WO2015026073A1 - Procédé de préparation d'ester de glycol par distillation réactive - Google Patents

Procédé de préparation d'ester de glycol par distillation réactive Download PDF

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WO2015026073A1
WO2015026073A1 PCT/KR2014/006912 KR2014006912W WO2015026073A1 WO 2015026073 A1 WO2015026073 A1 WO 2015026073A1 KR 2014006912 W KR2014006912 W KR 2014006912W WO 2015026073 A1 WO2015026073 A1 WO 2015026073A1
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Prior art keywords
distillation column
carboxylic acid
glycol
glycol ester
reactor
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PCT/KR2014/006912
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English (en)
Inventor
Min Gyoo Park
Dong Wook Kim
Jin Su Ham
Seol A Kim
Jeong Eop Choi
Suk Joon Kim
Hyun Chul Choi
Ki Nam Chung
Byung Pyo Park
Jae Ho Lee
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Sk Innovation Co.,Ltd.
Sk Global Chemical Co., Ltd.
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Application filed by Sk Innovation Co.,Ltd., Sk Global Chemical Co., Ltd. filed Critical Sk Innovation Co.,Ltd.
Priority to CN201480000762.XA priority Critical patent/CN104640836B/zh
Priority to MYPI2016000302A priority patent/MY179699A/en
Publication of WO2015026073A1 publication Critical patent/WO2015026073A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by 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
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/245—Stationary reactors without moving elements inside placed in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • 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
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/0004—Processes in series
    • 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
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/0072—Organic compounds
    • 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 a method for continuously preparing a glycol ester from a glycol ether and a carboxylic acid using a reactive distillation column filled with a catalyst.
  • the present invention relates to a method for continuously preparing a high purity glycol ester for electronics without including an azeotropic distillation apparatus at a subsequent step by injecting an excess amount of carboxylic acid as compared to a mole number of a glycol ether among introduced reactants.
  • glycol esters have been widely used as a solvent for a paint, an ink, an adhesive, a detergent, and the like.
  • Various researches into a method for reacting a glycol ether with a carboxylic acid to prepare or purify a glycol ester have been conducted.
  • a method of performing an addition reaction of a glycol ether and a carboxylic acid using benzene sulfonic acid to prepare a glycol ester and performing purification using cyclohexane, which is an azeotroping solvent, has been disclosed in U.S. Patent No. 5,618,973.
  • a product and a catalyst should be separated, and since the azeotroping solvent is used, the azeotroping solvent should be purified, such that a process becomes complicated.
  • the post processing is complicated, and in the case of purifying the product using the azeotroping solvent, the azeotroping solvent should be purified, it is not easy to operate a process, and losses of the glycol ether and the carboxylic acid, which are the reactants, and the glycol ester, which is the product, are generated.
  • a minimum azeotrope of unconverted propylene glycol mono methyl ether (PM) and water additionally exists in addition to a minimum azeotrope of propylene glycol mono methyl ether acetate (PMA) and water, such that a distillation boundary is formed, and losses of propylene glycol mono methyl ether acetate (PMA) and propylene glycol mono methyl ether (PM) are generated toward an upper portion of the distillation column.
  • Patent Document 1 U.S. Patent No. 4544453
  • Patent Document 2 U.S. Patent No. 5618973
  • An object of the present invention is to provide a method for preparing a glycol ester for electronics capable of increasing a conversion rate of a glycol ether under low temperature and pressure conditions using a reactor and a reactive distillation column, suppressing generation of a minimum azeotrope of the glycol ether and water, and simplifying a subsequent separation process without a separate azeotropic distillation apparatus (a decanter and an azeotroping solvent injection/recovery equipment).
  • Another object of the present invention is to provide a method for preparing a high purity glycol ester for electronics capable of suppressing production of impurities by decreasing an injection amount of a glycol ether and separating a carboxylic acid under a pressurized condition of an atmosphere pressure or more.
