Classifications

• • 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
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods
• • 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
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/30—Details relating to random packing elements
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
  • B01J2219/33—Details relating to the packing elements in general
  • B01J2219/3306—Dimensions or size aspects
• • 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 process for producing aromatic carbonates. More specifically, alkylaryl carbonate obtained by transesterification reaction between a dialkyl carbonate and an aromatic monohydroxy compound is used as a raw material, and this raw material is mainly used as a diaryl carbonate in a continuous multistage distillation column in which a catalyst exists.
• the present invention relates to a method for industrially producing a large amount of aromatic power carbonate useful as a raw material for transesterification polycarbonate by conversion to aromatic carbonates as products.
• 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 JP-A-51-105032, JP-A-56-123948, JP-A-56-123949 (West Germany) Patent Publication No. 2528412, British Patent No. 149 9530, U.S. Pat.No. 4,182,726), Japanese Patent Laid-Open No. 51-75044 (West German Patent Publication No. 2552907, U.S. Pat. No. 4045464)
• Tin compounds such as organotin alkoxides and organotinoxides
• Patent Document 2 JP 54-48733 A (West German Patent Publication No.
• Patent Document 4 Japanese Unexamined Patent Publication No. 57-176932, Japanese Unexamined Patent Publication No. 1-93560, metals such as copper, iron, zirconium, etc.
• Patent Document 5 JP-A-57-183745
• titanate esters Patent Document 6
• Patent Document 6 JP-A-58-185536 (US Pat. No. 4410464)
• JP-A-1 ⁇ See 265062 Lewis acid and protonic acid mixture
• Patent Document 7 Japanese Unexamined Patent Publication No. 60173016 (US Pat. No. 4,609,501)
• Sc, Mo, Mn, Bi, Te, etc. Patent Document 8: see JP-A-1-265064
• ferric acetate Patent Document 9: see JP-A-61-172852
• catalyst development alone cannot solve the problem of unfavorable equilibrium, there are a large number of issues to consider in order to achieve an industrial production method for mass production, including examination of reaction methods.
• Patent Document 10 Japanese Patent Laid-Open No. 54-48732 (West German Patent Publication) No. 736063, U.S. Pat. No. 4,252,737)
• Patent Document 11 Japanese Patent Laid-Open No. 58-185536 (US Pat. 410464)
• Patent Document 12 JP-A-56-123948 (US Pat. No. 4,182,726)), JP-A-56-25138, JP-A-60-169444 ( Example of US Pat. No. 4,554,110), Example of JP-A-60-169445 (US Pat. No. 4,552,704), JP-A-60-173016 (US Pat. No. 4,609,501) ), Examples of JP-A 61-172852, Examples of JP-A 61-291545, 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 to produce by-produced alcohol.
• a low-boiling component containing nitrogen is continuously extracted by distillation, and a component containing the generated alkylaryl carbonate is extracted from the bottom of the column (see Patent Document 13: Japanese Patent Publication No. Hei 3-291257).
• Low-boiling components including dialkyl force-bonate as a by-product are continuously extracted by distillation, and the produced diaryl carbonate is removed.
• Reactive distillation method for extracting components from the bottom of the column Heisei 4-9358) these reactions are carried out using two continuous multi-stage distillation towers, and diaryl carbonate is continuously produced while efficiently recycling the by-produced dialkyl carbonate.
• Reactive distillation method Patent Document 15: Japanese Patent Laid-Open No. Hei 4-2110378
• dialkyl carbonate and aromatic hydroxy compound are continuously supplied to a multistage distillation column, and the liquid flowing down in the column is distilled into the distillation column. After being extracted from the side outlet provided in the middle stage and Z or the lowermost stage of the reactor, introduced into the reactor provided outside the distillation column and reacted, the upper part of the stage above the stage having the outlet is provided.
• a reactive distillation method in which a reaction is carried out both in the reactor and in the distillation column by being introduced into a circulation inlet provided in a stage Patent Document 16: JP-A-4-224547, JP-A-4- No. 230242, Japanese Laid-Open Patent Publication No. 4 235951)) etc.
