WO2006033291A1 - Procédé de séparation industrielle d’alcools sous forme de produits dérivés - Google Patents

Procédé de séparation industrielle d’alcools sous forme de produits dérivés Download PDF

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Publication number
WO2006033291A1
WO2006033291A1 PCT/JP2005/017117 JP2005017117W WO2006033291A1 WO 2006033291 A1 WO2006033291 A1 WO 2006033291A1 JP 2005017117 W JP2005017117 W JP 2005017117W WO 2006033291 A1 WO2006033291 A1 WO 2006033291A1
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Prior art keywords
alcohols
distillation column
mass
carbonate
product
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PCT/JP2005/017117
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English (en)
Japanese (ja)
Inventor
Shinsuke Fukuoka
Hironori Miyaji
Hiroshi Hachiya
Kazuhiko Matsuzaki
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Asahi Kasei Chemicals Corporation
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Publication of WO2006033291A1 publication Critical patent/WO2006033291A1/fr

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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
    • 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
    • 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

Definitions

  • the present invention relates to an industrial separation apparatus for by-product alcohols. More specifically, alcohols by-produced when aromatic carbonates are continuously produced on an industrial scale of 1 ton or more per hour by transesterification of dialkyl carbonate and aromatic monohydroxy compound.
  • the present invention relates to an industrial separation apparatus for separating alcohols.
  • 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 aromatic carbonates a method based on a reaction between an aromatic monohydroxy compound and phosgene has been known for a long time, and various methods have been studied recently.
  • Aromatic carbonates produced by this method contain chlorine-based impurities that are difficult to separate, and cannot be used as a raw material for aromatic polycarbonate, for example, where high purity is required.
  • Patent Document 1 Japanese Patent Laid-Open No. 54-48732 (West German Patent Publication) 736063, U.S. Pat. No. 4,252,737)
  • Patent Document 2 JP-A-58-185536 U.S. Pat. No. 410464)
  • Patent Document 3-1 Examples of JP-A-56-123948 (US Pat. No. 4,182,726)); Patent Documents 3-2; Examples of JP-A-56-25138; Patent Documents 3-3: Examples of JP-A-60-169444 (US Pat. No. 4,554,110); Patent Document 3-4: JP-A-60-169445 (US Pat. No. 4,552,704) Examples; Patent Document 3 5: Example of JP-A-60-173016 (US Pat. No.
  • Patent Document 3-6 Example of JP-A-61-172852; Patent Document 3 — 7: Examples of JP-A 61-29 1545; Patent Document 3-8: Examples of JP-A 62-277345).
  • the inventors of the present invention continuously supply dialkyl carbonate and aromatic hydroxy compound to a multistage distillation column, continuously react in the column in the presence of a catalyst, and have a low boiling point containing alcohol as a by-product.
  • a reactive distillation method in which components are continuously extracted by distillation and a component containing the generated alkylaryl carbonate is extracted from the lower part of the column Patent Document 4: Japanese Patent Laid-Open No. 3-291257).
  • Patent Document 8 Italian Patent No. 01255746
  • Patent Document 9 JP-A-6-9506
  • Patent Document 10 Japanese Patent Laid-Open No. 6-41022 (European Patent 0572870, US Patent No. 5362901)
  • Patent Document 11 Japanese Patent Laid-Open No. 6-157424 (European Patent) No. 0582931, U.S. Pat. No.
  • Patent Document 12 JP-A-6-184058 (European Patent 0582930, US Pat. No. 5344954); Patent Document 13: JP-A-7 — Publication No. 304713; Patent Document 14: Japanese Patent Laid-Open No. 9-40616; Patent Document 15 : JP-A-9-59225; Patent Document 16: JP-A-9-110805; Patent Document 17: JP-A-9-165357; Patent Document 18: JP-A-9-173819; Patent Document 19- 1: JP-A-9-176094; Patent Document 19-2: JP-A 2000-191596; Patent Document 19-3: JP-A 2000-191597; Patent Document 20: JP-A-9-194436 (European Patent No.
  • Patent Document 21 International Publication No. 00Z1872 0 (US Pat. No. 6093842)
  • Patent Document 22-1 Japanese Patent Laid-Open No. 2001-64234
  • Patent Document 22-2 JP 2001-64235 A
  • Patent Document 23 International Publication No. 02Z 40439 (US Pat. No. 6,596,894, US Pat. No. 6596895, US Pat. No. 660 0061)).
