WO2006035642A1 - 芳香族カーボネートの工業的製造方法 - Google Patents
芳香族カーボネートの工業的製造方法 Download PDFInfo
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- WO2006035642A1 WO2006035642A1 PCT/JP2005/017358 JP2005017358W WO2006035642A1 WO 2006035642 A1 WO2006035642 A1 WO 2006035642A1 JP 2005017358 W JP2005017358 W JP 2005017358W WO 2006035642 A1 WO2006035642 A1 WO 2006035642A1
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- distillation column
- continuous multistage
- carbonate
- multistage distillation
- boiling point
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
- B01D3/146—Multiple effect distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/16—Fractionating columns in which vapour bubbles through liquid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to an industrial process for producing aromatic carbonates. More specifically, a raw material containing a dialkyl carbonate and an aromatic monohydroxy compound is subjected to a transesterification reaction in a continuous multistage distillation column in the presence of a catalyst, and a large amount of a low amount of alcohol containing by-products is produced.
- the present invention relates to a method for industrially producing a large amount of an aromatic carbonate useful as a raw material for a transesterification method polycarbonate while efficiently separating the alcohols from a boiling point reaction mixture.
- Aromatic carbonate is important as a raw material for producing aromatic polycarbonate, which is the most demanding engineering plastic, without using toxic phosgene.
- a method for producing an aromatic carbonate a method of reacting an aromatic monohydroxy compound with phosgene has been known for a long time, and various studies have been made recently.
- chlorinated impurities that are difficult to separate in the aromatic carbonate produced by this method, and as such, it cannot be used as a raw material for aromatic polycarbonate. Can not. This is because this chlorine-based impurity significantly inhibits the polymerization reaction of the transesterification polycarbonate carried out in the presence of a very small amount of a basic catalyst.
- Lewis acids such as transition metal halides or compounds that generate Lewis acids
- Patent Document 1-1 JP-A-51-105032
- Patent Document 1-2 JP-A-56-123948
- Patent Document 1-3 Japanese Patent Laid-Open No. 56-123949 (West German Patent Publication No. 2528412, British Patent No. 1499530, US Pat. No. 4,182,726)
- Patent Literature 1-4 Japanese Patent Laid-Open No. 51-51 No. 75044 (West German Patent Publication No. 2552907, US Pat. No. 4045464)
- tin compounds such as organotin alkoxides and organostannic oxides
- Patent Document 2-1 JP 54-48733 A (West Germany) Patent Publication No.
- Patent Document 2 736062 Patent Document 2-2: Japanese Patent Laid-Open No. 54-63023; Patent Document 2-3: Japanese Patent Laid-Open Publication No. 60-169444 (US Pat. No. 4,554,110); Patent Document 2-4: JP-A-60-169445 (US Pat. No. 4,552,704); Patent Document 2-5: JP-A-62 Patent No.
- Patent Document 2-6 JP-A-1-2655063
- Patent Document 3 JP-A-56-25138
- Patent Document 4-1 JP-A-57-176932
- Patent Document 4-2 JP-A-1-93560
- Patent Document 5 Special (Kaisho 57-183745), titanic acid esters
- Patent Document 6-1 JP-A 58-1 85536 (US Pat. No.
- Patent Document 6-2 JP-A 1-2650 62
- Patent Document 7 Japanese Patent Laid-Open No. 60-173016 (US Pat. No. 4,609501)), compounds such as Sc, Mo, Mn, Bi, Te, etc.
- Patent Document 8 JP-A-1-265064
- ferric acetate Patent Document 9: JP-A-61-172852
- catalyst development alone cannot solve the problem of unfavorable equilibrium, so there are a lot of issues to consider in order to achieve an industrial production method for mass production, including the study of reaction methods.
- Patent Document 10 Japanese Patent Laid-Open No. 54-48732 (West German Patent Publication No. 736063, US Patent) No. 4252737)
- Patent Document 11 Japanese Patent Laid-Open No. 58-185536 (US Pat. No. 410464)
- Patent Document 12-1 Example of JP-A-56-123948 (US Pat. No. 4,182,726)
- Patent Document 12-2 Example of JP-A-56-25138
- Patent Reference 12-3 Examples of JP-A-60-169444 (US Pat. No. 4,554,110)
- Patent Document 12-4 JP-A-60-169445 (US Pat. No. 4,552,704)
- Patent Examples 12-5 Examples of JP-A-60-173016 (US Pat. No. 4,609,501);
- Patent Documents 12-6 Examples of JP-A-61-172852;
- Patent Documents 12-7 Examples of JP-A-61-291545; Patent Documents 12-8: Examples of JP-A-62-277345).
- reaction systems are basically batch system force switching systems.
- the inventors of the present invention continuously supply dialkyl carbonate and aromatic hydroxy compound to a multistage distillation column and continuously react in the column in the presence of a catalyst.
- Reactive distillation method in which the low-boiling components contained are continuously extracted by distillation and the components containing the produced alkylaryl carbonate are extracted from the bottom of the column (Patent Document 13: (Kaihei 3-291257)), alkylaryl carbonate is continuously fed to a multi-stage distillation column and reacted continuously in the column in the presence of a catalyst to produce a low-boiling component containing dialkyl carbonate as a by-product.
- a reactive distillation method Patent Document 14: Japanese Patent Laid-Open No.
- the reaction mixture is extracted and introduced into a reactor provided outside the distillation column, reacted, and then introduced into a circulation inlet provided at a stage higher than the stage having the extraction port, thereby allowing the reaction to occur.
- Reactive distillation method in which the reaction is carried out both in the reactor and in the distillation column (Patent Document 16-1: JP-A-4-224547; Patent Document 16-2: JP-A-4-230242; Patent Document 16-3 : JP-A-4-235951) developed a reactive distillation method in which these transesterification reactions are carried out in a continuous multistage distillation column simultaneously with distillation and separation, and the reactive distillation method is used for these transesterification reactions. Disclosed for the first time in the world that it is useful.
- Patent Document 17 International Publication No. 00Z18720 (US Pat. No. 5,362,901)
- Patent Document 18 Italian Patent No. 01255746
- Patent Document 19 Special Kaihei 6-9506 (European Patent No. 05 60159, US Pat. No. 5,282,965)
- Patent Document 20 Japanese Patent Laid-Open No. 6-41022 (European Patent 0572870, US Pat. No. 5,362,901)
- Patent Document 21-1 JP-A-6-157424 (European Patent 0582931, US Patent No.