• Patent Document 16 JP-A-4-224547, JP-A-4- No. 230242, Japanese Laid-Open Patent Publication No. 4 235951)
• Patent Documents 17 to 32 Patent Document 17: International Publication No. 00Z18720 (U.S. Pat. No. 5,362,901); Patent Document 18: Italian Patent 01255746) Patent Document 19: JP-A-6-9506 (European Patent 0560159, US Pat. No. 5,282,965); Patent Document 20: JP-A-6-41022 (European Patent 0572870, US Patent No. 5 362901); Patent Document 21: JP-A-6-157424 (European Patent 0582931, US Pat. No.
• Patent Document 22 Japanese Patent Laid-Open No. 7-304713
• Patent Document 23 Japanese Patent Laid-Open No. 9-40616
• Patent Document 24 Japanese Patent Laid-Open No. 9-59225
• Patent Document 25 Japanese Patent Laid-Open No. 9-110805
• Patent Document 27 JP-A-9-173819
• Patent Document 28 JP-A-9-176094, JP-A 2000-191596, JP-A 2000-191597
• Patent Document 29 Special Kaihei 9-194436 (European Patent 0785184, US Pat. No. 5,705,673)
• Patent Document 30 International Publication No.
• Patent Document 31 Japanese Patent Laid-Open No. 2001-64234, Japanese Patent Laid-Open No. 2001-6423-5; Patent Document 32: International Publication No. 02Z40439 (US Pat. No. 6,596,894, US Pat. No. 6596895) U.S. Pat. No. 6600061))).
• the applicant of the present invention is a high-boiling point containing a catalyst component as a method for stably producing a high-purity aromatic carbonate for a long time without requiring a large amount of catalyst.
• a method of separating the substance after reacting with the active substance and recycling the catalyst component see Patent Document 31: JP 2001-64234 A, JP 2001-64235 A), and polyvalent aroma in the reaction system In which the group hydroxy compound is maintained at a mass ratio of 2.0 or less with respect to the catalyst metal (Patent Document 32: International Publication No. 02Z40439 (US Pat. No. 6,596,894, US Pat. No. 6596895, US Pat. No. 6600061) Proposal)) was proposed.
• the present inventors use a method in which 70 to 99% by mass of phenol produced as a by-product in the polymerization process is used as a raw material to produce diphenol carbonate by a reactive distillation method, and this is used as a polymerization raw material for aromatic polycarbonate.
• Patent Document 33 International Publication No. 97Z11049 (European Patent No. 0855384, US Patent No. 5872275)).
• Patent Document 34 JP-A-11-92429 (European Patent No. 1016648, US Patent (See Komi 6262210)
• Patent Document 35 Japanese Patent Laid-Open No. 9-255772 (see European Patent 0892001, US Patent No. 5747609)
• the problem to be solved by the present invention is to use alkylaryl carbonate obtained by a transesterification reaction of a dialkyl carbonate and an aromatic monohydroxy compound as a raw material, and to use this raw material as a catalyst using a continuous multistage distillation column.
• diaryl carbonate is produced in an amount of 1 ton or more per hour. It is intended to provide a concrete method that can be manufactured on an industrial scale with high selectivity and high productivity for a long period of time.
• the continuous multi-stage distillation column has a structure having end plates above and below a cylindrical body having a length L (cm) and an inner diameter D (cm), and an internal having n stages inside.
• the continuous multi-stage distillation column has a structure having end plates above and below a cylindrical body having a length L (cm) and an inner diameter D (cm), and an internal having n stages inside.
• the internal tray is a perforated plate tray having a perforated plate portion and a downcomer portion.
• the internal packing is one or more regular packings, and the tray is a perforated plate tray having a perforated plate portion and a downcomer portion. the method of,
• the regular packing is at least one selected from Mela Pack, Gem Pack, Techno Bag, Flexi Pack, Sulza Packing, Good Roll Packing, Glitch Grid Force, and the perforated plate tray has an area of the perforated plate part lm.
• a continuous multistage distillation column for carrying out the reaction and distillation
• End plate portions disposed above and below the body portion
• L, D, L / D, n, D / d, and D / d of the continuous multistage distillation column are 2000 ⁇
• Is a continuous multi-stage distillation column according to 20, 22.L, D, LZD, n, D / d, D / d of the continuous multistage distillation column are 2500 ⁇
• the internal packing is one or more regular packings
• the tray is a perforated plate tray having a perforated plate portion and a downcomer portion.