  • the gas in the gas phase part is extracted using a method of extracting the gas in the phase part, separating the gas in the distillation column after heat exchange (Patent Document 24: JP-A-2003-113144) or the same reactor, After this is heat-exchanged and liquidized, the pressure in the gas phase part of the reactor A high-pressure distillation separation method (Patent Document 25: Japanese Patent Laid-Open No. 2003-155264) has been proposed.
  • Patent Document 25 Japanese Patent Laid-Open No. 2003-155264
  • the purpose of these methods is to separate the gas components when they are reacted using the continuous stirring tank as described above as a reactor in an energy-saving manner.
  • Patent Document 25 a reactive distillation method
  • the composition of the low-boiling point reaction mixture containing by-product alcohols produced by the above is greatly different from the separation of alcohols from the low-boiling point reaction mixture by the reactive distillation method at a predetermined concentration.
  • a method of distilling a liquid containing about 10 to 74% by mass of methanol at about 30 gZhr from the top of a distillation column installed at the top of a tank reactor Patent Document 26: JP-A-6-157410) is also proposed. ing.
  • these patent documents are of small laboratory scale, or are there! /, Which are just a comparative calculation of the amount of energy required for distillation, both on an industrial scale. There is no specific description or suggestion regarding separation.
  • the alcohol produced as a by-product 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 14 Tower top while extracting carbonate Extractive distillation method for extracting methanol from the reactor
  • Patent Document 19 distillation at atmospheric pressure to obtain a mixture consisting of about 70% by mass of methanol and about 30% by mass of dimethyl carbonate
  • Patent Document 20 To obtain a mixture consisting of 64.5% by mass of methanol and 35.5% by mass of dimethyl carbonate
  • Patent Document 15 This is a method (Patent Document 15).
  • Patent Document 19 When the reactive distillation method is used, the maximum force is 2 weeks (Patent Document 19), and the others are 10 days (Patent Document 15) and the time until steady state (Patent Documents 14 and 27). It is very short, and does not give any disclosure or suggestion of an industrial separation method that performs distillation operations stably for a long period of several thousand hours, for example, 5,000 hours. In this way, when aromatic carbonates are produced industrially by reactive distillation, specific methods and equipment relating to industrial methods for efficiently and stably separating large amounts of by-produced alcohols over a long period of time. No specific disclosure or suggestion has been made so far.
  • the problem to be solved by the present invention is that when an aromatic carbonate is continuously produced on an industrial scale of 1 ton or more per hour by a transesterification reaction between a dialkyl carbonate and an aromatic monohydroxy compound.
  • Another object of the present invention is to provide an industrial separation apparatus for separating alcohols from a low boiling point reaction mixture containing alcohols as a by-product. Means for solving the problem [0011] As a result of repeated studies to solve the above-mentioned problems and to find out a specific industrial separation apparatus capable of efficiently and stably separating a large amount of by-product alcohols for a long time, the present invention has been achieved. did.
  • Alcohols produced as a by-product in the continuous production of aromatic carbonates on an industrial scale of 1 ton or more per hour by transesterification of dialkyl carbonates with aromatic monohydroxy compounds A low boiling point reaction mixture containing alcohol with a length L (cm), an inner diameter D (cm), and an internal number of stages n that satisfy the following formulas (1) to (8): Recovery part with internal, length L (cm), inner diameter D (cm), inside
  • An industrial separation apparatus for by-product alcohols characterized in that:
  • the soot-exchange reaction is carried out by a reactive distillation method, and the low boiling point reaction mixture is mixed with a top component having a concentration of the alcohols of 90% by mass or more and an alcohol content of 0.2% by mass or less.
  • the amount of alcohols separated into a tower bottom component and separated as the tower top component is 200 kg or more per hour, according to any one of the preceding items 1 to 7, Industrial separation equipment for by-product alcohols,
  • the content of the alcohol in the column bottom component is 0.1% by mass or less with respect to 100% by mass of the column bottom component, any one of the items 8 to 10 above Industrial separation apparatus for by-product alcohols as described in
  • the industrial separation apparatus is used in the case of continuously producing aromatic carbonates on an industrial scale of 1 ton or more per hour by transesterification reaction between a dialkyl carbonate and an aromatic monohydroxy compound.
