPh) ₃ , (MeO) ₂ Ti (OPh) ₂ , (MeO) ₃ Ti (OPh), Ti (OPh) ₄ ; SnCl ₄ , Sn (OPh) ₄ , Bu ₂ SnO, Bu ₂ Sn (OPh) ₂ ; FeCl _3, and the like will be processed by _{Fe (OH) 3, Fe (} OPh) 3 and the like, or these phenols or the reaction liquid or the like. The catalyst used in the first continuous multistage distillation column and the catalyst used in the second continuous multistage distillation column may be the same kind or may be different kinds.

1 is a schematic view of a first continuous multi-stage distillation column for carrying out the production method according to the present invention. With the first continuous multi-stage distillation column 101 used in the present invention, the length L ₁ (Cm), having a hard plate portion 5 above and below the cylindrical body portion 7 having an inner diameter D ₁ (cm), and having a internal 6 having a single stage n ₁ therein; Or a gas outlet 1 having an inner diameter d ₁₁ (cm) at the top of the tower close thereto, a liquid outlet 2 having an inner diameter d ₁₂ (cm) at the bottom of the tower or a bottom of the tower close thereto; It has a lower part and at least one inlet 3 at the top and / or middle part of the tower, and at least one inlet 4 at the lower part of the tower and above the liquid outlet.

Specifically, the first continuous multistage distillation column 101 according to the present invention,

(1) The length L ₁ (cm) satisfies the formula (1),

1500 ≤ L ₁ ≤ 8000 (1)

(2) The inner diameter D ₁ (cm) of the tower satisfies the formula (2),

100 ≤ D ₁ ≤ 2000 (2)

(3) The ratio between the length L ₁ (cm) and the inner diameter D ₁ (cm) of the tower satisfies the formula (3),

2 ≤ L ₁ / D ₁ ≤ 40 (3)

(4) The number n ₁ satisfies the formula (4),

20 ≤ n ₁ ≤ 120 (4)

(5) The ratio between the inner diameter D ₁ (cm) of the tower and the inner diameter d ₁₁ (cm) of the gas outlet port satisfies Expression (5),

5 ≤ D ₁ Of d ₁₁ ≤ 30 (5)

(6) It is necessary that the ratio between the inner diameter D ₁ (cm) of the tower and the inner diameter d ₁₂ (cm) of the liquid outlet port satisfies Expression (6).

3 ≤ D ₁ Of d ₁₂ ≤ 20 (6)

2 is a schematic view of a second continuous multi-stage distillation column for carrying out the production method according to the present invention. Here, the second continuous multi-stage distillation column 201 used in the present invention has a hard plate portion 5 above and below the cylindrical body portion 7 having a length L ₂ (cm) and an inner diameter D ₂ (cm). It has a structure having an internal number 6-1: filler, 6-2: tray having the number n ₂ at the upper side, and a gas outlet 1 having an inner diameter d ₂₁ (cm) at the top of the tower or near the top. ), A liquid outlet port 2 having an inner diameter d ₂₂ (cm) at the bottom of the tower or near the bottom thereof, one or more inlets 3 at the upper and / or middle portions of the tower and lower than the gas outlet port. In addition, the liquid outlet is higher than the outlet and has at least one inlet 4 at the bottom of the tower.

Specifically, the second continuous multi-stage distillation column 201 according to the present invention,

(1) Length L ₂ (cm) satisfies formula (7),

1500 ≤ L ₂ ≤ 8000 (7)

(2) The inner diameter D ₂ (cm) of the tower satisfies the formula (8),

100 ≤ D ₂ ≤ 2000 (8)

(3) The ratio of the length L ₂ (cm) and the inner diameter D ₂ (cm) of the tower satisfies the formula (9),

2 ≤ L ₂ / D ₂ ≤ 40 (9)

(4) The singular n ₂ satisfies the formula (10),

10 ≤ n ₂ ≤ 80 (10)

(5) The ratio between the inner diameter D ₂ (cm) of the tower and the inner diameter d ₂₁ (cm) of the gas outlet port satisfies Expression (11),

2 ≤ D ₂ Of d ₂₁ ≤ 15 (11)

(6) It is necessary that the ratio of the inner diameter D ₂ (cm) of the tower to the inner diameter d ₂₂ (cm) of the liquid outlet port satisfies Expression (12).

5 ≤ D ₂ Of d ₂₂ ≤ 30 (12)

In addition, since FIG.1 and FIG.2 is embodiment of the continuous multistage distillation column which implements the manufacturing method which concerns on this invention, arrangement | positioning of the internal 6 is not limited to the structure shown in FIG.1 and FIG.2. In addition, the term "upper portion of the column near to the top government or there" as used herein refers to means a moiety of 0.25L to about 0.25L ₁ or ₂ downward from the top state, and the term near the tower in the "column bottom or there "Lower of" means a portion up to about 0.25L ₁ or 0.25L ₂ from the bottom of the column. In addition, "L ₁ and L ₂ 'is equal to the one defined above.

By using a 1st continuous multistage distillation column and a 2nd continuous multistage distillation column which satisfy all of Formula (1)-(12) simultaneously, aromatic carbonate which makes a diaryl carbonate the main product from a dialkyl carbonate and an aromatic monohydroxy compound It is understood that the products can be stably manufactured for a long time at an industrial scale of 1 ton or more per hour, high selectivity and high productivity, and for example, 2000 hours or more, preferably 3000 hours or more, more preferably 5000 hours or more. It is paid. It is not clear why the production of aromatic carbonates on an industrial scale having such excellent effects is possible by carrying out the method of the present invention, but due to the combined effect caused when the conditions of the formulas (1) to (12) are combined Is estimated. In addition, the preferable range of each factor is shown below.

When L ₁ (cm) and L ₂ (cm) are smaller than 1500, respectively, the reaction rate is lowered, so that the target yield cannot be achieved, and the equipment cost is reduced while securing the reaction rate that can achieve the target yield. order, it is necessary that the L ₁ and L ₂ to 8,000 or less, respectively. More preferred ranges of L ₁ (cm) and L ₂ (cm) are 2000 ≦ L ₁ ≦ 6000 and 2000 ≦ L ₂ ≦ 6000, and more preferably 2500 ≦ L ₁ ≦ 5000 and 2500 ≦ L ₂ ≦ 5000.

If D ₁ (cm) and D ₂ (cm) are smaller than 100, respectively, the desired output cannot be achieved, and in order to reduce the equipment cost while achieving the target output, D ₁ and D ₂ are respectively 2000 or less. It is necessary to do More preferable ranges of D ₁ (cm) and D ₂ (cm) are 150 ≦ D ₁ ≦ 1000 and 150 ≦ D ₂ ≦ 1000, and more preferably 200 ≦ D ₁ ≦ 800 and 200 ≦ D ₂ ≦, respectively. 800. In addition, the first continuous multi-stage distillation column and in the second continuous multi-stage distillation column, and may be respectively the same inside diameter D ₁ and to D ₂ is from the top of, the tower is in the range of the bottom, may be partially different from the inner diameter. For example, in these continuous multistage distillation columns, the inner diameter of the upper part of the column may be smaller or larger than the inner diameter of the lower part of the column. Moreover, the tower from which internal diameters differ partially may be sufficient.

L ₁ / D ₁ and L ₂ When / D ₂ is smaller than 2 or greater than 40, respectively, stable operation becomes difficult, especially when larger than 40, the pressure difference in the upper and lower parts of the tower becomes too large, making long-term stable operation difficult and the temperature at the bottom of the tower. Since it is necessary to increase the side reaction, side reactions are likely to occur, resulting in a decrease in selectivity. More preferred L ₁ / D ₁ and L ₂ / D ₂ ranges, respectively, 3 ≤ L ₁ / D ₁ ≤ 30 and 3 ≤ L ₂ / D ₂ ≤ 30, more preferably 5 ≤ L ₁ / D ₁ ≤ 15 and 5 ≤ L ₂ / D ₂ ≤ 15.