- Patent Document 21-2 JP-A-6-184058 (European Patent 05) 82930, US Pat. No. 5344954); Patent Document 22 : JP-A-7-304 713; Patent Document 23: JP-A-9-40616; Patent Document 24: JP-A-9-59225; Patent Document 25: JP-A-9-110805; Patent Document 26 : JP-A-9-165 Patent Publication No. 357; Patent Literature 27: Japanese Patent Laid-Open No. 9-173819; Patent Literature 28-1: Japanese Patent Laid-Open No. 9-176094; Patent Literature 28-2: Japanese Patent Laid-Open No. 2000-191596; Patent Literature 28-3: Japanese Patent Application Laid-Open No.
- Patent Document 29 Japanese Patent Application Laid-Open No. 9-194436 (European Patent 0 785184, US Pat. No. 5,705,673)
- Patent Document 30 International Publication No. 00 Z18720 (US Patent) Patent No. 6093842)
- Patent Document 31-1 Japanese Patent Laid-Open No. 2001-64234
- Patent Document 31-2 Japanese Patent Laid-Open No. 2001-64235
- Patent Document 32 Japanese Laid-Open Patent Publication No. 02Z40439 (US Patent No. 6596894, US Pat. No. 6596895, US Pat. No. 6600061))).
- the applicant of the present invention has disclosed a high boiling point substance containing a catalyst component as an active substance as a method capable of stably producing a high-purity aromatic carbonate for a long time without requiring a large amount of catalyst in a reactive distillation system.
- Patent Document 33 WO 97Z11049 (European Patent No. 0855384, US Pat. No. 58 72275))
- Patent Document 34 JP-A-11-92429 (European Patent No. 1016648, US Patent) No. 6262210)
- Patent Document 35 Japanese Patent Laid-Open No. 9-255772 (European Patent No. 0892001, US Pat. No. 5,747,609)).
- Patent Document 37 JP-A-2003-155264.
- the purpose of these methods is to recover the heat energy of the gas component when the reaction is performed using the continuous stirring tank as described above as a reactor, by generating steam by heat exchange. It is to be. There is no disclosure or suggestion that the thermal energy of the gas component is used to heat the raw material.
- composition of the gas components by these reactions schemes dimethyl carbonate 97 parts by mass 0/0, methanol 1.5 mass 0/0, phenol 1.5 Quality Amount% (Patent Document 36), Dimethyl carbonate 98.1% by mass, Methanol 1.4% by mass, Phenolic, Methylphenol carbonate, etc. 0.5% by mass (Patent Document 37), produced by a reactive distillation method
- the composition of the low boiling point reaction mixture containing by-product alcohols is very different from that of the low boiling point reaction mixture obtained by the reactive distillation method.
- Patent Document 38 JP-A-6-157410
- JP-A-6-157410 a method of distilling a liquid containing about 10-74% by mass of methanol at about 30gZhr from the top of a distillation column installed at the top of a tank reactor
- the by-product alcohol When the transesterification reaction between a dialkyl carbonate and an aromatic hydroxy compound is carried out by reaction distillation, the by-product alcohol usually has a lower boiling point than the aromatic force-bonate present in the reaction system. These compounds are continuously extracted from the upper column of the reactive distillation column as a low-boiling reaction mixture containing, for example, raw material dialkyl carbonate and aromatic hydroxy compound, by-product alkylaryl ether and the like. Since this transesterification reaction is an equilibrium reaction with a very small equilibrium constant, by-product alcohols inhibit this reaction, so the low-boiling-point reaction mixture contains a low alcohol content component and alcohols. For industrial implementation, it is important to separate and recover from the main components efficiently and stably for a long period of time.
- Patent Document 29 Permissible literature 28
- Patent Document 24 a method of obtaining a mixture comprising 60 to 40% by mass of methanol and 40 to 60% by mass of dimethyl carbonate
- the problem to be solved by the present invention is to efficiently produce alcohols as a by-product in the production of aromatic carbonates from dialkyl carbonates and aromatic monohydroxy compounds by reactive distillation using a continuous multistage distillation column. It is intended to provide a specific method for stably producing aromatic carbonates on an industrial scale of 1 ton per hour or more for a long period of time.
- the present inventors disclosed a method for producing aromatic carbonates using a continuous multistage distillation column. Since then, there have been many proposals for the production of aromatic carbonates by reactive distillation, but these are all small-scale and short-term laboratory levels, enabling mass production on an industrial scale. Disclosure of specific methods and devices was absolutely impossible. Accordingly, the present inventors have found a specific method capable of stably producing aromatic carbonates over a long period of time on an industrial scale of 1 ton or more per hour while efficiently separating by-product alcohols. As a result of repeated studies, the present invention has been reached.
- a raw material containing a dialkyl carbonate and an aromatic monohydroxy compound is continuously fed into a continuous multistage distillation column A in which a catalyst exists, and in the distillation column A, a transesterification reaction and a distillation are simultaneously performed. Distilling the low boiling point reaction mixture (A) containing by-product alcohols
- a high-boiling-point reaction mixture (A) containing aromatic carbonates is continuously withdrawn in the gaseous state from the upper part of the column A, and the reaction is carried out by a reactive distillation method in which the liquid is continuously withdrawn from the lower part of the distillation column A.
- the continuous multistage distillation column A has an internal length L (cm) that satisfies the conditions of the following formulas (1) to (6), an inner diameter D (cm), and an internal number n of stages, A gas outlet of inner diameter d (cm) at the top of the tower or near the top of the tower, and an inner diameter d at the bottom of the tower or near the bottom of the tower.
- a low boiling point mixture (B) having a coal concentration of 90% by mass or more is introduced from the upper part of the distillation column B.
- the liquid is continuously extracted from the lower part of the liquid and the high boiling point mixture (B) is put into the continuous multistage distillation column A.
- a distillation column consisting of a concentrating part with an internal number n and an internal number can be used.
- the tray is a perforated plate tray having a perforated plate portion and a downcomer portion.
- the tray is a perforated plate tray having a perforated plate portion and a downcomer portion.
- the concentration of the alcohol in the low boiling point mixture (B) is 95% by mass or more.
- the concentration of the alcohol in the low boiling point mixture (B) is 97% by mass or more.
- the low boiling point mixture (B) is used as a raw material for producing dialkyl carbonate
- alcohol content is 0.2% by mass or less;
- the content of the alcohol in the high boiling point mixture (B) is 0.1% by mass or less.
- the by-product alcohols are efficiently separated from the dialkyl carbonate and the aromatic monohydroxy compound by 200 kg or more per hour, and 95% or more, preferably 97%.
- An industrial scale with a high selectivity of at least%, more preferably at least 99%, and aromatic carbonates of at least 1 ton per hour, preferably at least 2 ton per hour, more preferably at least 3 ton per hour Thus, it has been found that it can be stably produced for a long period of 2000 hours or more, preferably 3000 hours or more, more preferably 5000 hours or more.