  • the alcohols can be stably and efficiently separated for a long time from the low boiling point reaction mixture containing the resulting alcohols.
  • the amount of alcohol separated as the top component is more than 200kg per hour, It can be easily separated into a column top component having an alcohol content of 90% by mass or more and a column bottom component having an alcohol content of 0.2% by mass or less.
  • the dialkyl carbonate used in the present invention is represented by the general formula (9).
  • 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.
  • alkyl groups, alicyclic groups, and aralkyl groups may be substituted with other substituents such as a lower alkyl group, lower alkoxy group, cyan group, halogen, etc., or unsaturated. Have a bond.
  • dialkyl carbonate having R 1 examples include dimethyl carbonate, jetyl carbonate, dipropyl carbonate (each isomer), diaryl carbonate, dibutenyl carbonate (each isomer), and dibutyl.
  • R 1 is preferably a dialkyl carbonate composed of an alkyl group having 4 or less carbon atoms not containing a halogen, particularly preferably! / Is dimethyl carbonate, which is preferably used in the present invention.
  • dialkyl carbonates are preferred among the preferred dialkyl carbonates, more preferred are dialkyl carbonates produced in a state substantially free of halogen! /, For example, alkylene carbonates substantially free of halogen. Alcohol power substantially free of halogen and halogen is also produced.
  • the aromatic monohydroxy compound used in the present invention is represented by the following general formula (10), 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 alcohols such as methoxyphenol (each isomer) and ethoxyphenol (each isomer) Phenols; arylalkylphenols such as phenolpropylphenol (each isomer); naphthol (each isomer) and various substituted naphthols; hydroxypyridine (each isomer), hydroxycoumarin (each isomer), Heteroaromatic monohydroxy compounds such as hydroxyquinoline (each isomer) are used.
  • aromatic monohydroxy compounds those that are preferably used in the present invention are aromatic monohydroxy compounds in which Ar 1 also has an aromatic group having 6 to 10 carbon atoms. Preference is given to phenol.
  • aromatic monohydroxy compounds those preferably used in the present invention are It is substantially free of rogen.
  • the reaction for producing an aromatic carbonate and by-producing alcohols is represented by the following formulas (11, 12).
  • the reaction formula (11) The reaction is mainly occurring.
  • the molar ratio of the dialkyl carbonate and the aromatic monohydroxy compound used in the transesterification reaction of the present invention is required to be 0.5 to 3 in terms of molar ratio. Outside this range, the remaining unreacted raw material increases with respect to the predetermined production amount of the target 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 transesterification reaction of the present invention is a method capable of continuously producing an aromatic carbonate at a production rate of 1 ton or more per hour and producing a low boiling point reaction mixture containing by-produced alcohols. Any method can be used, but the reaction distillation method is particularly preferred.
  • the aromatic carbonate produced in the present invention is an alkyl aryl carbonate, diaryl carbonate, or a mixture thereof obtained by transesterification of a dialkyl carbonate and an aromatic monohydroxy compound. In this ester exchange reaction, one or two alkoxy groups of the dialkyl carbonate were exchanged with the aryloxy group of the aromatic monohydroxy compound to remove alcohols (formulas 11 and 12).
  • Alkylaryl carbonate A reaction that converts to diaryl carbonate and dialkyl carbonate by a disproportionation reaction (Equation 13), which is an ester exchange reaction between two molecules, may be included.
  • alkylaryl carbonate is mainly obtained.
  • This alkylaryl carbonate is further subjected to ester exchange reaction with an aromatic monohydroxy compound, or disproportionation reaction (formula 13 ) Can be used to make a gear reel carbonate.
  • This diaryl carbonate was completely free of halogen. Therefore, it is important as a raw material when industrially producing polycarbonate by the transesterification method.
  • a small amount of alkyl aryl ether is usually produced as a reaction byproduct.
  • the dialkyl carbonate and aromatic monohydroxy compound used as raw materials in the transesterification reaction of the present invention may have high purity, but may contain other compounds. .
  • it may contain compounds and reaction byproducts produced in this step and z or other steps.
  • these raw materials include dialkyl carbonates and aromatic monohydroxy compounds that are newly introduced into the reaction system, as well as those recovered from this step and Z or other steps. And are preferred.
  • the industrial separation apparatus of the present invention the low boiling point reaction mixture withdrawn from the upper part of the reactor is continuously distilled and separated, so that the component having a low alcohol content is used as a raw material for the transesterification reaction. It can be reused, and this is a particularly preferred method.