When n ₁ is less than 20, in order to reduce the equipment cost while ensuring the reaction rate which can achieve the target yield in a 1st continuous multistage distillation column, since the reaction rate will fall, n can be achieved, n It is necessary to set ₁ to 120 or less. In addition, when n ₁ is larger than 120, the pressure difference in the upper and lower parts of the tower becomes too large, so that not only the long-term stable operation of the first continuous multi-stage distillation column becomes difficult, but also the temperature at the bottom of the tower is high, so that side reactions are likely to occur. Lowering the selectivity. More preferably, the range of n ₁ is 30 ≦ n ₁ ≦ 100, and more preferably 40 ≦ n ₁ ≦ 90. In addition, when n ₂ is smaller than 10, in order to lower the equipment cost while ensuring a reaction rate that can achieve the desired yield in the second continuous multi-stage distillation column because the reaction rate decreases. , n ₂ needs to be 80 or less. In addition, when n ₂ is larger than 80, the pressure difference in the top and bottom of the tower becomes too large, which makes it difficult not only to make long-term stable operation of the second continuous multi-stage distillation column, but also to increase the temperature at the bottom of the column, so that side reactions are likely to occur. Lowering the selectivity. More preferably, the range of n ₂ is 15 ≦ n ₂ ≦ 60, and more preferably 20 ≦ n ₂ ≦ 50.

D ₁ If / d ₁₁ is less than 5, the equipment cost of the first continuous multi-stage distillation column is not only expensive, but a large amount of gas components are easily released out of the system, so that the stable operation of the first continuous multi-stage distillation column becomes difficult. The amount of extraction of the component is relatively small, which not only makes stable operation difficult, but also causes a decrease in the reaction rate. More preferred D ₁ / d ₁₁ range is 8 ≤ D ₁ / d ₁₁ ≤ 25, more preferably 10 ≤ D ₁ / d ₁₁ ≤ 20. D ₂ If / d ₂₁ is less than 2, the equipment cost of the second continuous multi-stage distillation column is not only expensive, but a large amount of gas components are easily released out of the system, and thus, the stable operation of the second continuous multi-stage distillation column becomes difficult. The amount of extracted N is relatively small, which not only makes stable operation difficult, but also causes a decrease in the reaction rate. More preferable D ₂ / d ₂₁ ranges from 5 ≤ D ₂ / d ₂₁ ≤ 12, more preferably 3 ≤ D ₂ / d ₂₁ ≤ 10.

D_One / d₁₂ If less than 3, the equipment cost of the first continuous multi-stage distillation column is not only expensive, but the amount of liquid discharged is relatively high, which makes it difficult to stably operate the first continuous multi-stage distillation column. This speeds up the process, making it easy to cause corrosion, resulting in corrosion of the device. More desirable D_One / d₁₂ The range of 5 ≤ D_One / d₁₂ ≤ 18, more preferably 7 ≤ D_One / d₁₂ ≤ 15. D again₂ / d₂₂ Is less than 5, the equipment cost of the second continuous multi-stage distillation column is not only expensive, and the amount of liquid extraction is relatively high, which makes it difficult to stably operate the second continuous multi-stage distillation column. This speeds up the process, making it easy to cause corrosion, resulting in corrosion of the device. More desirable D₂ / d₂₂ The range of 7 ≤ D₂ / d₂₂ ≤ 25, more preferably 9 ≤ D₂ / d₂₂ ≤ 20.

In the present invention, in the case of that the d ₁₁ and the d ₁₂ satisfy the formula (13), and that satisfy the d ₂₁ and the d ₂₂ (14), it was found that a more preferred.

1 ≤ d ₁₂ / d ₁₁ ≤ 5 equation (13)

1 ≤ d ₂₁ / d ₂₂ ≤ 6 equation (14)

Long-term stable operation in the present invention means 1000 hours or more, preferably 3000 hours or more, more preferably 5000 hours or more, there is no blockage or corrosion of the pipe, and operation can be continued in a normal state based on the operating conditions. This means that aromatic carbonates containing a predetermined amount of diaryl carbonate as the main product are being produced while maintaining the selectivity.

The present invention is characterized in that it is highly productive at least 1 ton per hour and produces aromatic carbonates with high selectivity and stable for a long time, but preferably at least 2 tons per hour, more preferably at least 3 tons per hour Is in producing. In addition, the present invention, L ₁ , D ₁ , L ₁ / D ₁ , n ₁ , D _{1 of} the first continuous multi-stage distillation column / d ₁₁ , D ₁ / d ₁₂ Respectively, 2000 ≤ L ₁ ≤ 6000, 150 ≤ D ₁ ≤ 1000, 3 ≤ L ₁ / D ₁ ≤ 30, 30 ≤ n ₁ ≤ 100, 8 ≤ D ₁ / d ₁₁ ≤ 25, 5 ≤ D ₁ / d ₁₂ ≤ 18, L ₂ , D ₂ , L ₂ of the second continuous multi-stage distillation column / D ₂ , n ₂ , D ₂ / d ₂₁ , D ₂ / d ₂₂ Respectively, 2000 ≤ L ₂ ≤ 6000, 150 ≤ D ₂ ≤ 1000, 3 ≤ L ₂ / D ₂ ≤ 30, 15 ≤ n ₂ ≤ 60, 2.5 ≤ D ₂ / d ₂₁ ≤ 12, 7 ≤ D ₂ In the case of / d ₂₂ ≤ 25, it is characterized in that aromatic carbonates are produced at least 2 tonnes per hour, preferably at least 2.5 tonnes per hour, more preferably at least 3 tonnes per hour. In addition, the present invention, L ₁ , D ₁ , L ₁ of the first continuous multi-stage distillation column / D ₁ , n ₁ , D ₁ / d ₁₁ , D ₁ / d ₁₂ Respectively, 2500 ≤ L ₁ ≤ 5000, 200 ≤ D ₁ ≤ 800, 5 ≤ L ₁ / D ₁ ≤ 15, 40 ≤ n ₁ ≤ 90, 10 ≤ D ₁ / d ₁₁ ≤ 25, 7 ≤ D ₁ / d ₁₂ ≤ 15, L ₂ , D ₂ , L ₂ of the second continuous multi-stage distillation column / D ₂ , n ₂ , D ₂ / d ₂₁ , D ₂ / d ₂₂ is 2500 ≤ L ₂ ≤ 5000, 200 ≤ D ₂ ≤ 800, 5 ≤ L ₂ / D ₂ ≤ 10, 20 ≤ n ₂ ≤ 50, 3 ≤ D ₂ / d ₂₁ ≤ 10, 9 ≤ D ₂ In the case of / d ₂₂ ≤ 20, it is characterized in that aromatic carbonates are produced at least 3 tonnes per hour, preferably at least 3.5 tonnes per hour, more preferably at least 4 tonnes per hour.

The selectivity of the aromatic carbonates referred to in the present invention refers to the reacted aromatic monohydroxy compound. In the present invention, the selectivity is usually 95% or higher, and preferably 97% or higher, and more preferably 98% or higher. Can be achieved.