- the dialkyl carbonate used in the present invention is represented by the general formula (15).
- R 1 represents an alkyl group having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, or an aralkyl group having 6 to 10 carbon atoms.
- R 1 include methyl, ethyl, propyl (each isomer), allyl, butyl (each isomer), butenyl (each isomer), pentyl (each isomer), hexyl (each Isomers), heptyl (each isomer), octyl (each isomer), nonyl (each isomer), decyl (each isomer), alkyl group such as cyclohexylmethyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl Cycloheptyl and other alicyclic groups; aralkyl groups such as benzyl, phenethyl (each isomer), phenyl
- alkyl groups, alicyclic groups, and aralkyl groups may be substituted with other substituents such as a lower alkyl group, a lower alkoxy group, a cyano group, or a halogen, and have an unsaturated bond. But, okay.
- dialkyl carbonate having R 1 examples include dimethyl carbonate, jetyl carbonate, dipropyl carbonate (each isomer), diallyl carbonate, dibutenyl carbonate (each isomer), and dibutyl.
- dialkyl carbonates in which R 1 consists of an alkyl group having 4 or less carbon atoms which does not contain halogen, particularly preferably, one is dimethyl carbonate.
- R 1 consists of an alkyl group having 4 or less carbon atoms which does not contain halogen, particularly preferably, one is dimethyl carbonate.
- dialkyl carbonates more preferred! / Are dialkyl carbonates prepared in a state substantially free of halogen, for example, alkylene carbonate substantially free of halogen. Alcohol power that is substantially free of nitrogen is also produced.
- the aromatic monohydroxy compound used in the present invention is represented by the following general formula (16), and if the hydroxyl group is directly bonded to the aromatic group, It can be anything.
- Ar 1 represents an aromatic group having 5 to 30 carbon atoms.
- aromatic monohydroxy compounds having Ar 1 include phenol, talesol (each isomer), xylenol (each isomer), trimethylphenol (each isomer), tetramethylphenol (each isomer), Ethylphenol (each isomer), Propylphenol (each isomer), Butylphenol (each isomer), Jetylphenol (each isomer), Methylethylphenol (each isomer), Methylpropylphenol (each Isomers), dipropylphenol (each isomer), methylbutylphenol (each isomer), pentylphenol (each isomer), hexylphenol (each isomer), cyclohexylphenol (each isomer), etc.
- alkylphenols various alkoxyphenols such as methoxyphenol (each isomer) and ethoxyphenol (each isomer); arylalkylphenols such as phenolpropyl (each isomer); naphthol ( Each isomer) and various substituted naphthols; hydroxypyridine (each isomer), hydroxycoumarin (each isomer) , Hydroxyquinoline (isomers) heteroaromatic monohydroxy I ⁇ thereof such to the like or the like is used.
- aromatic monohydroxy compounds various alkoxyphenols such as methoxyphenol (each isomer) and ethoxyphenol (each isomer); arylalkylphenols such as phenolpropyl (each isomer); naphthol ( Each isomer) and various substituted naphthols; hydroxypyridine (each isomer), hydroxycoumarin (each isomer) , Hydroxyquinoline (isomers) heteroaromatic monohydroxy I ⁇
- Ar 1 is preferably an aromatic monohydroxy compound having an aromatic group having 6 to 10 carbon atoms, particularly preferably phenol.
- aromatic monohydroxy compounds those that are preferably used in the present invention are those that do not substantially contain halogen.
- the molar ratio of the dialkyl carbonate and the aromatic monohydroxy compound used as a raw material in the present invention must be 0.5 to 3 in terms of molar ratio. Outside this range, the remaining unreacted raw material increases with respect to the desired production amount of the aromatic carbonate, which is not efficient, and requires a lot of energy to recover them. In this sense, this mono ktti is more preferably 0.8 to 2.5 force, and more preferably ⁇ ⁇ , 1.0 to 2.0.
- the aromatic carbonate produced in the present invention includes alkylaryl carbonate, diaryl carbonate obtained by transesterification of dialkyl carbonate and aromatic monohydroxy compound, and these It is a mixture of In this ester exchange reaction, one or two alkoxy groups of a dialkyl carbonate are used.
- the reaction of the reaction formula (17) mainly occurs.
- reaction 19 that is converted to diaryl carbonate and dialkyl carbonate by a disproportionation reaction, which is a transesterification reaction between the two molecules of alkylaryl carbonate.
- a force that mainly yields an alkylaryl carbonate A force that causes a transesterification reaction of this alkylaryl carbonate with an aromatic monohydroxyl compound further causes a disproportionation reaction (formula 19).
- Diaryl carbonate can be used. Since this diaryl carbonate does not contain any halogen, it is important as a raw material for the industrial production of polycarbonate by the transesterification method.
- dialkyl carbonate and aromatic monohydroxy compound used as raw materials for the transesterification reaction in the present invention each have a high purity, but these contain other compounds. For example, it may contain compounds and reaction by-products formed in this step and z or other steps.
- these raw materials include dialkyl carbonate and aromatic monohydric oxy compounds newly introduced into the reaction system, as well as those recovered from this process and Z or other processes. It is preferable to use it.
- the low-boiling point reaction mixture (A) continuously extracted from the continuous multistage distillation column A is continuously distilled and separated in the continuous multistage distillation column B and continuously as a bottom component.
- such recovered material containing other compounds can also be used as a raw material.
- dimethyl carbonate is used as a dialkyl carbonate
- phenol is used as an aromatic monohydroxy compound.
- the raw material may contain a small amount of methyl alcohol as a reaction product, methyl phenol carbonate and diphenyl carbonate.
- the reaction by-product including a high-boiling by-product, may be used.
- the catalyst used in the present invention for example, the following compound power is selected.
- Lead compounds > Lead oxides such as PbO, PbO and PbO; Lead sulfides such as PbS and Pb S; Pb (0
- Lead hydroxides such as Pb 2 O (OH); Na PbO, K PbO, NaHPbO, KHPbO, etc.
- Lead salts such as PbO and CaPbO
- Lead carbonates such as PbCO and 2PbCO 'Pb (OH) and
- Pb lead alloys such as Sb
- lead minerals such as howenite, senyanite, and hydrates of these lead compounds
- ⁇ Copper group metal compounds > CuCl, CuCl, CuBr, CuBr, Cul, Cul, Cu (OAc),
- acac represents a cetylacetone chelate ligand
- Alkali metal complexes such as Li (acac) and LiN (C H);
- Zinc complex such as Zn (acac);
- Cd complex such as Cd (acac);
- ⁇ Iron group metal compounds > Fe (C H) (CO), Fe (CO), Fe (C H) (CO), Co (Me
- Zirconium complexes such as Zr (acac) and zirconocene;
- Lewis acids > A1X, TiX, TiX, VOX, VX, ZnX, FeX, SnX (here And X is a halogen, acetoxy group, an alkoxy group or an aryloxy group. ) And other transition metal compounds that generate Lewis acids;
- Organotin compounds such as SnO (OH);
- a metal-containing compound such as is used as a catalyst may be solid catalysts fixed in a multistage distillation column, or may be soluble catalysts that dissolve in the reaction system.