  • a method for preparing a glycol ester includes: reacting a glycol ether and a carboxylic acid with each other using a first reactor and a first distillation column; producing unreacted materials and produced water toward an upper portion of the first distillation column and producing a glycol ester containing an unreacted carboxylic acid and impurities toward a lower portion thereof; separating the unreacted materials and produced water using a second distillation column and recycling the unreacted materials into the first reactor or the first distillation column; and separating the unreacted carboxylic acid produced toward the lower portion of the first distillation column using a third distillation column under a pressurized condition, wherein an amount of the carboxylic acid introduced in the first reactor is excess as compared to a mole number of the glycol ether, and the first distillation column is a reactive distillation column.
  • the conversion rate of the reactant at the low operation temperature and pressure may be increased, the reflux amount may be significantly decreased, and the production amount of the impurities may be decreased even under mild reaction conditions.
  • the separation process at the subsequent separation process may be simplified by injecting an excess amount of carboxylic acid so that the azeotrope of the glycol ether and the produced water does not exist, and the high purity glycol ester for electronics may be provided by easily separating the carboxylic acid through the column operated under the pressurized condition.
  • FIG. 1 is a mimetic view of a process for preparing a glycol ester according to the present invention.
  • FIG. 2 is a mimetic view of a reactive distillation column filled with a catalyst according to the present invention.
  • V-400 FOURTH DISTILLATION COLUMN
  • a method for preparing a glycol ester includes: reacting a glycol ether and a carboxylic acid with each other using a first reactor and a first distillation column; producing unreacted materials and produced water toward an upper portion of the first distillation column and producing a glycol ester containing an unreacted carboxylic acid and impurities toward a lower portion thereof; separating the unreacted materials and produced water using a second distillation column and recycling the unreacted materials into the first reactor or the first distillation column; and separating the unreacted carboxylic acid produced toward the lower portion of the first distillation column using a third distillation column under a pressurized condition, wherein an amount of carboxylic acid introduced in the first reactor is excess as compared to a mole number of the glycol ether, and the first distillation column is a reactive distillation column.
  • An esterification reaction of a glycol ether and a carboxylic acid according to the present invention is an equilibrium reaction, and it is preferable for a design for increasing a conversion rate that a predetermined reactor is provided before the glycol ether and the carboxylic acid are introduced in a reactive distillation column.
  • the following reaction is an esterification reaction of propylene glycol mono methyl ether (PM), which is an example of the glycol ether, and acetic acid (AA), which is an example of the carboxylic acid.
  • PM propylene glycol mono methyl ether
  • AA acetic acid
  • the esterification reaction according to the present invention may arrive at an equilibrium state before the reactants are introduced into the first distillation column V-100.
  • the first reactor R-100 may be a fixed bed reactor (FBR) filled with a catalyst.
  • FBR fixed bed reactor
  • the first reactor R-100 may be a fixed bed reactor (FBR) filled with a heterogeneous catalyst.
  • FBR fixed bed reactor
  • the above-mentioned process may be performed at a low temperature and a production amount of impurities may be minimized.
  • the first distillation column V-100 may include all types of reactive distillation columns capable of producing unreacted materials and produced water toward an upper portion thereof and producing a glycol ester containing an unreacted carboxylic acid and impurities toward a lower portion thereof while reacting the glycol ether and the carboxylic acid passing through the first reactor R-100 with each other.
  • the first distillation column V-100 may be a reactive distillation column producing unreacted materials and produced water toward the upper portion thereof and producing a glycol ester containing an unreacted carboxylic acid and impurities toward the lower portion thereof.
  • the first distillation column V-100 may be a reactive distillation column including all types of packing capable of being filled in the column such as structured packing, bale type packing, and the like, as a column type filled with the catalyst, in order to simultaneously perform the reaction and separation as shown in FIG. 2.
  • the reaction may occur in a reactive zone filled with the catalyst, and at the same time, separation of the product and the unreacted materials may proceed at a rectifying zone and a stripping zone positioned on and beneath the reactive zone.
  • the product is separated by the column, such that a partial pressure of the product in a reactive zone is decreased. Therefore, a production rate of the product may be increased according to Le Chatelier s principle, such that the conversion rate may be maximized.
  • the conversion rate may be defined as follows.