• the regular packing is at least one selected from Mela Pack, Gem Pack, Techno Bag, Flexi Pack, Sulza Packing, Good Roll Packing, Glitch Grid Force, and the perforated plate tray has an area of the perforated plate part lm.
• 100 per 2: L000 amino is a also has a hole, the continuous multi-stage distillation column according to item 27, wherein the cross-sectional area per porous plate tray hole is 0. 5 ⁇ 5cm 2 ,
• a dialkyl carbonate, an aromatic monohydroxyl compound, and an alkylaryl carbonate obtained as a raw material are used as raw materials of 95% or more, preferably 97% or more, more preferably 99% or more.
• the diaryl carbonate obtained by separating and purifying aromatic carbonates mainly composed of diaryl carbonate obtained by the present invention by distillation or the like has high purity, and is a transesterified polycarbonate or polyester. It is useful as a raw material for carbonates and the like, and as a raw material for non-phosgene isocyanates and urethanes.
• the halogen content of the resulting diaryl carbonate is not more than 0.1 ppm, preferably not more than lOppb, more preferably lppb or less.
• the dialkyl carbonate used for obtaining the alkylaryl carbonate which is the raw material of the present invention is represented by the general formula (8).
• 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 isomer).
• Heptyl (each isomer), octyl (each isomer), nonyl (each isomer), decyl (each isomer), an alkyl group such as cyclohexylmethyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo Examples include alicyclic groups such as heptyl; aralkyl groups such as benzyl, phenethyl (each isomer), phenylpropyl (each isomer), phenylbutyl (each isomer), and methylbenzyl (each isomer). .
• alkyl groups alicyclic groups, and aralkyl groups
• substituents such as lower alkyl It may be substituted with an alkyl group, lower alkoxy group, cyano group, halogen or the like, or may have an unsaturated bond.
• dialkyl carbonate having R 1 examples include dimethyl carbonate, jetyl carbonate, dipropyl carbonate (each isomer), diallyl 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 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 that is substantially free of halogens, for example, alkylene carbonates substantially free of halogens. Alcohol power substantially free of halogen is also produced.
• the aromatic monohydroxy compound used in the present invention is represented by the following general formula (9), and any hydroxyl group directly bonded to the aromatic group may be used. 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 Isomers), jetylphenol (each isomer), methylethylphenol (each isomer), methylpropylphenol (each isomer), dipropylphenol (each isomer), methylbutyrphenol (each isomer) ), Pentylphenol (each isomer), hexylphenol (each isomer), various alkylphenols such as cyclohexylphenol (each isomer); methoxyphenol (each isomer), ethoxyphenol (each) Various alkoxyphenols such as iso
• aromatic monohydroxy compounds those that are preferably used in the present invention are aromatic monohydroxy compounds in which Ar 1 has an aromatic group having 6 to 10 carbon atoms. Particularly preferred is phenol. Of these aromatic monohydroxy compounds, those that are preferably used in the present invention are those that do not substantially contain halogen.
• the amount ratio of the dialkyl carbonate and the aromatic monohydroxy compound used to obtain the alkylaryl carbonate as the raw material of the present invention is such that the dialkyl carbonate is in a molar ratio with respect to the aromatic monohydroxy compound. 0. It should be 4-4. Outside this range, the unreacted residual amount increases relative to the desired amount of alkylaryl carbonate, which is not efficient, and requires a lot of energy to recover them. In this sense, the molar ratio is 0.5 to 3 force, 0.8 to 2.5 is more preferable, and 1.0 to 2.0 is more preferable.
• the force for continuously producing 1 ton or more of diaryl carbonate per hour is the alkylaryl carbonate continuously supplied.
• the diaryl carbonate to be produced Is usually 5P ton Zhr, preferably 3P ton Zhr, more preferably 2P ton Zhr. In a more preferred case, it can be less than 1.8 P tons Zhr.
• the aromatic carbonates produced in the present invention are aromatic carbonates mainly comprising diaryl carbonate obtained by transesterification of alkylaryl carbonate.
• alkylary This is a disproportionation of two reactions: a reaction in which the alkoxy group of an alkyl carbonate is exchanged with an alkyl group of an aromatic monohydroxy compound present in the system to remove alcohols, and a transesterification reaction between two alkylaryl carbonates. It includes a reaction that is converted to diaryl carbonate and dialkyl carbonate by the conversion reaction.