- organic compounds in which these catalyst components are present in the reaction system for example, aliphatic alcohols, aromatic monohydroxy compounds, alkylaryl carbonates, diaryl carbonates, dialkyl carbonates, etc. It may be reacted, or may be heat-treated with raw materials or products prior to the reaction.
- catalysts When the present invention is carried out with a soluble catalyst that dissolves in the reaction system, these catalysts preferably have high solubility in the reaction solution under the reaction conditions.
- Preferred catalysts in this sense include, for example, PbO, Pb (OH), Pb (OPh); TiCl, Ti (OMe), (Me
- Examples thereof include those treated with phenol or a reaction solution.
- FIG. 1 is a schematic diagram showing an example of a continuous multi-stage distillation column A that performs the reactive distillation of the present invention.
- the continuous multistage distillation column A used for reactive distillation is a length L (cm) that satisfies the conditions (1) to (6), an inner diameter D (cm), and the number of stages inside.
- Liquid discharge port 2 the gas discharge
- a distillation column having one or more inlets 3 in the lower part of the tower and in the upper part of the tower and in the Z or intermediate part, and one or more inlets 4 in the upper part of the liquid outlet and in the lower part of the tower. It is necessary.
- top of the tower or near the top of the tower means a portion of about 0.25 L downward from the top of the tower, and the term “bottom of the tower or near the bottom of the tower” It means the part up to about 0.25L from the bottom of the tower. “L” is as defined above.
- FIG. 2 shows the distillation separation of the low boiling point reaction mixture (A) containing the alcohol of the present invention.
- FIG. 2 is a schematic view showing an example of a continuous multistage distillation column B.
- FIG. 1 the low boiling point reaction mixture (A) from which the upper force of the continuous multistage distillation column A is also continuously extracted is used to concentrate the alcohols.
- Continuous multistage distillation column B used for continuous distillation separation into high-boiling mixture (B)
- a steam consisting of a concentrating part ES with an internal (for example, tray 8) with n stages inside.
- Continuous multi-stage distillation column A satisfying the expressions (1) to (6) simultaneously and simultaneously satisfying the expressions (7) to (14)
- continuous multi-stage distillation column B By using continuous multi-stage distillation column B, unreacted raw materials can be efficiently recovered while separating by-product alcohols stably and efficiently from dialkyl carbonates and aromatic monohydroxy compounds.
- Reusable on an industrial scale of 1 ton or more per hour, high selectivity and high productivity for example, 2000 hours or more, preferably 3000 hours or more, more preferably 5000 hours or more
- aromatic carbonates can be produced.
- the conditions of the formulas (1) to (14) are not clear. This is presumed to be due to the combined effect brought about when the two are combined.
- L (cm) is less than 1500, the reaction rate decreases and the target production volume cannot be achieved.To reduce the equipment cost while securing the reaction rate that can achieve the target production volume, L is set at 8000. It is necessary to make it smaller. A more preferable range of L (cm) is 2000 ⁇ L ⁇ 6000, and more preferably 2500 ⁇ L ⁇ 5000.
- D (cm) is smaller than 100, the target production volume cannot be achieved, and D must be smaller than 2000 in order to reduce the equipment cost while achieving the target production volume. is there.
- the more preferable range of D (cm) is 150 ⁇ D ⁇ 1000, and more preferably 200 ⁇ D ⁇ 800.
- LZD is less than 2 or greater than 40
- stable operation becomes difficult.
- LZD is greater than 40
- the pressure difference between the top and bottom of the tower becomes too large, so long-term stable operation becomes difficult. Since the temperature at the bottom must be increased, side reactions are likely to occur, leading to a decrease in selectivity.
- the more preferable range of LZD is 3 ⁇ LZD ⁇ 30, and more preferably 5 ⁇ LZD ⁇ 15.
- n is less than 20, the reaction rate decreases, the target production volume cannot be achieved, and the facility cost can be reduced while securing the reaction rate that can achieve the target production volume. It is necessary to make n smaller than 120. Furthermore, if n is greater than 120, the pressure difference between the top and bottom of the column will become too large, and long-term stable operation will become difficult.In addition, the temperature at the bottom of the column will have to be raised. Resulting in a decline in rate. Yo The preferred range of n is 30 ⁇ n ⁇ 100, more preferably 40 ⁇ n ⁇ 90
- D / d force is smaller, not only will the equipment cost be increased, but a large amount of gas components will be discharged out of the system, which makes stable operation difficult. It becomes relatively small, and the reaction rate is lowered just as stable operation becomes difficult.
- the more preferable range of D / d is 8 ⁇ D / d ⁇ 25, and more preferably 10 ⁇ D / d ⁇ 20.
- L (cm) is smaller than 500, the separation efficiency of the recovery unit is reduced, so that the target separation efficiency cannot be achieved, and the facility cost can be reduced while ensuring the target separation efficiency. It is necessary to make the power less than 3 000 S.
- a more preferable range of L (cm) is 800 ⁇ L ⁇ 250 0, and more preferably 1000 ⁇ L ⁇ 2000.
- D (cm) is smaller than 100, the target distillation amount cannot be achieved, and in order to reduce the equipment cost while achieving the target distillation amount, it is necessary to make D smaller than 500. is there.
- a more preferable range of D (cm) is 120 ⁇ D ⁇ 400, and more preferably 150 ⁇ D ⁇ 300.
- L / repulsive force is less than or greater than 30, long-term stable operation becomes difficult.
- a more preferred range of L / ⁇ is 5 ⁇ L ZD ⁇ 20, more preferably 7 ⁇ L / ⁇ ⁇ 15.
- n is less than 10
- the separation efficiency of the recovery unit is reduced, so that the target separation efficiency cannot be achieved.
- n is less than 40. It is necessary to drill.
- a more preferable range of n is 13 ⁇ n ⁇ 25, and more preferably 15 ⁇ n ⁇ 20.
- the range is 1500 ⁇ L ⁇ 3500, more preferably 2000 ⁇ L ⁇ 3000.
- D (cm) is less than 50, the target distillation amount cannot be achieved, and the target distillation amount cannot be achieved.