  • the transesterification reaction of the present invention is usually carried out in the presence of a known catalyst.
  • these catalysts may be solid catalysts fixed in a multistage distillation column that performs reactive distillation, or may be soluble catalysts that are dissolved in the reaction system. May be.
  • these catalyst components reacted with organic compounds present in the reaction system, such as aliphatic alcohols, aromatic monohydroxy compounds, alkyl aryl carbonates, diaryl carbonates, dialkyl carbonates and the like. It may be a product, or it may have been heat-treated with raw materials and products prior to the reaction!
  • catalysts in this sense include, for example, PbO, Pb (OH), Pb (0
  • the continuous multi-stage steaming is performed.
  • Any method may be used in which the catalyst is present in the distillation column (hereinafter referred to as “continuous multistage distillation column A”).
  • continuous multistage distillation column A When the catalyst is in a solid state insoluble in the reaction solution, Multi-stage distillation column There are methods such as installing in the column in column A, or fixing it in the column by installing it in a packed form. Further, in the case of a catalyst that dissolves in the raw material or the reaction solution, it is preferable to supply it into the upper force distillation column from the middle part of the distillation column A.
  • 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 is usually expressed as a ratio with respect to the total weight of the raw material, which varies depending on the type of catalyst used, the type of raw material and its ratio, reaction temperature and reaction pressure, and other reaction conditions 0.0001 to 30% by mass, preferably 0.005 to 10% by mass, more preferably 0.001 to 1% by mass.
  • FIG. 1 is a schematic diagram showing an example of a continuous multi-stage distillation column A that performs reactive distillation, which is a preferred reaction method for performing a transesterification reaction of the present invention.
  • the continuous multistage distillation column A used as the reactive distillation column is long in the production amount of 1 ton or more of at least one aromatic carbonate per hour. Any material can be used as long as it can be stably produced over a period of time.
  • a length L (cm) that satisfies the conditions of the following formulas (14) to (19) and an inner diameter D (cm ), And has an internal structure (for example, tray 6) with an internal stage number n, and a gas outlet 1 with an inner diameter d (cm) at the top of the tower or near the top of the tower, a tower at or near the bottom of the tower.
  • 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.
  • continuous multistage distillation column A that simultaneously satisfies the formulas (14) to (19) as a reactive distillation column, 1 ton or more per hour from a dialkyl carbonate and an aromatic monohydroxy compound, usually 1 to :
  • aromatic carbonates have high selectivity and high productivity. For example, 2000 hours or more, preferably 3000 hours or more, more preferably 5000 hours or more Can be manufactured.
  • the transesterification reaction carried out in the present invention is carried out continuously, and the reaction time is considered to correspond to the average residence time of the reaction liquid in the reactor. It varies depending on the amount supplied, the type and amount of the catalyst, the reaction conditions, etc. In the case of the reactive distillation method, it varies depending on the internal shape of the distillation column, the number of stages, the distillation conditions, etc. 0.05 to 5 hours, more preferably 0.1 to 3 hours.
  • the reaction temperature varies depending on the type of raw material compound used and the type and amount of the catalyst, but is usually 100 to 350 ° C. In order to increase the reaction rate, it is preferable to increase the reaction temperature. If the reaction temperature is high, side reactions are liable to occur.
  • reaction temperature is 130 to 280. C, more preferably 150-260. C, more preferably 180-250. C range.
  • the reaction pressure varies depending on the type and composition of the raw materials used, the reaction temperature, etc. 1S reduced pressure, normal pressure, or pressurized pressure is usually 0.1-2 X 10 7 Pa, preferably Is carried out in the range of 10 5 to: L0 7 Pa, more preferably 2 ⁇ 10 5 to 5 ⁇ 10 6 .
  • a low-boiling point reaction containing alcohols produced by continuously supplying a raw material dialkyl carbonate and an aromatic monohydroxy compound to a reactor in which a catalyst exists.
  • Aromatic carbonates are continuously produced by continuously withdrawing the mixture in gaseous form from the upper part of the reactor and continuously withdrawing the high boiling point reaction mixture containing the aromatic carbonates in liquid form from the lower part of the tower.
  • a reactive distillation system in which the reactor is a continuous multistage distillation column A is preferred.