• the disproportionation reaction of alkyl aryl carbonate mainly occurs.
• raw materials and catalysts that do not contain any halogen can be used.
• the aromatic carbonate mainly composed of diaryl force-bonate does not contain any halogen. Therefore, it is important as a raw material for industrial production of polycarbonate.
• the aromatic carbonates mainly composed of diaryl carbonate obtained in the present invention are separated by distillation or the like.
• the purified diaryl carbonate is highly pure and does not contain any halogen. It is very useful as a raw material for the production of aromatic polycarbonates by transesterification with aromatic dihydroxy compounds.
• the alkylaryl carbonate used as a raw material in the present invention may be highly pure or may contain other compounds. For example, this alkylaryl carbonate is obtained.
• the dialkyl carbonate and aromatic monohydroxy compound used to obtain the alkyl aryl carbonate which is the raw material of the present invention, is newly added to the reaction system. It is preferable to use the recovered dialkyl carbonate and aromatic monohydroxy compound in this process and / or other processes.
• the catalyst used in the present invention may be selected from the following compounds, for example, and may be the same as the catalyst used to obtain the raw material alkylaryl carbonate. Preferably, it is used for the reaction of dialkyl carbonate and aromatic monohydroxy compound. The catalyst is used as it is without separation.
• 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 2 -Pb (OH)
• Ph represents a full group.
• lead alloys such as howenite, senyanite, and hydrates of these lead compounds;
• ⁇ Copper group metal compounds > CuCl, CuCl, CuBr, CuBr, Cul, Cul, Cu (OAc), C
• acac represents a cetylacetone chelate ligand
• Alkali metal complexes such as Li (acac) and LiN (C H);
• Zinc complex such as Zn (acac);
• Zirconium complexes such as Zr (acac) and zirconocene;
• Lewis acids > A1X, TiX, TiX, VOX, VX, ZnX, FeX, SnX (where
• X is halogen, acetoxy group, an alkoxy group, or an aryloxy group.
• Lewis acids such as) and transition metal compounds that generate Lewis acids;
• 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 one that has reacted, or it may have been 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), (MeO
• Examples thereof include those treated with a diol or a reaction solution.
• FIG. 1 is a schematic view of a continuous multistage distillation column for carrying out the production method according to the present invention.
• the continuous multi-stage distillation column 10 used in the present invention has end plate parts 5 above and below a cylindrical body part 7 having a length L (cm) and an inner diameter D (cm), and the number of stages n therein.
• internal 6 (6-1: packing, 6-2: tray)
• a gas outlet 1 with an inner diameter d (cm)
• FIG. 1 is one embodiment of the continuous multistage distillation column according to the present invention, the arrangement of the internal 6 is not limited to the configuration shown in FIG.
• the continuous multi-stage distillation column according to the present invention is not only stable in terms of distillation capability but also stable. In combination with the conditions required for the reaction to proceed with high selectivity,
• 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.
• diaryl carbonate is produced on an industrial scale of 1 ton or more per hour, with high selectivity and high productivity, for example, 2000 hours or more, preferably It has been found that it can be stably produced for a long period of 3000 hours or more, more preferably 5000 hours or more.
• L (cm) is less than 1500, the reaction rate decreases, so the target production volume cannot be achieved, and in order to reduce the equipment cost while ensuring the reaction rate that can achieve the target production volume, L must be 8000 or less.
• a more preferable range of L (cm) is 2000 ⁇ L ⁇ 6000, and further preferably 2500 ⁇ L ⁇ 5000.
• D (cm) is smaller than 100, the target production volume cannot be achieved, and in order to reduce the equipment cost while achieving the target production volume, D must be 2000 or less. is there.
• a more preferable range of D (cm) is 150 ⁇ D ⁇ 1000, and more preferably 200 ⁇ D ⁇ 800.
• LZD is smaller than 2 or larger than 40
• stable operation becomes difficult.
• LZD is larger 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.
• a more preferred range of LZD is 3 ⁇ L / D ⁇ 30, and even more preferred is 5 ⁇ L / D ⁇ 15.