- the preferred range of D (cm) is 70 ⁇ D ⁇ 200, more preferably 80 ⁇ D ⁇ 15
- L ZD is less than 10 or greater than 50, long-term stable operation becomes difficult. More preferred
- the new L ZD range is 15 ⁇ L ZD ⁇ 30, more preferably 20 ⁇ L / D ⁇
- n is less than 35, the separation efficiency of the concentrating part is lowered, so the target separation efficiency is achieved.
- n is less than 100.
- n is greater than 100, the pressure difference between the top and bottom of the tower is large.
- n 40 ⁇ n
- the present invention is characterized in that aromatic carbonate is produced with high productivity at a high productivity of 1 ton or more per hour for a long period of time, preferably 2 ton or more per hour, Preferably, 3 tons or more of aromatic carbonate is produced per hour.
- the present invention also provides L, D, LZD, n, D / d, D / d force S of the continuous multistage distillation column A.
- the selectivity of the aromatic carbonate referred to in the present invention is relative to the reacted aromatic monohydroxy compound, and in the present invention, it is usually a high selectivity of 95% or more, preferably 97%. As described above, a high selectivity of 99% or more can be achieved.
- the continuous multistage distillation column A used in the present invention is preferably a distillation column having a tray and Z or packing as an internal.
- the term “internal” as used in the present invention means a portion of the distillation column that actually makes the gas-liquid contact.
- a tray for example, a foam tray, a perforated plate tray, a valve tray, a counterflow tray, a super flux tray, a max flack tray, etc. are preferred packings such as Raschig rings, less ring rings, and pole rings.
- a multi-stage distillation column having both a tray part and a packed part can also be used.
- the term “internal plate number n” used in the present invention means the number of trays in the case of trays, and the theoretical plate number in the case of packing. Therefore, in the case of a continuous multistage distillation column having both a tray part and a packed part, n is the total number of trays and the number of theoretical plates.
- the transesterification reaction between the dialkyl carbonate and the aromatic monohydroxy compound of the present invention has an extremely small equilibrium constant and a slow reaction rate. Therefore, the continuous multistage distillation column A used for the reactive distillation is an internal unit. It has been found that a plate-type distillation column in which is a tray is more preferable. Furthermore, it has been found that a perforated plate tray having a perforated plate portion and a downcomer portion is particularly excellent in terms of function and equipment costs. It is preferable that the perforated plate tray has 100 to 1000 holes per area lm 2 of the perforated plate portion. Was also found. A more preferable number of holes is 120 to 900 per lm 2 , and more preferably 150 to 800.
- the cross-sectional area per hole of the perforated plate tray is preferably 0.5 to 5 cm 2 .
- the cross-sectional area per hole is more preferably 0.7 to 4 cm 2 , and still more preferably 0.9 to 3 cm 2 .
- the perforated plate tray has 100 to L000 holes per area lm 2 of the perforated plate portion, and the cross-sectional area per hole is 0.5 to 5 cm 2 . It has been found to be particularly preferred. It has been found that by adding the above conditions to the continuous multistage distillation column A, the object of the present invention can be achieved more easily.
- the continuous multistage distillation column B used in the present invention is preferably a distillation column having the tray and Z or packing as the internals of the concentrating part ES and the recovery part SS. It is even more preferable if the internals of the concentrating part ES and the collecting part SS are both trays. Furthermore, it has been found that a perforated plate tray having a perforated plate portion and a downcomer portion is particularly excellent in terms of function and equipment cost. And the concentration unit ES and the recovery unit
- the preferred number of holes and the cross-sectional area of the perforated plate portion of the perforated plate tray in SS are the same as those of the perforated plate portion of the continuous multistage distillation column A described above.
- the raw material dialkyl carbonate and the aromatic monohydroxy compound are continuously fed into the continuous multistage distillation column A where the catalyst is present, and the reaction and distillation are simultaneously performed in the column.
- the aromatic carbonates are continuously produced on an industrial scale by continuously extracting the high-boiling point reaction mixture containing aromatic carbonates in the liquid state from the bottom of the tower, while the low-boiling point containing by-product alcohols is produced.
- Reaction mixture (A) is gas from the top of the tower
- the low boiling point reaction mixture (A) is continuously extracted into a continuous multistage distillation column B.
- the low boiling point mixture (B) mainly composed of alcohols is connected in a gaseous form from the top of the tower.
- the high boiling point mixture (B) is continuously extracted in liquid form from the bottom of the column.
- the point reaction mixture (A) When the point reaction mixture (A) is supplied into the continuous multistage distillation column B, it may be supplied in gaseous form.
- the heat of the low boiling point reaction mixture (A) extracted in a gaseous form from the continuous multistage distillation column A is heated to other substances, for example, into the continuous multistage distillation column A.
- the low boiling point reaction mixture supplied into the continuous multistage distillation column B is used.
- Compound (A) is in the form of gas, gas-liquid mixture, or liquid.
- the low boiling point reaction mixture (A) is continuously used.
- This raw material Prior to feeding into the multistage distillation column B, heating or cooling is preferably performed in order to obtain a temperature close to the liquid temperature near the supply port of the distillation column B.
- This raw material contains reaction by-products such as alcohols, alkylaryl carbonates, diaryl carbonates, alkylaryl ethers, and high-boiling compounds as reaction products! ⁇ ⁇ As described above. Considering the equipment and cost required for separation and purification in other processes, it is preferable to contain a small amount of these compounds in the case of the present invention which is actually carried out industrially! / ,.
- the gas is extracted from the upper part of the distillation column A. It may be supplied in liquid and Z or gaseous form from one or several inlets installed in the upper part or middle part of the tower but below the mouth, and contains a large amount of aromatic monohydroxy compounds.
- the raw material is supplied in liquid form from the inlet at the upper part of the distillation column, and the dialkyl power-the raw material containing a large amount of bonate is higher than the liquid outlet at the lower part of the distillation column and the inlet power installed at the lower part of the tower is also gaseous It is also the preferred method to supply in Z and liquid.
- any method may be used for allowing the catalyst to be present in the continuous multistage distillation column A.
- the catalyst when the catalyst is in a solid state insoluble in the reaction solution, There are methods such as installing on a stage in a multistage distillation column and fixing it in the column by installing it in a packed form.
- the catalyst solution dissolved in the raw material or the reaction solution may be introduced together with the raw material, or the catalyst solution may be introduced from an inlet different from the raw material.
- the amount of catalyst used in the present invention varies depending on the type of catalyst used, the type of raw material and its ratio, the reaction temperature, and the reaction conditions such as the reaction pressure, but is expressed as a percentage of the total mass of the raw material. Usually, it is used at 0.0001 to 30% by mass, preferably 0.005 to 10% by mass, more preferably 0.001 to 1% by mass.