  • the raw material is continuously fed into the continuous multistage distillation column A in which a catalyst is present, Simultaneous reaction and distillation
  • the low boiling point reaction mixture (hereinafter referred to as “A”) containing the generated alcohols is
  • the aromatic carbonate is continuously withdrawn in a gaseous state, and a high boiling point reaction mixture containing aromatic carbonates (hereinafter referred to as “A”) is continuously withdrawn in liquid form from the bottom of the column.
  • A a high boiling point reaction mixture containing aromatic carbonates
  • the amount of the low boiling point reaction mixture (A) continuously withdrawn from the reactor depends on the raw material composition and amount, the reactive distillation conditions, and the reaction.
  • the force varies depending on the response rate, selectivity, etc. Usually, it is 10 tons Zhr or more and 1000 tons Zhr or less.
  • the composition of the low boiling point reaction mixture (A) to be separated has reaction conditions! /,
  • the low boiling point reaction mixture (A) is usually used as a by-product alcohol 1.5 to 100% by mass.
  • FIG. 2 is a schematic diagram showing an example of a continuous multistage distillation column (hereinafter referred to as “continuous multistage distillation column B”) which is an industrial separation apparatus for by-product alcohols of the present invention.
  • the present invention provides a separation apparatus suitable for efficiently distilling and separating the low boiling point reaction mixture having such a composition containing by-product alcohol on an industrial scale, and the separation apparatus comprises: A recovery section SS having an internal length (for example, tray 7) having a length L (cm), an inner diameter D (cm), and an internal number n (for example, tray 7) satisfying the formulas (1) to (8), and a length L (cm), inner diameter D (cm), and n steps inside
  • a recovery section SS having an internal length (for example, tray 7) having a length L (cm), an inner diameter D (cm), and an internal number n (for example, tray 7) satisfying the formulas (1) to (8), and a length L (cm), inner diameter D (cm), and n steps
  • FIG. 2 A distillation column consisting of a concentrating section ES with two internals (eg, tray 8) is required.
  • Reference numerals 1 to 4 in FIG. 2 denote the same members as in FIG.
  • L (cm) force is less than 00, the separation efficiency of the recovery unit will decrease, and the target separation efficiency will not be achieved.To reduce the equipment cost while ensuring the target separation efficiency, L should be It is necessary to make it smaller.
  • a more preferable range of L (cm) is 800 ⁇ L ⁇ 2500, and more preferably 1 000 ⁇ L ⁇ 2000.
  • D (cm) is smaller than 100, the target distillation amount cannot be achieved, and D must be smaller than 500 in order to reduce the equipment cost while achieving the target distillation amount. is there.
  • a more preferable range of D (cm) is 120 ⁇ D ⁇ 400, and more preferably 150 ⁇ D ⁇ 300.
  • L ZD When it is less than L ZD 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 lowered, 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.
  • L (cm) is less than 700, the separation efficiency of the concentrating part is lowered, so that the desired separation effect is achieved.
  • 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
  • the range of new L / 15 is 15 ⁇ L ZD ⁇ 30, more preferably 20 ⁇ L / ⁇ ⁇
  • n is less than 35, the separation efficiency of the concentrating part decreases, and 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 continuous multistage distillation column B used for industrial separation of by-product alcohols of the present invention is a distillation having a tray and Z or a packing as an internal in a recovery part SS and a concentrating part ES.
  • a tower is preferred.
  • the term “internal” as used in the present invention means a portion where gas-liquid contact is actually performed in a distillation column.
  • a tray for example, a foam tray, a perforated plate tray, a valve tray, a counterflow tray, a super flack tray, a max flutter tray, etc.
  • Irregular packing such as Nolenore Sad Nore, Interlocks Saddle, Dixon Packing, McMahon Packing, Helical Pack, etc. I like it.
  • a multistage 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 sum of the number of trays and the number of theoretical plates.
  • the internals of the recovery section SS and the concentration section ES of the continuous multistage distillation column B are trays. It was also 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 has also been found that it is preferred that the perforated plate tray has 100-: LOOO holes per area lm 2 of the perforated plate portion! More preferably! / The number of fistulas is 120-900 per lm 2 of the area, and more preferably 150-800. It has also been found that the cross-sectional area per hole of the perforated plate lay is preferably 0.5 to 5 cm 2 .
  • the cross-sectional area per hole is more preferably 0.7 to 4 cm 2 , and further preferably 0.9 to 3 cm 2 . Further, when the perforated plate tray has 100 to: LOOO 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.