• n is less than 10, the reaction rate decreases, the target production volume cannot be achieved, and the facility cost can be reduced while ensuring the reaction rate that can achieve the target production volume.
• n must be 80 or less. Furthermore, if n is greater than 80, the pressure difference between the top and bottom of the column becomes too large, and long-term stable operation becomes difficult, and the temperature at the bottom of the column must be increased. This leads to a decrease in selectivity.
• a more preferred range of n is 15 ⁇ n ⁇ 60, more preferably 20 ⁇ n ⁇ 50.
• D / d force is smaller than ⁇ , 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. However, the reaction rate is reduced as well as the stable operation becomes difficult.
• a more preferable range of DZd is 2.5 ⁇ D / d ⁇ 12, and further preferably 3 ⁇ D / ⁇ ⁇ 10.
• the long-term stable operation as used in the present invention means that the operation can be continued in a steady state based on the operation condition where there is no piping clogging or erosion for 1000 hours or more, preferably 3000 hours or more, more preferably 5000 hours or more. This means that a predetermined amount of jar reel carbonate is produced while maintaining high selectivity.
• the present invention is characterized in that diaryl carbonate is stably produced at a high selectivity for a long period of time with a high productivity of 1 ton or more per hour, but preferably 2 tons or more per hour. More preferably, it is to produce diallyl carbonate of 3 tons or more per hour.
• the present invention also provides L, D, LZD, n, D / d, D / d force S of the continuous multistage distillation column.
• the present invention relates to L, D, L / D, n, D / d, and D / d of the continuous multistage distillation column.
• diallyl carbonate of 3 tons or more per hour, preferably 3.5 tons or more per hour, more preferably 4 tons or more per hour.
• the selectivity for diaryl carbonate in the present invention refers to the reacted alkylaryl carbonate, and in the present invention, the selectivity is usually 95% or more, preferably 97%. As described above, a high selectivity of 99% or more can be achieved.
• the continuous multistage distillation column 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 where the gas-liquid contact is actually performed in the distillation column.
• a tray for example, a foam tray, a perforated plate tray, a valve tray, a counter-flow tray, a super flake tray, a max flack tray, etc.
• packings such as Raschig rings, Lessing rings, and pole rings. , Berle saddles, Interlocks saddles, Dixon packing, McMahon packing, irregular packings such as Helicac, etc. and regular packings such as Melapack, Gempack, Technoback, Flexipack, Sulza Packing, Goodroll Packing, Glitch Grid, etc. Better ,.
• a multi-stage distillation column having both a tray part and a packed part can also be used.
• the term “internal plate number n” 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 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 reaction of the alkylaryl carbonate of the present invention with the aromatic monohydroxy compound present in the system has an extremely small equilibrium constant and a slow reaction rate, and is the main reaction. Carbonate disproportionation is also an equilibrium reaction, with a low equilibrium constant and a slow reaction rate.
• a continuous multistage distillation column for reactive distillation for carrying out the reaction of the present invention it has been found that a multistage distillation column in which the internal has both a packing and a tray is preferable. In this distillation column, it is more preferable that the packed portion is installed at the upper portion and the tray portion is installed at the lower portion.
• the packing is a regular packing. Further, it is preferable that one or two or more regular packings are used.
• the regular packing is preferably at least one selected from mela pack, gem pack, techno bag, flexi pack, snow leather packing, good roll packing, and glitch grid.
• the perforated plate tray in which the internal tray has a perforated plate portion and a downcomer portion is particularly excellent in terms of function and equipment cost. It was done. It has also been found that it is preferred that the perforated plate tray has 100-: LOOO holes per lm 2 area of the perforated plate portion. More preferred The number of fistulas is the area lm 2 The number is 120 to 900, more preferably 150 to 800. It has also been found that 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 further preferably 0.9 to 3 cm 2. Further, when 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 was found particularly favorable. Further, the regular packing is at least one selected from a mela pack, a gem pack, a techno bag, a flexi pack, a sulza packing, a good roll packing, and a glitch grid, and the perforated plate tray has an area lm of the perforated plate portion. have 2 per 100 to 000 holes, if the continuous multi-stage distillation column cross-sectional area per porous plate tray hole is 0. 5 ⁇ 5c m 2, was also found particularly preferable . It has been found that the object of the present invention can be achieved more easily by adding the above conditions to a continuous multistage distillation column.