- the reaction time of the transesterification reaction performed in the present invention is considered to correspond to the average residence time of the reaction liquid in the continuous multistage distillation column A.
- it varies depending on the supply amount, the type and amount of the catalyst, the reaction conditions, etc., it is usually 0.01 to 10 hours, preferably 0.05 to 5 hours, more preferably 0.1 to 3 hours.
- the reaction temperature is usually 100 to 350 ° C., although it varies depending on the type of raw material used and the type and amount of catalyst. In order to increase the reaction rate, it is preferable to increase the reaction temperature. However, if the reaction temperature is high, side reactions are liable to occur. For example, by-products such as alkylaryl ethers are increased, which is not preferable.
- a preferable reaction temperature is 130 to 280 ° C, more preferably 150 to 260 ° C, and still more preferably 180 to 250 ° C.
- the reaction pressure varies depending on the type and composition of the starting compound used, the reaction temperature, etc., but it may be any of reduced pressure, normal pressure, and pressurized pressure, usually 0.1 to 2 X 10 7 Pa, preferably , 10 5 to 10 7 Pa, more preferably 2 ⁇ 10 5 to 5 ⁇ 10 6 .
- the upper force of the continuous multistage distillation column A The position where the low boiling point reaction mixture (A) continuously extracted is fed into the continuous multistage distillation column B is the recovery section SS and the concentration section ES.
- the continuous multistage distillation column B preferably has a reboiler for heating the distillate and a reflux device.
- the low boiling point reaction mixture (A) is usually 10 to: LOOO ton Zhr,
- the alcohol in the low-boiling mixture (B) is used.
- the concentration of rutile is 90% by mass or more with respect to 100% by mass of the low boiling point mixture (B).
- the alcohols need to be 200 kgZhr or more, preferably 500 kgZhr or more, more preferably 1 to 20 tons Zhr, and can be stably and continuously separated for a long time.
- the low boiling point mixture (B) separated in the present invention contains 90% by mass or less of by-produced alcohols.
- the low boiling point mixture (B) should be used as a dialkyl carbonate production raw material.
- the low boiling point mixture (B) is Reaction raw materials and
- the alcohololysis reaction of alkylene carbonate is an equilibrium reaction, it is preferable to use a raw material having a high alcohol concentration. Therefore, the low boiling point mixture (B) obtained in the present invention is preferably used as a raw material for this reaction. is there. This
- the alcohol concentration in the low boiling point mixture (B) is 100% of the low boiling point mixture (B).
- the high boiling point mixture (B) separated in the present invention is a component of the low boiling point reaction mixture (A).
- the component power of the low boiling point mixture (B) is extracted from
- this high boiling point mixture (B) is continuously supplied to the continuous multistage distillation column A because it contains a small amount of aromatic carbonates.
- the amount of dialkyl carbonate in the raw material supplied to the continuous multistage distillation column A is insufficient only by the amount in the high boiling point mixture (B).
- the raw material containing dialkyl carbonate newly added to the continuous multistage distillation column A may be supplied directly to the continuous multistage distillation column A or supplied to the continuous multistage distillation column B, and the high boiling point mixture (B).
- raw material power including this newly added dialkyl carbonate For example, when it contains more than 0.1% by mass of alcohol, it is supplied to an appropriate position in the continuous multistage distillation column B and the content of the alcohol is contained. After reducing the volume, continuous multistage distillation column A as part of the high-boiling mixture (B) It is preferable to supply to.
- the raw material supplied to the continuous multistage distillation column A is composed of the raw material 1 and the raw material 2.
- the raw material 1 contains a disproportionation reaction of alkylaryl carbonate (formula 19). ) And dialkyl carbonate produced in the main process. Therefore, in the continuous multistage distillation column A, about half the amount of dialkyl carbonate consumed by the reaction to produce alkylaryl carbonate is the power that can be provided by the dialkyl carbonate in raw material 1 produced and recycled by this disproportionation reaction. About half of the shortage needs to be added as fresh dialkyl carbonate. This allows reactive distillation to be continued in a steady state. In the present invention, this shortage is usually added to the raw material 1 as well as the power to add dialkyl carbonate to the raw material 2.
- the distillation conditions of the continuous multistage distillation column B carried out in the present invention are as follows.
- the column bottom temperature is 150 to 300 ° C, preferably 170 to 270 ° C, more preferably 190 to 250 ° C, and the column top pressure
- the reflux ratio is 0.1 to 20 , Preferably 0.5 to 15, more preferably 1.0 to 10
- the long-term stable operation in the present invention refers to a continuous multistage distillation column A in which reactive distillation is performed for 1000 hours or more, preferably 3000 hours or more, and more preferably 5000 hours or more, and the low boiling point reaction mixture (A All of the continuous multistage distillation columns B that perform distillation separation of
- a certain amount of aromatics of 1 ton or more per hour can be maintained in a steady state based on the operating conditions where piping clogging and erosion can occur, while maintaining high productivity and high selectivity.
- the material constituting the continuous multistage distillation column used in the present invention is preferably stainless steel from the viewpoint of the quality of the aromatic carbonate produced mainly by a metal material such as carbon steel and stainless steel.
- the present invention will be described more specifically with reference to the following examples. It is not limited to.
- the composition of the mixture was measured by gas chromatography, and the halogen was measured by ion chromatography.
- the catalyst is Pb (OPh), and the reaction solution is about 70 ppm.
- the production amount of methylphenyl carbonate per hour is 8.3 tons (the actual production amount excluding the amount introduced into distillation column A is 7.5 tons Zhr), and the production amount of diphenyl carbonate per hour was found to be 0.22 tons.
- the combined selectivity of methyl phenol carbonate and diphenyl carbonate for the reacted phenol was 99%.
- a long-term continuous operation was performed under these conditions. After 500 hours, 2000 hours, 4000 hours, 5000 hours, 6000 hours, the production volume per hour is methylphenol carbonate. 8.3, 8.3, 8.3 8.3 centimeters, 8.3 centimeters, and the production per hour of diphenyl carbonate is 0.22 centimeters, 0.22 centimeters, 0.22 centimeters, 0.22 centimeters. 0.22%, and the combined selectivity of methyl and diphenyl carbonate is 99%, 99%, 99%, 99%, 99%, 99%, 99%, which is very stable. It was. In addition, the produced aromatic carbonate did not substantially contain halogen (lppb or less).
- the low boiling point reaction mixture (A) has a liquid temperature near the inlet 31 provided between the recovery part and the concentration part of the continuous multistage distillation column B.
- the distillation column B After being brought to a close temperature, the distillation column B was continuously supplied from the inlet 31. On the other hand, fresh dimethyl carbonate was continuously introduced from the inlet 41 at the bottom of the distillation column B at 2.53 ton Zhr in order to make up for the lack of dimethyl carbonate.