  • Total conversion rate of glycol ether [Amount of glycol ether introduced in reactor - Amount of glycol ether discharged from reactive distillation column]/ [Amount of glycol ether introduced in reactor] x 100
  • a ratio of the glycol ester lost toward the upper portion to the glycol ester generated from the first distillation column V-100 may be more than 0wt% but 1.0wt% or less, preferably more than 0wt% but 0.5wt% or less.
  • glycol ester containing the unreacted carboxylic acid and impurities may be produced toward the lower portion of the first distillation column V-100 according to the present invention.
  • glycol ester which is a desired product according to the present invention
  • materials except for the glycol ester, which is a desired product according to the present invention may be contained in the impurities.
  • metals may be contained in the impurities.
  • a content of the impurities contained in the glycol ester produced toward the lower portion of the first distillation column V-100 may be more than 0wt% but 1.0wt% or less, preferably more than 0wt% but 0.5wt% or less, but is not limited thereto.
  • the unreacted materials and produced water may be separated using the second distillation column V-200, and the unreacted materials separated from the second distillation column V-200 may be recycled into the first reactor R-100 or the first distillation column V-100.
  • Most of the unreacted materials recycled into the first reactor R-100 is the carboxylic acid, and a trace amount of the glycol ether may be contained therein.
  • the recycled carboxylic acid may react with the glycol ether in the first reactor R-100 and the first distillation column V-100 to prepare the glycol ester.
  • the unreacted carboxylic acid discharged toward the lower portion of the first distillation column V-100 according to the present invention acts as a limiting material in preparing a high purity glycol ester for electronics, and in order to separate the unreacted carboxylic acid, a separate distillation column may be provided.
  • the unreacted carboxylic acid discharged toward the lower portion of the first distillation column V-100 according to the present invention may be separated using the third distillation column V-300 under the pressurized condition.
  • the pressurized condition means a pressure condition of an atmospheric pressure or more.
  • any pressure condition may be used as long as the pressure is an atmospheric pressure or more at which the glycol ester and the carboxylic acid according to the present invention may be separated, but the pressure may be set in consideration of a high temperature pyrolysis problem of the glycol ester that may be generated as a temperature of the lower portion of the third distillation column V-300 is increased by an increase in the pressure.
  • temperature is dependent on pressure and the increase of top pressure means the increase of bottom temperature.
  • the pressure condition may be a pressure condition of 1 to 4.0bar, preferably, 1.1 to 2.0bar.
  • the glycol ester containing the unreacted carboxylic acid and impurities may be separated by the third distillation column V-300 according to the present invention, such that the high purity glycol ester for electronics may be prepared, and a design of the present invention that the excess amount of carboxylic acid is injected into the first reactor R-100 as compared to the mole number of the glycol ether may be achieved.
  • the glycol ether passing through a reactor and produced water form a minimum azeotrope, and thus, a distillation boundary is formed together with the minimum azeotrope of the glycol ester and the produced water, such that losses of the glycol ester and the glycol ether may be generated toward an upper portion of a distillation column.
  • formation of the distillation boundary may be suppressed by minimizing an unreacted amount of the glycol ether passing through the first reactor R-100 and the first distillation column V-100 operating at a low temperature, and the unreacted carboxylic acid discharged toward the lower portion of the first distillation column V-100 may be usefully removed by operating the third distillation column V-300 under the pressurized condition, such that an initial injection of the excess amount of carboxylic acid in preparing a high purity glycol ester for electronics may be made possible without causing a corrosive problem.
  • an excess amount of the carboxylic acid may be injected as compared to the mole number of the glycol ether.
  • injection of the excess amount of the carboxylic acid means that in adjusting a molar ratio of the glycol ether and the carboxylic acid corresponding to the reactants introduced into the first reactor R-100, a mole number of the carboxylic acid is higher than that of the glycol ether.
  • an injection amount of the carboxylic acid may be 1.01 to 1.5 moles, preferably 1.1 to 1.3 moles based on 1 mole of the glycol ether.
  • Impurities may be contained in the glycol ester passing through the third distillation column V-300 according to the present invention, and in order to remove these impurities, a fourth distillation column V-400 may be provided.
  • the fourth distillation column V-400 according to the present invention may include all types of distillations columns serving to separate pure glycol ester from the impurities contained in the glycol ester.