• a dialkyl carbonate produced by continuously supplying a raw material containing an alkylaryl carbonate into a continuous multistage distillation column in which a catalyst is present, and simultaneously performing reaction and distillation in the column.
• a low-boiling reaction mixture containing alcohol and alcohol is continuously withdrawn from the top of the column in the form of a gas, and an aromatic force-bonate containing diaryl carbonate as the main reaction product is liquidized from the bottom of the column.
• diaryl carbonate is continuously produced.
• This low boiling point reaction mixture may contain aromatic monohydroxy compounds, alkyl aryl ethers, and unreacted alkyl aryl carbonates present in the system.
• the high boiling point reaction mixture may contain an aromatic monohydroxy compound, unreacted alkylaryl carbonate, and the like.
• this raw material includes dialkyl carbonates and alcohols, which are reaction products, aromatic monohydroxy compounds, diaryl carbonates and alkylaryl ethers, high boiling point reaction byproducts, etc. Is included, even though it is as described above. Considering the equipment and cost for separation in other processes, in the case of the present invention which is actually carried out industrially, it is preferable to contain a small amount of these compounds. .
• the reflux ratio is in the range of 0.01 to 10, preferably 0.08 to 5, and more preferably 0.1 to 2.
• the raw material containing alkylaryl carbonate in order to continuously supply the raw material containing alkylaryl carbonate into the continuous multistage distillation column, it is installed below the gas outlet at the top of the distillation column but at the top or middle of the column.
• At least one of the inlets may be installed between the packed portion and the tray portion.
• the packing is composed of two or more regular packings, it is also preferable to install an introduction port in the interval constituting the plurality of regular packings.
• any method may be used for allowing the catalyst to be present in the continuous multistage distillation column.
• the continuous multistage distillation is not limited. There are methods such as installing in a column in the distillation column or 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 pressure, etc., but it is expressed as a percentage of the total mass of the raw materials. 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 carried out in the present invention is considered to correspond to the average residence time of the reaction liquid in the continuous multistage distillation column, and this is the internal shape and number of stages of the distillation column, the amount of raw material supply Depending on the type and amount of the catalyst, reaction conditions and the like, it is usually 0.01 to 10 hours, preferably 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. For example, alkylaryl ether is a fleece transfer product of diaryl carbonate and its ester compound. By-product Is not preferable because it increases. In this sense, the preferred reaction temperature is 130 to 280 ° C, more preferably 150 to 260 ° C, and still more preferably 180 to 240 ° C.
• the reaction pressure varies depending on the type and composition of the starting compound used, the reaction temperature, etc., but the pressure at the top of the column, which can be any of reduced pressure, normal pressure, and increased pressure, is usually 0.1 to 2 X 10 7 Pa, preferably, 1 0 3 ⁇ 10 6 Pa, more preferably at a range of 5 X 10 3 ⁇ 10 5 Pa.
• the material constituting the continuous multi-stage distillation column used in the present invention is preferably stainless steel from the viewpoint of the quality of dial reel carbonate produced mainly by a metal material such as carbon steel and stainless steel.
• the halogen content was measured by an ion chromatography method.
• a mixture containing 18% by mass of methylphenol obtained by subjecting a mixture of dimethyl carbonate / phenol 1.3 (mass ratio) to a transesterification reaction was used as a raw material.
• This raw material is actually halogen
• This raw material was introduced into the continuous multistage distillation column at a flow rate of 66 ton Zhr from a raw material introduction port installed between the melapack and the perforated plate tray.
• the temperature at the bottom of the tower is 210 ° C
• Reactive distillation was carried out continuously under conditions of a top pressure of 3 ⁇ 10 4 Pa and a reflux ratio of 0.3. After 24 hours, stable steady operation was achieved.
• the liquid was continuously withdrawn from the bottom, Mechirufue - Le carbonate 38.4 wt%, Jifue - Le carbonate contained 55.6 wt 0/0 /, was.
• the production of diphenol carbonate from methyl phenol was found to be 5.13 tons per hour.
• the selectivity for diphenol carbonate was 99% with respect to the reacted methylphenol carbonate.