  • the ester exchange reaction of the present invention is carried out by the reactive distillation method, it is preferable to use the above-mentioned internal also for the continuous multistage distillation column A used as the reactive distillation column, and particularly the formulas (11) and (12).
  • a tray for a reactive distillation column that mainly performs the reaction of (3) and an internal tray and a regular packing for a reactive distillation column that mainly performs the reaction of the formula (13).
  • a low boiling point reaction mixture of a transesterification reaction containing by-product alcohols may be supplied in a gaseous state into the continuous multistage distillation column B.
  • the heat of the low boiling point reaction mixture usually extracted in the form of gas can be used for heating other substances, for example, the raw material of the transesterification supplied to the reactor. This is a particularly preferable method.
  • the low boiling point reaction mixture supplied to the continuous multistage distillation column B becomes gaseous, gas-liquid mixed, or liquid. Further, the position where the low boiling point reaction mixture is fed into the continuous multistage distillation column B is between the recovery unit SS and the concentrating unit ES.
  • the continuous multistage distillation column B preferably has a reboiler for heating the distillate and a reflux device.
  • a by-product is produced when an aromatic carbonate is continuously produced on an industrial scale of 1 ton Zhr or more by a transesterification reaction between a dialkyl carbonate as a raw material and an aromatic monohydroxy compound.
  • the low-boiling point reaction mixture containing alcohols is usually provided with an industrial distillation apparatus that separates 10 to LO 00 tons Zhr.
  • the concentration power of the alcohols is 90% by mass or more, preferably Is 95% by mass or more, more preferably 97% or more of the top component (hereinafter referred to as “B”) and the alcohol content is 0.2% by mass.
  • % Preferably 0.1% by mass or less, more preferably 0.07% by mass or less of the bottom component (hereinafter referred to as “B”) for stable and efficient separation over a long period of time. Is possible.
  • the amount of alcohol separated as the top component (B) is reduced to 200k.
  • gZhr or more, preferably 500 kgZhr or more, more preferably 1 to 20 tons Zhr.
  • the column top component (B) contains 90% by-product alcohols.
  • the tower top component (B) is used as a dialkyl carbonate production raw material.
  • dialkyl carbonate a method using a carbonylation reaction of alcohols and a method using an alcohololysis reaction of alkylene carbonate are industrially carried out. Any reaction
  • the alcohololysis reaction of alkylene carbonate is an equilibrium reaction, it is preferable to use a raw material having a high alcohol concentration. It is a preferred method to use the top component (B) as a raw material for this reaction. In this case, the top of the tower
  • the alcohol concentration in component (B) is 95% by mass or more, more preferably 97% by mass or more.
  • the bottom component (B) is mixed with the low boiling point reaction mixture.
  • the component power of the column top component (B) is extracted from the component of the product, and the column bottom component (B) 10
  • the content of by-product alcohols is 0.2% by mass or less, preferably 0.1% by mass or less with respect to 0% by mass.
  • the main components are a dialkyl carbonate and an aromatic monohydroxy compound. And a small amount of by-produced alkyl aryl ether and a small amount of aromatic strength bonates. Therefore, this bottom component B is transesterified.
  • the distillation conditions of the continuous multistage distillation column B are such that the column bottom temperature is 150 to 300 ° C., preferably 170 to 270 °. C, more preferably 190 to 250 ° C., and the top pressure is 2 ⁇ 10 5 to 5 ⁇ 10 6 Pa, preferably 4 ⁇ 10 5 to 3 ⁇ 10 6 Pa, more preferably 6 ⁇ 10 5 to 2 X 10 6 Pa and the reflux specific force is 0.1 to 20, preferably 0.5 to 15, and more preferably 1.0 to 10.
  • the long-term stable operation in the present invention refers to a steady state based on operating conditions where there is no flooding or piping clogging or erosion for 1000 hours or more, preferably 3000 hours or more, more preferably 5000 hours or more. While the operation can be continued and the predetermined separation efficiency is maintained, a predetermined amount of by-product alcohol of 200 kgZhr or more is distilled and separated as the top component (B).
  • the material constituting the continuous multistage distillation column, internal, piping, etc. of the present invention is preferably mainly carbon steel, stainless steel or the like.
  • Examples 3 to 7 are examples for showing the performance of the industrial separation apparatus of the present invention.