The first continuous multistage distillation column and the second continuous multistage distillation column used in the present invention are preferably distillation columns having trays and / or packings as internals. The term "internal" used in the present invention means a portion in the distillation column where gas and liquid are actually brought into contact with each other. As such a tray, for example, a foam tray, a porous plate tray, a valve tray, a counterflow tray, a super freck tray, a max freck tray, and the like are preferable. As the filler, lashing ring, wrestling ring, polling, etc. Irregular fillers, such as boat birds, intalox birds, Dixon packing, McMahon packing, and Helipack, or regular fillers such as Mela Pack, Gem Pack, Techno Pack, Flexi Pack, Sulzer Packing, Good Roll Packing, Glitch Grid, etc. are preferred. A multi-stage distillation column that combines a tray portion and a filled portion of the packing may also be used. In addition, the term "the number of stages n of internal" used in the present invention means the number of trays in the case of trays, and the theoretical number of stages in the case of a filling material. Therefore, in the case of a multi-stage distillation column having a tray section and a filled portion of the packing, n is the sum of the number of trays and the theoretical number of stages.

In the first continuous multi-stage distillation column of the present invention, a reaction for producing alkylaryl carbonates mainly from dialkyl carbonates and aromatic monohydroxy compounds is carried out. This reaction has an extremely small equilibrium constant and a slow reaction rate. As a 1st continuous multistage distillation column used for reaction distillation, it discovered that the shelf single distillation column whose internal is a tray is more preferable. In the second continuous multi-stage distillation column, a reaction for disproportionating the alkylaryl carbonate is mainly performed. The reaction also has a small equilibrium constant and a slow reaction rate, but as a second continuous multi-stage distillation column used for reactive distillation, It has been found that distillation columns with both nulls and packings are more preferred. Moreover, it discovered that it is preferable to provide a packing material in the upper part and a tray in the lower part as a 2nd continuous multistage distillation column. The filling of the second continuous multi-stage distillation column is preferably a regular filling, and among the regular fillings, it has also been found that Melapak is particularly preferable.

In addition, it has been found that the trays provided in the first continuous multistage distillation column and the second continuous multistage distillation column, respectively, are particularly excellent in terms of function and equipment cost, with the porous plate tray having the porous plate portion and the downcomer portion. And, it has been found that it is desirable that a sieve tray having a sieve portion that the area of 1m 100 ~ 1000 holes per ^second. The more preferable number of holes is 120-900 pieces per 1m <^2> of those areas, More preferably, it is 150-800 pieces. Moreover, it also discovered that it is preferable that the cross-sectional area per hole of the said perforated plate tray is 0.5-5 cm <^2> . The cross-sectional area per one more preferable hole is 0.7-4 cm <^2> , More preferably, it is 0.9-3 cm <^2> . Furthermore, when the porous plate tray has 100-1000 holes per 1 m <^2> of the area of the said porous plate part, and also the cross-sectional area per hole is 0.5-5 cm <^2> , it discovered that it was especially preferable. By adding said conditions to a continuous multi-stage distillation column, it turns out that the subject of this invention is achieved more easily.

When carrying out the present invention, dialkyl carbonate and an aromatic monohydroxy compound as raw materials are continuously supplied into a first continuous multistage distillation column in which a catalyst is present, and reaction and distillation are simultaneously performed in the column to produce alcohols. The first tower low boiling point reaction mixture containing was continuously extracted from the top of the first column in gaseous form, and the first tower high boiling point reaction mixture containing the resulting alkylaryl carbonates was continuously released from the bottom of the first column into the liquid phase. Extracting the first tower high boiling point reaction mixture into the second continuous multi-stage distillation column in which the catalyst is present, and simultaneously reacting and distilling in the second column to contain the resulting dialkyl carbonates. The two tower low boiling point reaction mixture was continuously discharged in gaseous form from the top of the second tower, and the resulting diarylka The second tower high boiling point reaction mixture containing carbonates is continuously withdrawn from the bottom of the second column in the liquid phase, while the second tower low boiling point reaction mixture containing dialkyl carbonates is continuously in the first continuous multistage distillation column. By supplying with, aromatic carbonates containing diaryl carbonates as a main product are continuously produced. It is as above-mentioned that this raw material may contain reaction by-products, such as alcohol, alkylaryl carbonate, diaryl carbonate, an alkylaryl ether, and a high boiling point compound which are reaction products. In consideration of equipment and costs involved in separation and purification in other processes, in the case of the present invention which is actually carried out industrially, it is preferable to contain a small amount of these compounds.

In the present invention, in order to continuously supply the dialkyl carbonate and the aromatic monohydroxy compound as raw materials into the first continuous multi-stage distillation column, 1 is provided below the gas outlet of the upper part of the first distillation column but installed in the upper or middle part of the column. You may supply in a liquid phase and / or gas form from the inlet of several points or several points, The raw material containing many aromatic monohydroxy compounds may be supplied in a liquid phase from the inlet of the upper part of the 1st distillation column, and dialkyl carbonate may be supplied. It is also a preferred method to supply a large amount of raw material in a gaseous form from an inlet provided above the liquid outlet of the lower part of the first distillation column and provided in the lower part of the column.

In the present invention, the first tower high boiling point reaction mixture containing alkylaryl carbonates continuously discharged from the bottom of the first continuous multi-stage distillation column is continuously supplied to the second continuous multi-stage distillation column, but the supply position is the second distillation column. It is preferable to supply in a liquid phase and / or gas shape from the inlet of one point or several points provided below the gas outlet of the upper part of the upper part but installed in the upper part or the middle part of the tower. Moreover, when using the distillation column which has a packing part in the upper part and a tray part in the lower part which is a preferable embodiment of this invention, it is preferable that at least 1 point of an inlet is provided between a packing part and a tray part. Moreover, when a filling consists of two or more regular fillings, it is also a preferable method to provide an inlet in the space which comprises these several fillings.

Moreover, in this invention, it is also preferable to perform the reflux operation which returns a part to the top of each distillation column after condensing the top gas extraction component of a 1st continuous multistage distillation column and a 2nd continuous multistage distillation column, respectively. In this case, the reflux ratio of the first continuous multistage distillation column is 0 to 10, and the reflux ratio of the second continuous multistage distillation column is in the range of 0.01 to 10, preferably 0.08 to 5, and more preferably 0.1 to 2.0. In the first continuous multi-stage distillation column, reflux ratio 0 without reflux operation is also a preferred embodiment.

In the present invention, any method of allowing the catalyst to be present in the first continuous multi-stage distillation column may be used. However, when the catalyst is a solid phase insoluble in the reaction liquid, the method is provided at the stage in the first continuous multi-stage distillation column, or the filling It is preferable to fix in a tower by the method of providing as a water phase. Moreover, in the case of the catalyst which melt | dissolves in a raw material or a reaction liquid, it is preferable to supply in a distillation column from the position higher than the intermediate part of the 1st distillation column. In this case, the catalyst liquid dissolved in the raw material or the reaction liquid may be introduced together with the raw material, or the catalyst liquid may be introduced from an introduction port separate from the raw material. The amount of the catalyst used in the first continuous multi-stage distillation column of the present invention is different depending on the reaction conditions such as the type of catalyst used, the type of raw material and its ratio, the reaction temperature, and the reaction pressure. It is represented by a ratio and is usually 0.0001-30 mass%, Preferably it is 0.005-10 mass%, More preferably, it is used at 0.001-1 mass%.

In the present invention, any method of allowing the catalyst to exist in the second continuous multi-stage distillation column may be used. However, when the catalyst is a solid phase insoluble in the reaction liquid, the method may be provided at the stage in the second continuous multi-stage distillation column. Some things are fixed in a tower by the method of installing as a packing material. Moreover, in the case of the catalyst which melt | dissolves in a raw material or a reaction liquid, it is preferable to supply in a distillation column from the position higher than the middle part of the 2nd distillation column. In this case, the catalyst liquid dissolved in the raw material or the reaction liquid may be introduced together with the raw material, or the catalyst liquid may be introduced from an introduction port separate from the raw material. The amount of the catalyst used in the second continuous multi-stage distillation column of the present invention is different depending on the reaction conditions such as the type of catalyst used, the type of raw material and the ratio thereof, the reaction temperature and the reaction pressure, It is represented by a ratio and is usually 0.0001-30 mass%, Preferably it is 0.005-10 mass%, More preferably, it is used at 0.001-1 mass%.