- the distillation column B is continuously subjected to distillation separation at a column bottom temperature of 226 ° C, a column top temperature of 155 ° C, and a reflux ratio of 3, and a low boiling point mixture (B) is 1.73 tons Zhr from the outlet 39, High boiling point mixture (B) is extracted
- the composition of the low boiling point mixture (B) is 97% by mass of methanol and 3% by mass of dimethyl carbonate.
- the amount of methanol continuously distilled off was 1.68 tons Zhr.
- the low boiling point mixture (B) is reacted with ethylene carbonate to give dimethyl carbonate and ethyl acetate.
- continuous multistage distillation column B was performed in accordance with the continuous operation of continuous multistage distillation column A, but the separation efficiencies after 500 hours, 2000 hours, 4000 hours, 5000 hours, and 6000 hours were the same as in the initial stage. It was stable.
- the raw material 2 consisting of methanol 0.1 wt% was continuously introduced from the lower inlet 11 of the distillation column A at a flow rate of 86.6 tons Zhr.
- the raw material contained substantially no halogen (less than the limit of detection by ion chromatography, lppb or less).
- the catalyst is Pb (OPh), and the distillation column A is adjusted so as to have about lOOppm in the reaction solution.
- the production amount of methylphenol carbonate per hour is 11.8 tons (the actual production amount excluding the amount introduced into the distillation column A is 10.7 tons Zhr), and the diphenyl carbonate production per hour Production is 0.6 tons I found out that The combined selectivity of methyl phenol carbonate and diphenol carbonate for the reacted phenol was 98%.
- the low-boiling point reaction mixture (A) continuously extracted in gaseous form from the top of the continuous multistage distillation column A is heated to 161 ° C by using the heat to heat the raw material 1 in the heat exchange ⁇ 27. Reduced
- the low boiling point reaction mixture (A) is a liquid near the inlet 31 provided between the recovery part and the concentration part of the continuous multistage distillation column B.
- distillation column B After being brought to a temperature close to the temperature, it was continuously supplied to the distillation column B from the inlet 31. On the other hand, fresh dimethyl carbonate was continuously introduced into the distillation column B at 3.98 tons Zhr from the inlet 51 in the fourth stage of the lowering force of the concentrating unit in order to compensate for the lack of dimethyl carbonate.
- the distillation column B is continuously distilled and separated at a bottom temperature of 213 ° C, a top temperature of 138 ° C, and a reflux ratio of 2.89, and a low boiling point mixture (B) is discharged from the outlet 39 to 2.78 tons Zhr.
- the point mixture (B) was continuously withdrawn from the outlet 35 at 86.6 tons Zhr.
- the high-boiling mixture (B) has a methanol content of 0.1% by mass or less, and its composition is
- composition of the low boiling point mixture (B) is 93.3 mass% methanol, dimethyl carbonate 6.7.
- continuous multi-stage distillation column B Used as a raw material for producing ethylene glycol.
- the operation of continuous multi-stage distillation column B was performed in accordance with the continuous operation of continuous multi-stage distillation column A, but the separation efficiency after 500 hours, 1000 hours, and 2000 hours was the same as in the initial stage, and it moved stably. .
- the reaction mixture (A) was subjected to heat exchange 27 in the same manner as in Example 1 and the same continuous mixture as in Example 1 was obtained.
- a fresh raw material consisting of 99% by weight of dimethyl carbonate and 1% by weight of methanol is concentrated to supply dimethyl carbonate continuously.
- the lower force of the section was continuously introduced into the distillation column B at 1.76 ton Zhr from the fourth stage inlet 51.
- the bottom temperature was 219 ° C
- the top temperature was 151 ° C
- the reflux ratio was 6.74
- the distillation separation was performed continuously, and the low boiling point mixture (B) was formed.
- the high boiling point mixture (B) has a methanol content.
- composition of the low boiling point mixture (B) is 99% by mass of methanol and 1% by mass of dimethyl carbonate.
- the amount of methanol continuously distilled off was 1.18 tons Zhr.
- the low boiling point mixture (B) is reacted with ethylene carbonate to give dimethyl carbonate and ethyl acetate.
- continuous multi-stage distillation column B was performed in accordance with the continuous operation of continuous multi-stage distillation column A, but the separation efficiency after 500 hours, 1000 hours, and 2000 hours was the same as in the initial stage, and it moved stably.
- Reactive distillation was carried out in the same manner using the same continuous multistage distillation column A as in Example 1, and 2.8% by mass of methanol, 61.0% by mass of dimethyl carbonate from the outlet 26 at the top of the column, Phenol 26.4 mass 0/0, ⁇ - Sole 9.6 mass 0/0, Mechirufue - consisting Le carbonate 0.2 wt% low boiling point reaction mixture (A) was withdrawn at 57.45 t ZHR.
- the reaction mixture (A) was subjected to heat exchange 27 in the same manner as in Example 1 and the same continuous mixture as in Example 1 was obtained.
- Ton Zhr was each continuously extracted.
- the high boiling point mixture (B) contains methanol.
- the amount was 0.08% by mass, and this was recycled in the continuous multistage distillation column A as a raw material for reactive distillation.
- composition of the low boiling point mixture (B) is 94.9% by mass of methanol, dimethyl carbonate 5.1.
- the amount of methanol continuously distilled off was 1.6 tons Zhr.
- the low boiling point mixture (B) is reacted with ethylene carbonate to form dimethyl carbonate and ester.
- continuous multistage distillation column B was performed in accordance with the continuous operation of continuous multistage distillation column A, but the separation efficiency after 500 hours and 1000 hours was the same as the initial stage and remained stable.
- Reactive distillation was carried out in the same manner using the same continuous multistage distillation column A as in Example 1, and methanol 3.0 mass%, dimethyl carbonate 62.8 mass%, phenol 28.0 mass 0 from the top outlet 26 of the column. / 0, ⁇ - sole 6.1 mass 0/0, Mechirufue - consisting Le carbonate 0.1 wt% low boiling point reaction mixture (A) was withdrawn at 57.11 t ZHR.
- the reaction mixture (A) was subjected to heat exchange 27 in the same manner as in Example 1 and the same continuous mixture as in Example 1 was obtained.
- the point mixture (B) was continuously withdrawn from the outlet 35 at 58.07 tons Zhr.
- the high-boiling mixture (B) has a methanol content of 0.009% by mass, which is reactive distillation.
- composition of the low boiling point mixture (B) is 93.3 mass% methanol, dimethyl carbonate 6.7
- continuous multi-stage distillation column B was performed in accordance with the continuous operation of continuous multi-stage distillation column A, but the separation efficiency after 500 hours, 1000 hours, and 2000 hours was the same as in the initial stage, and it moved stably. .