  • the composition of the mixture was measured by gas chromatography, and the halogen was measured by ion chromatography.
  • the catalyst is Pb (OPh) so that the reaction solution is about 70 ppm.
  • the amount of methyl phenyl carbonate produced per hour was 8.3 tons (excluding the amount introduced into distillation column A, the actual amount produced was 7.5 tons Zhr), and the production of diphenyl carbonate per hour Production was found to be 0.22 tons.
  • the combined selectivity of methyl phenol carbonate and diphenyl carbonate with respect to 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. Meanwhile, fresh dimethyl carbonate was continuously introduced from the inlet 41 at the bottom of the distillation column B at 2.53 tons Zhr.
  • the distillation column B is continuously distilled and separated 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 discharged from the outlet 39 to 1.73 tons Zh
  • the high boiling point mixture (B) is continuously extracted from the extraction port 35 to 86 tons Zhr. It was.
  • the high boiling point mixture (B) has a methanol content of 0.1% by mass or less.
  • the composition was the same as that of the raw material 2 of the continuous multistage distillation column A, and this was recycled and reused as the raw material 2.
  • 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.
  • a long-term continuous operation was performed under these conditions. After 500 hours, 1000 hours, and 2000 hours, the production volume per hour is 1,8 tons, 11.8 tons, and 11.8 tons of methylphenol carbonate, and per hour of diphenyl carbonate.
  • the production rate is 0.6 tons, 0.6 tons, and 0.6 tons, and the combined selectivity of methylphenol carbonate and diphenol carbonate is 98%, 98%, 98%, which is very It was stable.
  • the produced aromatic strength boronate was substantially free of halogen (lppb or less).
  • 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 ton Zhr from the inlet 51 in the fourth stage of the lower part of the concentration section.
  • the distillation column B is continuously distilled and separated at a column bottom temperature of 213 ° C, a column top temperature of 138 ° C, and a reflux ratio of 2.89, and a low boiling point mixture (B) is formed.
  • the high boiling point mixture (B) has a methanol content.
  • composition of the low boiling point mixture (B) is 93.3 mass% methanol, dimethyl carbonate 6.7.
  • the low boiling point mixture (B) is reacted with ethylene carbonate to form dimethyl carbonate and
  • 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. .
  • 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 3 was obtained.
  • the mixture (B) was continuously withdrawn from the outlet 35 at 80.83 ton Zhr.
  • the high boiling point mixture (B) has a methanol content of 0.1% by mass or less, which is a reactive distillation.
  • 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 performed in the same manner using the same continuous multi-stage distillation column A as in Example 3, Tower top withdrawal 26 Methanol 2.8% by mass, dimethyl carbonate 61.0% by weight, phenol 26.4 wt 0/0, ⁇ - Sole 9.6 mass 0/0, Mechirufue - Le carbonate 0.2 wt%
  • a low boiling point reaction mixture (A) consisting of was extracted at 57.45 ton Zhr.
  • 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 3 was obtained.
  • the point mixture (B) was continuously withdrawn from the outlet 35 at 58.2 tons Zhr.
  • the high boiling point mixture (B) has a methanol content of 0.08% by mass
  • 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.
  • 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 3 was obtained.
  • the high boiling point mixture (B) has a methanol content of 0.
  • composition of the low-boiling 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 relates to alcohols produced as a by-product when an aromatic carbonate is continuously produced on an industrial scale of 1 ton or more per hour by a transesterification reaction between a dialkyl carbonate and an aromatic monohydroxy compound.
  • the low boiling point reaction mixture containing alcohol can be suitably used as an industrial separation apparatus for separating alcohols.
  • FIG. 1 is a schematic diagram showing an example of a continuous multistage distillation column A that performs reactive distillation, which is a preferred reaction system for performing the transesterification reaction 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 continuous multistage distillation column which is an industrial separation apparatus for by-product alcohols of the present invention. Internal is installed inside. Internally, the collection unit (for example, tray 7) has n stages and the concentration unit (for example, tray 8) has n.
  • FIG. 3 is a schematic diagram showing a connection between reactive distillation and an apparatus for performing distillation separation of by-product alcohols of the present invention.