In the present invention, the catalyst used in the first continuous multistage distillation column and the catalyst used in the second continuous multistage distillation column may be the same kind or different kinds, but preferably the same kind of catalyst is used. will be. More preferred is the same kind of catalyst which can be dissolved in both reaction liquids. In this case, the catalyst is usually discharged from the lower portion of the first distillation column together with the alkylaryl carbonate and the like in the state dissolved in the high boiling point reaction mixture of the first continuous multistage distillation column, and supplied to the second continuous multistage distillation column as it is. It is an aspect. It is also possible to add a catalyst to the second continuous multi-stage distillation column as needed.

Although the reaction time of the transesterification reaction carried out in the present invention is considered to correspond to the average residence time of each reaction liquid in the first continuous multistage distillation column and the second continuous multistage distillation column, Although it varies depending on the shape, the number of stages, the amount of raw material feed, the type and amount of the catalyst, the reaction conditions, and the like, each in the first continuous multistage distillation column and the second continuous multistage distillation column is usually 0.01 to 10 hours, preferably 0.05 to 5 hours. More preferably, it is 0.1 to 3 hours.

Although the reaction temperature of a 1st continuous multistage distillation column changes with the kind of raw material compound to be used, and the kind and quantity of a catalyst, it is the range of 100-350 degreeC normally. In order to increase the reaction rate, it is preferable to increase the reaction temperature. However, when the reaction temperature is high, side reactions are liable to occur. For example, byproducts such as alkylaryl ethers increase, which is not preferable. In this sense, the preferred reaction temperature in the first continuous multi-stage distillation column is in the range of 130 to 280 ° C, more preferably 150 to 260 ° C, still more preferably 180 to 250 ° C.

Although the reaction temperature of a 2nd continuous multistage distillation column changes with the kind of raw material compound to be used, and the kind and quantity of a catalyst, it is the range of 100-350 degreeC normally. In order to increase the reaction rate, it is preferable to increase the reaction temperature. However, when the reaction temperature is high, side reactions are liable to occur. For example, a fleece transition reaction product of an alkylaryl ether, a raw material or a product, an alkali aryl carbonate or a diaryl carbonate, or its It is not preferable because by-products such as derivatives increase. In this sense, the preferred reaction temperature in the second continuous multi-stage distillation column is in the range of 130 to 280 ° C, more preferably 150 to 260 ° C, still more preferably 180 to 250 ° C.

In addition, although the reaction pressure of a 1st continuous multistage distillation column changes with kinds, a composition, reaction temperature, etc. of the raw material compound to be used, any of pressure reduction, normal pressure, and pressurization may be sufficient in a 1st continuous multistage distillation column, and a column top pressure is 0.1 -2 * 10 <^7> Pa, Preferably it is 10 <^5> -10 <^7> Pa, More preferably, it is performed in the range of 2 * 10 <^5> -5 * 10 <^6> .

Although the reaction pressure of a 2nd continuous multi-stage distillation column changes with kinds, compositions, reaction temperature, etc. of the raw material compound to be used, any of reduced pressure, normal pressure, and pressurization may be sufficient, and a tower top pressure is 0.1-2 * 10 <^7> Pa, Preferably Preferably 10 ³ to 10 ⁶ Pa, more preferably 5 × 10 ³ to 10 ⁵ Pa It is performed in the range of.

Moreover, two or more distillation columns can also be used as a 1st continuous multistage distillation column in this invention. In this case, it is also possible to connect two or more distillation columns in series, to connect in parallel, or to connect in series and in parallel.

Moreover, two or more distillation columns can also be used as a 2nd continuous multistage distillation column in this invention. In this case, it is also possible to connect two or more distillation columns in series, to connect in parallel, or to connect in series and in parallel.

The material which comprises a 1st continuous multistage distillation column and a 2nd continuous multistage distillation column used by this invention is mainly metal materials, such as carbon steel and stainless steel, but stainless steel is preferable at the quality of the aromatic carbonate to manufacture.

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

Halogen content was measured by the ion chromatography method.

EXAMPLE 1

〈First Continuous Multistage Distillation Column (101)〉

Continuous multistage distillation column with L ₁ = 3300 cm, D ₁ = 500 cm, L ₁ / D ₁ = 6.6, n ₁ = 80, D ₁ / d ₁₁ = 17, D ₁ / d ₁₂ = 9 as shown in FIG. Was used. In this example, a porous plate tray having a cross-sectional area = about 1.5 cm 2 and a hole number = about 250 holes / m 2 per hole was used as an internal.

<Second Continuous Multistage Distillation Column 201>

Continuous multistage distillation column with L ₂ = 3100 cm, D ₂ = 500 cm, L ₂ / D ₂ = 6.2, n ₂ = 30, D ₂ / d ₂₁ = 3.85, D ₂ / d ₂₂ = 11.1 as shown in FIG. Was used. Further, in this embodiment, a perforated plate having two Melapacks (11 total theoretical stages) is provided as an internal at the top, and has a cross-sectional area = about 1.3 cm 2 and a hole number = about 250 / m 2 per hole at the bottom. The tray was used.

<Reactive distillation>

Reactive distillation was performed using the apparatus with which the 1st continuous multistage distillation column 101 and the 2nd continuous multistage distillation column 201 as shown in FIG. 3 were connected, and diphenyl carbonate was manufactured.

The raw material 1 consisting of phenol / dimethyl carbonate = 1.9 (mass ratio) was continuously introduced from the upper inlet port 11 of the first continuous multistage distillation column 101 at a flow rate of 50 tons / hr in the liquid phase. On the other hand, the raw material 2 which consists of dimethyl carbonate / phenol = 3.6 (mass ratio) was continuously introduced in the gaseous form from the lower inlet 12 of the 1st continuous multistage distillation column 101 by 50 ton / hr. The molar ratio of the raw material introduced into the first continuous multistage distillation column 101 was dimethyl carbonate / phenol = 1.35. This raw material was substantially free of halogen (1 ppb or less outside the detection limit in ion chromatography). The catalyst was Pb (OPh) ₂ introduced from the upper inlet port 11 of the first continuous multi-stage distillation column 101 to be about 100 ppm in the reaction liquid. In the first continuous multi-stage distillation column 101, the temperature at the bottom of the column was 225 ° C, and the reaction distillation was continuously performed under the condition of 7 × 10 ⁵ Pa. The first tower low boiling point reaction mixture containing methyl alcohol, dimethyl carbonate, phenol and the like is continuously extracted in a gaseous form from the tower top 13 of the first tower, through the heat exchanger 14 and from the outlet 16. Extracted at a flow rate of 34 tons / hr. On the other hand, the first tower high boiling point reaction mixture containing methylphenyl carbonate, dimethyl carbonate, phenol, diphenyl carbonate, catalyst and the like was continuously extracted from the lower part of the first column 17 in the liquid phase.

Since the stable steady state was reached after 24 hours, from the raw material introduction port 21 provided between the melapak of the second continuous multi-stage distillation column 201 and the porous plate tray as it was, the first tower high boiling point reaction mixture, 66 Continuously fed at a flow rate of tons / hr. The liquid supplied to the 2nd continuous multi-stage distillation column 201 contained 18.2 mass% of methylphenyl carbonates, and 0.8 mass% of diphenyl carbonates. In the second continuous multi-stage distillation column 201, the reaction distillation was continuously performed under the condition that the temperature of the bottom of the column was 210 ° C, the pressure of the tower top was 3 × 10 ⁴ Pa, and the reflux ratio was 0.3. After 24 hours, stable normal operation was achieved. The 2nd tower low boiling point reaction mixture containing 35 mass% of dimethyl carbonate and 56 mass% of phenols was continuously extracted from the tower top part 23 of a 2nd tower, and the flow volume in the exit port 26 was 55.6 ton / hr. The second tower low boiling point reaction mixture was continuously supplied from the inlet port 11 and / or the inlet port 12 to the first continuous multistage distillation column 101. At this time, the amount of dimethyl carbonate and phenol newly supplied was adjusted to maintain the composition and amount of the raw material 1 and the raw material 2 after considering the composition and amount of the second tower low boiling point reaction mixture.