• a long-term continuous operation was performed under these conditions. After 500 hours, 2000 hours, 4000 hours, 5000 hours, and 6000 hours, the amount of diphenyl carbonate produced (excluding diphenyl carbonate contained in the raw material) is 5.13 tons per hour. 5.13 tons, 5.14 tons, 5.14 tons, 5.13 tons, the selectivity is 99%, 99%, 99%, 99%, very stable It was.
• the produced aromatic carbonate contained substantially no halogen (lppb or less).
• Dimethyl carbonate / phenol 1.9 (mass ratio)
• a mixture containing 21% by mass of methyl phenyl carbonate obtained by subjecting a mixture of potassium carbonate to a transesterification reaction was used as a raw material.
• This raw material is actually halogen
• This raw material was introduced into the continuous multi-stage distillation column at a flow rate of 80 ton Zhr from a raw material introduction port installed between the melapack and the perforated plate tray. Reactive distillation was continuously carried out under the conditions that the temperature at the bottom of the column was 205 ° C., the pressure at the top of the column was 2 ⁇ 10 4 Pa, and the reflux ratio was 0.5. After 24 hours, stable steady operation was achieved. The liquid was continuously withdrawn from the bottom, Mechirufue - Le carbonate 36.2 wt%, Jifue - Le carbonate contained 60.8 wt 0/0 /, was. The production of diphenol carbonate from methyl phenol carbonate was found to be 8.06 tons per hour. Reacted methyl ferrule The selectivity for diphenyl carbonate relative to the bonate was 99%.
• diphenyl carbonate production (excluding diphenyl carbonate contained in the raw material) is 8.06 tons per hour.
• 8.07 tons, 8.07 tons, 8.06 tons, 8.07 tons, and the selection rates were 99%, 99%, 99%, 99%, 99%, and were very stable .
• the produced aromatic carbonate contained substantially no halogen (lppb or less).
• Reactive distillation was performed under the following conditions using the same continuous multi-stage distillation column as in Example 1 except that the cross-sectional area per hole of the perforated plate tray was about 1.8 cm 2 .
• Dimethyl carbonate / phenol 1.4 (mass ratio)
• a mixture containing 16% by mass of methylphenol obtained by transesterification of a mixture was used as a raw material.
• dimethyl carbonate 27 wt%, Ma two ,, one Le 7 mass 0/0, phenol 49 mass 0/0, Jifue - Ri Contact contains Le carbonate 0.5 mass 0/0, further
• the catalyst power SPb (OPh) was about 200ppm. This raw material contains halogen
• This raw material was introduced into the continuous multi-stage distillation column at a flow rate of 94 ton Zhr from a raw material introduction port installed between the melapack and the perforated plate tray. Reactive distillation was continuously carried out under the conditions that the temperature at the bottom of the column was 215 ° C, the pressure at the top of the column was 2.5 X 10 4 Pa, and the reflux ratio was 0.4. After 24 hours, stable steady operation was achieved.
• the liquid continuously withdrawn from the bottom of the column contained 35.5% by mass of methylphenol carbonate and 59.5% by mass of diphenyl carbonate. Diphenyl carbonate production from methylphenol carbonate was found to be 7.28 tons per hour. The selectivity for diphenol carbonate was 99% with respect to the reacted methylphenol carbonate.
• An alkylaryl carbonate obtained by a transesterification reaction between a dialkyl carbonate and an aromatic monohydroxy compound is used as a raw material, and this raw material is placed in a continuous multistage distillation column in which a catalyst exists using a continuous multistage distillation column.
• Continuous supply and continuous production of aromatic carbonates with diaryl carbonate as the main product, high selectivity on the industrial scale of 1 ton or more per hour of dialyl carbonate 'It is suitable as a specific method that can be manufactured stably for a long period of time with high productivity.
• FIG. 1 is a schematic view of a continuous multistage distillation column for carrying out the present invention. Internal 6 is installed inside the trunk.
• the symbols used in Fig. 1 are as follows: 1: Gas outlet, 2: Liquid outlet, 3: Inlet, 4: Inlet, 5: End plate, 6-1: Internal (packing), 6-2: Internal (tray), 7: Body part, 10: Continuous multistage distillation column, L: Body length (cm), D: Body inner diameter (cm), d: Gas Drain port inner diameter (cm), d: Inside liquid discharge port

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