  • 1 Gas outlet
  • 2 Liquid outlet
  • 3 Inlet
  • 5 End plate
  • 6, 7, 8 Tray
  • SS Recovery section
  • ES Concentration section
  • L Continuous multistage distillation column A Length (cm)
  • D inner diameter of continuous multistage distillation column A (cm)
  • d inner diameter of gas outlet of continuous multistage distillation column A (cm)
  • d continuous multistage
  • Diameter (cm), D Inner diameter of concentrating part of continuous multistage distillation column B (cm), 10, 11, 20, 21, 31, 41,

Abstract

L’invention porte sur un séparateur industriel permettant de séparer un alcool de manière efficace et stable sur une longue période à partir d'une grande quantité d'un mélange de réaction à faible point d'ébullition d’une composition spécifique en soumettant un carbonate dialkyle et un composé monohydroxyle aromatique à un phénomène de transestérification dans une colonne de distillation réactive en présence d’un catalyseur afin de produire en grande quantité à échelle industrielle au rythme d’une tonne par heure ou plus un carbonate aromatique qui contient de l’alcool comme produit dérivé. L’invention propose une colonne de distillation continue à plusieurs étages ayant une structure spécifique comme séparateur industriel d’alcools sous forme de produits dérivés susceptible d’atteindre l’objectif.
PCT/JP2005/017117 2004-09-21 2005-09-16 Procédé de séparation industrielle d’alcools sous forme de produits dérivés WO2006033291A1 (fr)

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DE102008029514A1 (de) 2008-06-21 2009-12-24 Bayer Materialscience Ag Verfahren zur Herstellung von Diarylcarbonaten aus Dialkylcarbonaten
EP2239249A1 (fr) 2009-04-08 2010-10-13 Bayer MaterialScience AG Procédé de fabrication de carbonates de diaryle ou d'alkylaryle à partir de carbonates de dialkyle
DE102010042937A1 (de) 2010-10-08 2012-04-12 Bayer Materialscience Aktiengesellschaft Verfahren zur Herstellung von Diarylcarbonaten aus Dialkylcarbonaten
EP2650278A1 (fr) 2012-04-11 2013-10-16 Bayer MaterialScience AG Procédé de fabrication de diarylcarbonates à partir de dialkylcarbonates

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JP2001064235A (ja) * 1999-08-27 2001-03-13 Chiyoda Corp ジアリールカーボネートの製造方法
JP2003516376A (ja) * 1999-12-08 2003-05-13 ゼネラル・エレクトリック・カンパニイ ジアリールカーボネートの連続生産法及び装置
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JPH09176094A (ja) * 1995-12-27 1997-07-08 Jiemu P C Kk 芳香族カーボネートの連続的製造方法
JP2001064235A (ja) * 1999-08-27 2001-03-13 Chiyoda Corp ジアリールカーボネートの製造方法
JP2003516376A (ja) * 1999-12-08 2003-05-13 ゼネラル・エレクトリック・カンパニイ ジアリールカーボネートの連続生産法及び装置
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DE102008029514A1 (de) 2008-06-21 2009-12-24 Bayer Materialscience Ag Verfahren zur Herstellung von Diarylcarbonaten aus Dialkylcarbonaten
US9040732B2 (en) 2008-06-21 2015-05-26 Bayer Materialscience Ag Process for preparing diaryl carbonates from dialkyl carbonates
EP2239249A1 (fr) 2009-04-08 2010-10-13 Bayer MaterialScience AG Procédé de fabrication de carbonates de diaryle ou d'alkylaryle à partir de carbonates de dialkyle
DE102009016853A1 (de) 2009-04-08 2010-10-14 Bayer Materialscience Ag Verfahren zur Herstellung von Diaryl- oder Alkylarylcarbonaten aus Dialkylcarbonaten
US8952189B2 (en) 2009-04-08 2015-02-10 Bayer Materialscience Ag Process for preparing diaryl carbonates or alkyl aryl carbonates from dialkyl carbonates
DE102010042937A1 (de) 2010-10-08 2012-04-12 Bayer Materialscience Aktiengesellschaft Verfahren zur Herstellung von Diarylcarbonaten aus Dialkylcarbonaten
EP2457891A1 (fr) 2010-10-08 2012-05-30 Bayer MaterialScience AG Procédé de fabrication de diarylcarbonates à partir de dialkylcarbonates
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EP2650278A1 (fr) 2012-04-11 2013-10-16 Bayer MaterialScience AG Procédé de fabrication de diarylcarbonates à partir de dialkylcarbonates

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