From the top bottom part 27 of a 2nd tower, the 2nd tower high boiling point reaction mixture containing 38.4 mass% of methylphenyl carbonates, and 55.6 mass% of diphenyl carbonates was extracted continuously. The yield of diphenyl carbonate was found to be 5.74 tons per hour. The selectivity of diphenyl carbonate was 98% with respect to the reacted phenol.

Long-term continuous operation was performed under this condition. After 500 hours, after 2000 hours, after 4000 hours, after 5000 hours, and after 6000 hours, the yield of diphenyl carbonate (excluding diphenyl carbonate contained in the raw materials) is 5.74 tons, 5.75 tons, 5.74 tons, 5.74 per hour. Ton, 5.75 ton, with selectivities of 98%, 98%, 98%, 98%, 98% and very stable. In addition, the produced aromatic carbonate did not substantially contain halogen (1 ppb or less).

EXAMPLE 2

Reaction distillation was performed on the following conditions using the apparatus similar to Example 1.

The raw material 1 consisting of phenol / dimethyl carbonate = 1.1 (mass ratio) was continuously introduced from the upper inlet port 11 of the first continuous multistage distillation column 101 at a flow rate of 40 tons / hr in the liquid phase. On the other hand, the raw material 2 which consists of dimethyl carbonate / phenol = 3.9 (mass ratio) was continuously introduced in the gaseous form from the lower inlet port 12 of the 1st continuous multistage distillation column 101 at 43 ton / hr. The molar ratio of the raw material introduced into the first continuous multistage distillation column 101 was dimethyl carbonate / phenol = 1.87. This raw material was substantially free of halogen (1 ppb or less outside the detection limit in ion chromatography). The catalyst was introduced from the upper inlet port 11 of the first continuous multi-stage distillation column 101 as Pb (OPh) ₂ to be about 250 ppm in the reaction liquid. In the first continuous multi-stage distillation column 101, the temperature of the bottom of the column was 235 ° C, and the reaction distillation was performed continuously under the condition that the pressure of the tower was 9 × 10 ⁵ Pa. The first tower low boiling point reaction mixture containing methyl alcohol, dimethyl carbonate, phenol and the like is continuously extracted in a gaseous form from the tower top 13 of the first tower, through the heat exchanger 14 and from the outlet 16. Extracted at a flow rate of 43 tons / hr. On the other hand, the first tower high boiling point reaction mixture containing methylphenyl carbonate, dimethyl carbonate, phenol, diphenyl carbonate, catalyst and the like was continuously extracted from the lower part of the first column 17 in the liquid phase.

Since the stable steady state was reached after 24 hours, from the raw material introduction port 21 provided between the melapak of the second continuous multi-stage distillation column 201 and the porous plate tray, the first tower high boiling point reaction mixture was left as it is. Continuously fed at a flow rate of tons / hr. The liquid supplied to the 2nd continuous multistage distillation column 201 contained 20.7 mass% of methylphenyl carbonates, and 1.0 mass% of diphenyl carbonates. In the second continuous multi-stage distillation column 201, the reaction distillation was performed continuously under the condition that the temperature of the column bottom was 205 ° C, the pressure at the top of the column was 2 x 10 ⁴ Pa, and the reflux ratio was 0.5. After 24 hours, stable normal operation was achieved. The second tower low boiling point reaction mixture was continuously extracted from the tower top 23 of the second tower, and the flow rate at the outlet 26 was 33.3 ton / hr.

The second tower low boiling point reaction mixture was continuously supplied from the inlet port 11 and / or the inlet port 12 to the first continuous multistage distillation column 101. At this time, the amount of dimethyl carbonate and phenol newly supplied was adjusted to maintain the composition and amount of the raw material 1 and the raw material 2 after considering the composition and amount of the second tower low boiling point reaction mixture.

From the top bottom part 27 of a 2nd tower, the 2nd tower high boiling point reaction mixture containing 35.5 mass% of methylphenyl carbonate and 61.2 mass% of diphenyl carbonate was extracted continuously. The yield of diphenyl carbonate was found to be 4.1 tons per hour. The selectivity of diphenyl carbonate was 97% with respect to the reacted phenol.

Long-term continuous operation was performed under this condition. After 500 hours, after 1000 hours, the amount of diphenyl carbonate produced per hour was 4.1 tons, 4.1 tons, and 4.1 tons, and the selectivity was 97%, 97%, and 97% with respect to the reacted phenol. In addition, the produced aromatic carbonate was substantially free of halogen (1 ppb or less).

EXAMPLE 3

Reactive distillation was performed on condition of the following using the same apparatus as Example 1 except having made cross section area per hole of the perforated plate tray in the 2nd continuous multi-stage distillation column 201 = about 1.8 cm <2>.

The raw material 1 consisting of phenol / dimethyl carbonate = 1.7 (mass ratio) was continuously introduced from the upper inlet port 11 of the first continuous multistage distillation column 101 at a flow rate of 86 tons / hr in the liquid phase. On the other hand, the raw material 2 which consists of dimethyl carbonate / phenol = 3.5 (mass ratio) was continuously introduced in the gaseous form from the lower inlet 12 of the 1st continuous multistage distillation column 101 at 90 ton / hr. The molar ratio of the raw material introduced into the first continuous multistage distillation column 101 was dimethyl carbonate / phenol = 1.44. This raw material was substantially free of halogen (1 ppb or less outside the detection limit in ion chromatography). The catalyst was introduced as Pb (OPh) ₂ from the upper inlet port 11 of the first continuous multi-stage distillation column 101 so as to be about 150 ppm in the reaction liquid. In the first continuous multi-stage distillation column 101, the temperature of the column bottom was 220 ° C., and the reaction distillation was performed continuously under the condition that the pressure of the column top was 8 × 10 ⁵ Pa. The first tower low boiling point reaction mixture containing methyl alcohol, dimethyl carbonate, phenol and the like is continuously extracted in a gaseous form from the tower top 13 of the first tower, through the heat exchanger 14, and then at the outlet 16. Extracted at a flow rate of 82 tons / hr. On the other hand, the first tower high boiling point reaction mixture containing methylphenyl carbonate, dimethyl carbonate, phenol, diphenyl carbonate, catalyst and the like was continuously extracted from the lower part of the first column 17 in the liquid phase.

After 24 hours, a stable steady state was reached. From the raw material introduction port 21 provided between the melapak of the second continuous multi-stage distillation column 201 and the porous plate tray as it was, 94 Continuously fed at a flow rate of tons / hr. The liquid supplied to the 2nd continuous multi-stage distillation column 201 contained 16.0 mass% of methylphenyl carbonates, and 0.5 mass% of diphenyl carbonates. In the second continuous multi-stage distillation column 201, reaction distillation was continuously performed under the condition that the temperature at the bottom of the column was 215 ° C, the pressure at the top of the column was 2.5 10 ⁴ Pa, and the reflux ratio was 0.4. After 24 hours, stable normal operation was achieved. The second tower low boiling point reaction mixture was continuously extracted from the tower top 23 of the second tower, and the flow rate at the outlet 26 was 81.7 ton / hr. The second tower low boiling point reaction mixture was continuously supplied from the inlet port 11 to the first continuous multistage distillation column 101. At this time, the amount of dimethyl carbonate and phenol newly supplied was adjusted to maintain the composition and amount of the raw material 1 and the raw material 2 after considering the composition and amount of the second tower low boiling point reaction mixture.