- the present invention efficiently separates by-product alcohols when producing aromatic carbonates from dialkyl carbonates and aromatic monohydroxy compounds by a reactive distillation system using a continuous multistage distillation column.
- it can be suitably used as a specific method capable of stably producing aromatic carbonates on an industrial scale of 1 ton or more per hour for a long period of time.
- FIG. 1 is a schematic view showing an example of a continuous multistage distillation column A for performing the reactive distillation of the present invention.
- An internal for example, tray 6) with n stages is installed inside.
- FIG. 2 is a schematic view showing an example of a multistage distillation column B.
- FIG. Internal is installed inside.
- the internal unit has n stages in the collection section (eg, tray 7) and n stages in the concentrating section (eg, tray 8).
- FIG. 3 is a schematic view of an apparatus for performing reactive distillation and distillation separation of by-product alcohols according to the present invention.
- 1 Gas outlet
- 2 Liquid outlet
- 3 Inlet
- 5 End plate section
- 6 Internal
- SS Recovery section
- ES Concentration section
- L Continuous multistage distillation column A Length (cm)
- D inner diameter (cm) of continuous multistage distillation column A
- d inner diameter (cm) of gas outlet of continuous multistage distillation column A
- d continuous multistage distillation
- L Length of the recovery section of the continuous multistage distillation column B (cm)
- L L:
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Description
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JP2006537690A JP4229395B2 (ja) | 2004-09-27 | 2005-09-21 | 芳香族カーボネートの工業的製造方法 |
US11/660,932 US20080223711A1 (en) | 2004-09-27 | 2005-09-21 | Industrial Process for Production of Aromatic Carbonate |
EP05785287A EP1795522A4 (en) | 2004-09-27 | 2005-09-21 | PROCESS FOR THE MANUFACTURE OF AROMATIC CARBONATE IN INDUSTRIAL STANDARD |
EA200700740A EA010579B1 (ru) | 2004-09-27 | 2005-09-21 | Промышленный способ получения ароматического карбоната |
BRPI0514936-3A BRPI0514936A (pt) | 2004-09-27 | 2005-09-21 | aperfeiçoamento em um processo industrial para a produção de um carbonato aromático |
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JP2009051814A (ja) * | 2007-05-25 | 2009-03-12 | Bayer Materialscience Ag | ジアルキルカーボネートからのジアリールカーボネートまたはアリールアルキルカーボネートの調製方法 |
RU2490251C2 (ru) * | 2007-09-14 | 2013-08-20 | Байер Матириальсайенс Аг | Способ получения диарилкарбонатов или алкиларилкарбонатов из диалкилкарбонатов |
RU2515993C2 (ru) * | 2008-06-21 | 2014-05-20 | Байер Матириальсайенс Аг | Способ получения по меньшей мере одного диарилкарбоната по меньшей мере из одного диалкилкарбоната и по меньшей мере из одного ароматического гидроксисоединения |
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JP4224510B2 (ja) | 2004-07-13 | 2009-02-18 | 旭化成ケミカルズ株式会社 | 芳香族カーボネート類の工業的製造法 |
WO2006022294A1 (ja) | 2004-08-25 | 2006-03-02 | Asahi Kasei Chemicals Corporation | 高純度ジフェニルカーボネートの工業的製造方法 |
WO2008099370A2 (en) | 2007-02-16 | 2008-08-21 | Sabic Innovative Plastics Ip Bv | Process for manufacturing dimethyl carbonate |
IN2014DN07584A (ja) | 2007-02-16 | 2015-07-10 | Sabic Innovative Plastics Ip | |
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- 2005-09-21 BR BRPI0514936-3A patent/BRPI0514936A/pt not_active IP Right Cessation
- 2005-09-21 CN CNB2005800326768A patent/CN100554240C/zh active Active
- 2005-09-21 KR KR1020077006640A patent/KR100870849B1/ko not_active IP Right Cessation
- 2005-09-21 EP EP05785287A patent/EP1795522A4/en not_active Withdrawn
- 2005-09-21 JP JP2006537690A patent/JP4229395B2/ja active Active
- 2005-09-21 EA EA200700740A patent/EA010579B1/ru not_active IP Right Cessation
- 2005-09-21 US US11/660,932 patent/US20080223711A1/en not_active Abandoned
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009051814A (ja) * | 2007-05-25 | 2009-03-12 | Bayer Materialscience Ag | ジアルキルカーボネートからのジアリールカーボネートまたはアリールアルキルカーボネートの調製方法 |
EP1995233A3 (de) * | 2007-05-25 | 2010-06-02 | Bayer MaterialScience AG | Verfahren zur Herstellung von Diaryl- oder Arylalkylcarbonaten aus Dialkylcarbonaten |
US8003817B2 (en) | 2007-05-25 | 2011-08-23 | Bayer Materialscience Ag | Process for the preparation of diaryl carbonates or arylalkyl carbonates from dialkyl carbonates |
RU2480448C2 (ru) * | 2007-05-25 | 2013-04-27 | Байер Матириальсайенс Аг | Способ и колонна для получения по меньшей мере одного диарилкарбоната и/или арилалкилкарбоната |
RU2490251C2 (ru) * | 2007-09-14 | 2013-08-20 | Байер Матириальсайенс Аг | Способ получения диарилкарбонатов или алкиларилкарбонатов из диалкилкарбонатов |
RU2490251C9 (ru) * | 2007-09-14 | 2014-01-27 | Байер Матириальсайенс Аг | Способ получения диарилкарбонатов или алкиларилкарбонатов из диалкилкарбонатов |
RU2515993C2 (ru) * | 2008-06-21 | 2014-05-20 | Байер Матириальсайенс Аг | Способ получения по меньшей мере одного диарилкарбоната по меньшей мере из одного диалкилкарбоната и по меньшей мере из одного ароматического гидроксисоединения |
Also Published As
Publication number | Publication date |
---|---|
JP4229395B2 (ja) | 2009-02-25 |
EA200700740A1 (ru) | 2007-10-26 |
EP1795522A1 (en) | 2007-06-13 |
CN100554240C (zh) | 2009-10-28 |
CN101027275A (zh) | 2007-08-29 |
JPWO2006035642A1 (ja) | 2008-05-15 |
BRPI0514936A (pt) | 2008-07-01 |
KR20070047357A (ko) | 2007-05-04 |
US20080223711A1 (en) | 2008-09-18 |
KR100870849B1 (ko) | 2008-11-27 |
EP1795522A4 (en) | 2008-08-06 |
EA010579B1 (ru) | 2008-10-30 |
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