From the tower bottom 27 of a 2nd tower, the 2nd tower high boiling point reaction mixture containing 35.5 mass% of methylphenyl carbonates, and 59.5 mass% of diphenyl carbonates was extracted continuously. The yield of diphenyl carbonate was found to be 7.32 tons per hour. The selectivity of diphenyl carbonate was 98% with respect to the reacted phenol.

Long-term continuous operation was performed under this condition. After 500 hours, after 1000 hours, the yield per hour of diphenyl carbonate after 2000 hours was 7.32 tons, 7.33 tons and 7.33 tons, and the selectivity was 98%, 98% and 98% with respect to the reacted phenol and was very stable. In addition, the produced aromatic carbonate was substantially free of halogen (1 ppb or less).

The present invention provides a high selectivity and high productivity on an industrial scale of at least 1 ton per hour of an aromatic carbonate containing a diaryl carbonate as a main product from a dialkyl carbonate and an aromatic monohydroxy compound using two continuous multistage distillation columns. It is preferable as a specific method which can manufacture stably for a long time.

1 is a schematic diagram of a first continuous multi-stage distillation column according to the present invention. An internal 6 is provided inside the fuselage section.

2 is a schematic diagram of a second continuous multi-stage distillation column suitable for practicing the present invention. Inside the fuselage part, internals 6-1 and 6-2, each of which consists of a regular filler at the top and a perforated plate tray at the bottom, are provided.

3 is a schematic diagram of a preferred apparatus for implementing the present invention. In addition, description of the code | symbol used in each drawing is as follows:

1 ： gas outlet,

2: liquid outlet,

3, 4, 15, 19, 25, 29: inlet,

5: hard board part,

6: Internal,

6-1 ： Internal (filling),

6-2 ： Internal (tray),

7: body part,

L ₁ , L _2: body part length (cm),

D ₁ , D _2: fuselage inner diameter (cm),

d ₁₁ and d _{21 :} gas outlet inner diameter (cm),

d ₁₂ , d _22: liquid outlet diameter (cm),

101: first continuous multistage distillation column,

201 ： second continuous multistage distillation column,

11, 12, 21: Inlet,

13, 23 ： top gas outlet,

14, 24, 18, 28 ： heat exchanger,

15, 25: reflux inlet,

16, 26: top component outlet,

17, 27 ： Top bottom liquid outlet,

31: The bottom component outlet of a 2nd continuous multistage distillation column.

Claims (33)

As a method for producing aromatic carbonates using dialkyl carbonates and aromatic monohydroxy compounds as raw materials, and diaryl carbonates as main products, (i) continuously supplying the raw materials into the first continuous multistage distillation column in which the catalyst is present; (ii) reacting the raw materials in the first column to produce alcohols and alkylaryl carbonates; (iii) continuously extracting the first low boiling point reaction mixture containing the resulting alcohols from the top of the first column, and the first tower high boiling point reaction mixture containing the resulting alkylaryl carbonates in the first column. Continuous extraction from the lower portion into the liquid phase, (iv) the first tower high boiling point reaction mixture is continuously fed into a second continuous multistage reaction distillation column in which a catalyst is connected to the first continuous multistage distillation column, and dialkyl carbonates and diaryl carbonates Reacting in the second column to produce (v) The second tower high boiling point reaction mixture containing the produced dialkyl carbonates is continuously extracted in a gaseous form from the top of the second column, and the second tower high boiling point reaction containing the produced diaryl carbonates is produced. Continuously extracting the mixture from the lower part of the second column into the liquid phase, (a) The dialkyl carbonate continuously supplied into the first continuous multistage distillation column is 0.1 to 10 in molar ratio with respect to the aromatic monohydroxy compound, (b) The first continuous multi-stage distillation column has a hard plate portion above and below a cylindrical body portion having a length L ₁ (cm) and an inner diameter D ₁ (cm), and has an internal having a single stage n ₁ therein. The gas outlet has an internal diameter d ₁₁ (cm) at the top of the tower or near the tower, and the liquid outlet at an inner diameter d ₁₂ (cm) at the bottom of the tower or at the bottom of the tower close thereto. Having at least one inlet above the outlet and above the liquid outlet and above the liquid outlet and at least one inlet below the tower, (1) The length L ₁ (cm) satisfies the formula (1), 1500 ≤ L ₁ ≤ 8000 (1) (2) The inner diameter D ₁ (cm) of the tower satisfies the formula (2), 100 ≤ D ₁ ≤ 2000 (2) (3) The ratio between the length L ₁ (cm) and the inner diameter D ₁ (cm) of the tower satisfies the formula (3), 2 ≤ L ₁ Of D ₁ ≤ 40 (3) (4) The number n ₁ satisfies the formula (4), 20 ≤ n ₁ ≤ 120 (4) (5) The ratio between the inner diameter D ₁ (cm) of the tower and the inner diameter d ₁₁ (cm) of the gas outlet port satisfies Expression (5), 5 ≤ D ₁ / d ₁₁ ≤ 30 (5) (6) The ratio between the inner diameter D ₁ (cm) of the tower and the inner diameter d ₁₂ (cm) of the liquid outlet port satisfies Expression (6), 3 ≤ D ₁ Of d ₁₂ ≤ 20 (6) (c) The second continuous multi-stage distillation column has a structure having a hard plate portion above and below a cylindrical body portion having a length L ₂ (cm) and an inner diameter D ₂ (cm) and having an internal number having a single stage n ₂ therein. A gas outlet having an inner diameter d ₂₁ (cm) at the top of the tower, or near the top thereof, a liquid outlet having an inner diameter d ₂₂ (cm) at the bottom of the tower, or a lower portion of the tower close thereto; Having at least one inlet at the top and / or middle of the tower, at least one inlet above the liquid outlet and at the bottom of the tower, (1) Length L ₂ (cm) satisfies formula (7), 1500 ≤ L ₂ ≤ 8000 (7) (2) The inner diameter D ₂ (cm) of the tower satisfies the formula (8), 100 ≤ D ₂ ≤ 2000 (8) (3) The ratio of the length L ₂ (cm) and the inner diameter D ₂ (cm) of the tower satisfies the formula (9), 2 ≤ L ₂ Of D ₂ ≤ 40 (9) (4) The singular n ₂ satisfies the formula (10), 10 ≤ n ₂ ≤ 80 (10) (5) The ratio between the inner diameter D ₂ (cm) of the tower and the inner diameter d ₂₁ (cm) of the gas outlet port satisfies Expression (11), 2 ≤ D ₂ Of d ₂₁ ≤ 15 (11) (6) The ratio between the inner diameter D ₂ (cm) of the tower and the inner diameter d ₂₂ (cm) of the liquid outlet port satisfies Equation (12). 5 ≤ D ₂ Of d ₂₂ ≤ 30 (12) Characterized by the above. The method of claim 1, In the steps (ii) and (iv), distillation is also performed at the same time. The method according to claim 1 or 2, The production of diaryl carbonate is at least 1 ton per hour. Using the dialkyl carbonate and the aromatic monohydroxy compound as raw materials, the raw materials are continuously supplied into the first continuous multistage distillation column in which the catalyst is present, and the reaction and distillation are simultaneously performed in the first column to produce the alcohols. The first tower low boiling point reaction mixture containing was continuously extracted from the top of the first column in gaseous form, and the first tower high boiling point reaction mixture containing the resulting alkylaryl carbonates was continuously released from the bottom of the first column into the liquid phase. Extracting the first tower high boiling point reaction mixture into the second continuous multi-stage distillation column in which the catalyst is present, and simultaneously reacting and distilling in the second column to contain the resulting dialkyl carbonates. The two tower low boiling point reaction mixture was continuously discharged in gaseous form from the top of the second tower, and the resulting arylcarbone The second tower high boiling point reaction mixture containing trute was continuously drawn out from the bottom of the second column in the liquid phase, while the second tower low boiling reaction mixture containing dialkyl carbonates was continuously supplied into the first continuous multistage distillation column. By continuously producing aromatic carbonates containing diaryl carbonates as a main product, (a) The dialkyl carbonate continuously supplied into the first continuous multistage distillation column is 0.1 to 10 in molar ratio with respect to the aromatic monohydroxy compound, (b) The first continuous multi-stage distillation column has a structure having a hard plate portion above and below a cylindrical body portion having a length L ₁ (cm) and an inner diameter D ₁ (cm) and having an internal number having a single stage n ₁ therein. A gas outlet having an inner diameter d ₁₁ (cm) at the top of the tower, or near the top thereof, a liquid outlet having an inner diameter d ₁₂ (cm) at the bottom of the tower, or a lower portion of the tower close thereto, lower than the gas outlet; Having at least one inlet at the top and / or middle of the tower, at least one inlet above the liquid outlet and at the bottom of the tower, (1) The length L ₁ (cm) satisfies the formula (1), 1500 ≤ L ₁ ≤ 8000 (1) (2) The inner diameter D ₁ (cm) of the tower satisfies the formula (2), 100 ≤ D ₁ ≤ 2000 (2) (3) The ratio between the length L ₁ (cm) and the inner diameter D ₁ (cm) of the tower satisfies the formula (3), 2 ≤ L ₁ Of D ₁ ≤ 40 (3) (4) The number n ₁ satisfies the formula (4), 20 ≤ n ₁ ≤ 120 (4) (5) The ratio between the inner diameter D ₁ (cm) of the tower and the inner diameter d ₁₁ (cm) of the gas outlet port satisfies Expression (5), 5 ≤ D ₁ Of d ₁₁ ≤ 30 (5) (6) The ratio between the inner diameter D ₁ (cm) of the tower and the inner diameter d ₁₂ (cm) of the liquid outlet port satisfies Expression (6), 3 ≤ D ₁ Of d ₁₂ ≤ 20 (6) (c) The second continuous multi-stage distillation column has a structure having a hard plate portion above and below a cylindrical body portion having a length L ₂ (cm) and an inner diameter D ₂ (cm) and having an internal number having a single stage n ₂ therein. A gas outlet having an inner diameter d ₂₁ (cm) at the top of the tower, or near the top thereof, a liquid outlet having an inner diameter d ₂₂ (cm) at the bottom of the tower, or a lower portion of the tower close thereto; Having at least one inlet at the top and / or middle of the tower, at least one inlet above the liquid outlet and at the bottom of the tower, (1) Length L ₂ (cm) satisfies formula (7), 1500 ≤ L ₂ ≤ 8000 (7) (2) The inner diameter D ₂ (cm) of the tower satisfies the formula (8), 100 ≤ D ₂ ≤ 2000 (8) (3) the ratio between the length L ₂ (cm) and the inner diameter D ₂ (cm) of the tower satisfies the formula (9), 2 ≤ L ₂ Of D ₂ ≤ 40 (9) (4) The singular n ₂ satisfies the formula (10), 10 ≤ n ₂ ≤ 80 (10) (5) The ratio between the inner diameter D ₂ (cm) of the tower and the inner diameter d ₂₁ (cm) of the gas outlet port satisfies Expression (11), 2 ≤ D ₂ Of d ₂₁ ≤ 15 (11) (6) The ratio between the inner diameter D ₂ (cm) of the tower and the inner diameter d ₂₂ (cm) of the liquid outlet port satisfies Equation (12). 5 ≤ D ₂ Of d ₂₂ ≤ 30 (12) Industrial production method of the aromatic carbonates which have a diaryl carbonate as a main product characterized by the above-mentioned. The method of claim 4, wherein Process for producing a diaryl carbonate is more than 1 ton per hour. The method according to any one of claims 1, 2, 4 or 5, D ₁₁ and d ₁₂ satisfy equation (13), and d ₂₁ and d ₂₂ satisfy equation (14). 1 ≤ d ₁₂ / d ₁₁ ≤ 5 (13) 1 ≤ d ₂₁ / d ₂₂ ≤ 6 (14) Characterized by the above. The method according to any one of claims 1, 2, 4 or 5, L ₁ , D ₁ , L ₁ / of the first continuous multi-stage distillation column D ₁ , n ₁ , D ₁ / d ₁₁ , D ₁ / d ₁₂ is 2000 ≤ L ₁ ≤ 6000, 150 ≤ D ₁ ≤ 1000, 3 ≤ L ₁ / D ₁ ≤ 30, 30 ≤ n ₁ ≤ 100, 8 ≤ D ₁ / d ₁₁ ≤ 25, 5 ≤ D ₁ / d ₁₂ ≤ 18, and, L ₂ , D ₂ , L ₂ / of the second continuous multi-stage distillation column D ₂ , n ₂ , D ₂ / d _21, D ₂ / d ₂₂ is 2000 ≤ L ₂ ≤ 6000, 150 ≤ D ₂ ≤ 1000, 3 ≤ L ₂ / D ₂ ≤ 30, 15 ≤ n ₂ ≤ 60, 2.5 ≤ D ₂ / d ₂₁ ≤ 12, 7 ≤ D ₂ / d ₂₂ ≦ 25. The method according to any one of claims 1, 2, 4 or 5, L ₁ , D ₁ , L ₁ / of the first continuous multi-stage distillation column D ₁ , n ₁ , D ₁ / d _11, D ₁ / d ₁₂ is 2500 ≤ L ₁ ≤ 5000, 200 ≤ D ₁ ≤ 800, 5 ≤ L ₁ / D ₁ ≤ 15, 40 ≤ n ₁ ≤ 90, 10 ≤ D ₁ / d ₁₁ ≤ 25, 7 ≤ D ₁ / d ₁₂ ≤ 15, and, L ₂ , D ₂ , L ₂ / of the second continuous multi-stage distillation column D ₂ , n ₂ , D ₂ / d _21, D ₂ / d ₂₂ is 2500 ≤ L ₂ ≤ 5000, 200 ≤ D ₂ ≤ 800, 5 ≤ L ₂ / D ₂ ≤ 15, 20 ≤ n ₂ ≤ 50, 3 ≤ D ₂ / d ₂₁ ≤ 10, 9 ≤ D ₂ / d ₂₂ ≦ 20. The method according to any one of claims 1, 2, 4 or 5, The first continuous multistage distillation column and the second continuous multistage distillation column are distillation columns each having a tray and / or a packing as its internal. The method of claim 9, The first continuous multistage distillation column is a shelf single distillation column having a tray as its internal, and the second continuous multistage distillation column is a distillation column having both a packing and a tray as its internal. The method of claim 9, The tray of each of the first continuous multistage distillation column and the second continuous multistage distillation column is a porous plate tray having a porous plate portion and a downcomer portion. The method of claim 11, The porous plate tray has 100 to 1000 holes per square meter of area of the porous plate portion. The method of claim 11, A cross-sectional area per hole in the perforated plate tray is 0.5 to 5 cm 2. The method of claim 9, The second continuous multi-stage distillation column is a distillation column having a charge at the top and a tray at the bottom thereof as the internals. The method of claim 9, The filling of the internal of the second continuous multi-stage distillation column is one or two or more regular fillings. The method of claim 15, The regular fillings of the second continuous multi-stage distillation column are Melapak, Gempak, TECHNO-PAK, FLEXI-PAK, Sulzer packing, Goodroll packing. ), At least one selected from Glitchgrid. The method according to any one of claims 1, 2, 4 or 5, The first continuous multi-stage distillation column is characterized by using two or more distillation columns. The method according to any one of claims 1, 2, 4 or 5, A method of using the distillation column of two or more groups as the second continuous multi-stage distillation column. delete A reactive distillation apparatus comprising a first continuous multistage distillation column for carrying out reaction and distillation, and a second continuous multistage distillation column for carrying out reaction and distillation, connected to the first continuous multistage distillation column, comprising: (a) the first continuous Multistage distillation column, length L ₁ (Cm), having a hard plate portion above and below a cylindrical body portion having an inner diameter D ₁ (cm), and having a internal structure having a singular number n ₁ therein, and having an inner diameter d _{11 at} the top of the tower or near the top thereof. (Cm) gas outlet, the bottom of the column or the bottom of the tower close to it, the liquid outlet of the inner diameter d ₁₂ (cm), lower than the gas outlet, at least one inlet at the top and / or middle of the tower At least one inlet at the bottom of the tower and above the liquid outlet, (1) The length L ₁ (cm) satisfies the formula (1), 1500 ≤ L ₁ ≤ 8000 (1) (2) The inner diameter D ₁ (cm) of the tower satisfies the formula (2), 100 ≤ D ₁ ≤ 2000 (2) (3) The ratio between the length L ₁ (cm) and the inner diameter D ₁ (cm) of the tower satisfies the formula (3), 2 ≤ L ₁ / D ₁ ≤ 40 (3) (4) The number n ₁ satisfies the formula (4), 20 ≤ n ₁ ≤ 120 (4) (5) The ratio between the inner diameter D ₁ (cm) of the tower and the inner diameter d ₁₁ (cm) of the gas outlet port satisfies Expression (5), 5 ≤ D ₁ / d ₁₁ ≤ 30 Equation (5) (6) The ratio between the inner diameter D ₁ (cm) of the tower and the inner diameter d ₁₂ (cm) of the liquid outlet port satisfies Expression (6), 3 ≤ D ₁ / d ₁₂ ≤ 20 (6) (b) The second continuous multi-stage distillation column has a structure having a hard plate portion above and below a cylindrical body portion having a length L ₂ (cm) and an inner diameter D ₂ (cm), and having an internal having a single stage n ₂ therein. A gas outlet having an inner diameter d ₂₁ (cm) at the top of the tower, or near the top thereof, a liquid outlet having an inner diameter d ₂₂ (cm) at the bottom of the tower, or a lower portion of the tower close thereto; Having at least one inlet at the top and / or middle of the tower, at least one inlet above the liquid outlet and at the bottom of the tower, (1) Length L ₂ (cm) satisfies formula (7), 1500 ≤ L ₂ ≤ 8000 (7) (2) The inner diameter D ₂ (cm) of the tower satisfies the formula (8), 100 ≤ D ₂ ≤ 2000 Equation (8) (3) The ratio of the length L ₂ (cm) and the inner diameter D ₂ (cm) of the tower satisfies the formula (9), 2 ≤ L ₂ / D ₂ ≤ 40 (9) (4) The singular n ₂ satisfies the formula (10), 10 ≤ n ₂ ≤ 80 (10) (5) Inner diameter D ₂ (cm) of tower and inner diameter of gas outlet d ₂₁ The ratio of (cm) satisfies the formula (11), 2 ≤ D ₂ / d ₂₁ ≤ 15 Equation (11) (6) The ratio between the inner diameter D ₂ (cm) of the tower and the inner diameter d ₂₂ (cm) of the liquid outlet port satisfies Equation (12). 5 ≤ D ₂ / d ₂₂ ≤ 30 Equation (12) Reactive distillation apparatus, characterized in that. The method of claim 20, D ₁₁ and d ₁₂ satisfy equation (13), and d ₂₁ and d ₂₂ satisfy equation (14). 1 ≤ d ₁₂ / d ₁₁ ≤ 5 Equation (13) 1 ≤ d ₂₁ / d ₂₂ ≤ 6 Equation (14) Reactive distillation apparatus, characterized in that. The method of claim 20 or 21, L ₁ , D ₁ , L ₁ of the first continuous multi-stage distillation column / D ₁ , n ₁ , D ₁ / d _{11 ,} D ₁ / d ₁₂ is 2000 ≤ L ₁ ≤ 6000, 150 ≤ D ₁ ≤ 1000, 3 ≤ L ₁ / D ₁ ≤ 30, 30 ≤ n ₁ ≤ 100, 8 ≤ D ₁ / d ₁₁ ≤ 25, 5 ≤ D ₁ / d ₁₂ ≤ 18, and, L ₂ , D ₂ , L ₂ of the second continuous multi-stage distillation column / D ₂ , n ₂ , D ₂ / d _{21 ,} D ₂ / d ₂₂ is 2000 ≤ L ₂ ≤ 6000, 150 ≤ D ₂ ≤ 1000, 3 ≤ L ₂ / D ₂ ≤ 30, 15 ≤ n ₂ ≤ 60, 2.5 ≤ D ₂ / d ₂₁ ≤ 12, 7 ≤ D ₂ Reactive distillation apparatus, characterized in that / d ₂₂ ≤ 25. The method of claim 20 or 21, L ₁ , D ₁ , L ₁ / D ₁ , n ₁ , D ₁ / d ₁₁ , of the first continuous multi-stage distillation column D ₁ / d ₁₂ is 2500 ≤ L ₁ ≤ 5000, 200 ≤ D ₁ ≤ 800, 5 ≤ L ₁ / D ₁ ≤ 15, 40 ≤ n ₁ ≤ 90, 10 ≤ D ₁ / d ₁₁ ≤ 25, 7 ≤ D ₁ / d ₁₂ ≤ 15, and, L ₂ , D ₂ , L ₂ / D ₂ , n ₂ , D ₂ / d _{21, and} D ₂ / d ₂₂ of the second continuous multi-stage distillation column are 2500 ≤ L ₂ ≤ 5000, 200 ≤ D ₂ ≤ 800, Reactive distillation apparatus, characterized in that 5 ≤ L ₂ / D ₂ ≤ 15, 20 ≤ n ₂ ≤ 50, 3 ≤ D ₂ / d ₂₁ ≤ 10, 9 ≤ D ₂ / d ₂₂ ≤ 20. The method of claim 20 or 21, The first continuous multistage distillation column and the second continuous multistage distillation column are distillation columns each having a tray and / or a packing as its internal. The method of claim 24, The first continuous multistage distillation column is a shelf single distillation column having a tray as its internal, and the second continuous multistage distillation column is a distillation column having both a packing and a tray as its internal. The method of claim 24, Each of the trays of the first continuous multistage distillation column and the second continuous multistage distillation column is a porous plate tray having a porous plate portion and a downcomer portion. The method of claim 26, The porous plate tray has 100 to 1000 holes per square meter of area of the porous plate portion. The method of claim 26, The reactive distillation apparatus characterized by the cross-sectional area per hole of the perforated plate tray of 0.5-5 cm <2>. The method of claim 24, The second continuous multi-stage distillation column is a distillation column having a packing at the bottom and a tray at the bottom thereof as the internal. The method of claim 24, A reactive distillation apparatus, characterized in that the packing of the internal of the second continuous multi-stage distillation column is a regular packing having one group or two or more groups. The method of claim 30, The regular packing of the second continuous multi-stage distillation column is at least one selected from melapack, gempack, technopack, flexipack, sulzer packing, good roll packing, and glitch grid. The method of claim 20 or 21, A distillation column of two or more groups is used as the first continuous multi-stage distillation column. The method of claim 20 or 21, A distillation column of two or more groups is used as the second continuous multi-stage distillation column.

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