  • the fourth distillation column V-400 may separate the pure glycol ester toward an upper portion of the column and separate heavy impurities toward a lower portion thereof.
  • the glycol ether includes all glycol ethers capable of achieving the object of the present invention.
  • glycol ether according to the present invention may include ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, diethylene glycol mono butyl ether, or the like.
  • the glycol ether may be propylene glycol monomethyl ether (PM).
  • the carboxylic acid may include all carboxylic acids capable of producing the glycol ester according to the present invention.
  • a non-restrictive example of the carboxylic acid may include propionic acid, iso-butyric acid, normal-butyric acid, or the like.
  • the carboxylic acid may be acetic acid (AA), but the present invention is not limited thereto.
  • the prepared glycol ester may be propylene glycol monomethyl ether acetate (PMA).
  • the propylene glycol monomethyl ether acetate (PMA) prepared as described above may be prepared from the first reactor and the first to fourth distillation columns and be high purity propylene glycol monomethyl ether acetate (PMA) for electronics, having a low content of acetic acid (AA).
  • PMA propylene glycol monomethyl ether acetate
  • a content of acetic acid (AA) for preparing propylene glycol monomethyl ether acetate (PMA) for electronics may be 200wtppm or less.
  • the content can be produced 200wtppm or desirably 20wtppm or less in the present invention.
  • the content of acetic acid (AA) may be lowered to 200wtppm or less, preferably, 20wtppm or less under the pressurized condition by suitably finding a column operation condition for separating propylene glycol monomethyl ether acetate (PMA) and acetic acid (AA) from each other.
  • a content of propylene glycol monomethyl ether may be 0.1wt% or less, preferably 0.05wt% or less, and a content of metals may be 20ppb or less, preferably 10ppb or less.
  • a reaction temperature of the first reactor R-100 according to the present invention may include all low temperature conditions at which corrosion by the carboxylic acid is not generated, but the reaction temperature may be preferably, 60 to 90°C, and more preferably, 70 to 80°C.
  • a temperature condition of the lower portion of the first distillation column V-100 and a pressure condition of the upper portion thereof may include all temperature and pressure conditions for preparing the glycol ester according to the present invention.
  • a temperature of the lower portion of the first distillation column V-100 according to the present invention may be 80 to 110°C, preferably 90 to 100°C, and a pressure of the upper portion thereof may be 0.13 to 0.27bar, preferably, 0.13 to 0.2bar.
  • Propylene glycol monomethyl ether (PM) and acetic acid (AA) were mixed at a molar ratio of 1:1.3 and used as raw materials.
  • PM propylene glycol monomethyl ether
  • AA acetic acid
  • FBR fixed bed reactor
  • 52.14% of propylene glycol monomethyl ether (PM) was converted into propylene glycol monomethyl ether acetate (PMA).
  • the produced product was continuously injected into a first distillation column serving as a reactive distillation column filled with a catalyst at a central portion of the distillation column.
  • the raw materials were continuously injected at operation conditions of the first distillation column at which a pressure of an upper portion of the column was maintained at 0.173319bar, and a temperature of a lower portion of the column was maintained at 98°C.
  • a reflux ratio in the upper portion of the column shown in FIG. 2 was maintained at 1.6.
  • the product was analyzed using gas chromatography, and as a result, a conversion rate of propylene glycol monomethyl ether (PM) into propylene glycol monomethyl ether acetate (PMA) was 99.9% or more.
  • Propylene glycol monomethyl ether (PM) and acetic acid (AA) were mixed at a molar ratio of 1:1.18 and used as raw materials.
  • PM propylene glycol monomethyl ether
  • AA acetic acid
  • FBR fixed bed reactor
  • 49.42% of propylene glycol monomethyl ether (PM) was converted into propylene glycol monomethyl ether acetate (PMA).
  • the produced product was continuously injected into a first distillation column serving as a reactive distillation column filled with a catalyst at a central portion of the distillation column.
  • the raw materials were continuously injected at operation conditions of the first distillation column at which a pressure of an upper portion of the column was maintained at 0.173319bar, and a temperature of a lower portion of the column was maintained at 98°C.
  • a reflux ratio in the upper portion of the column shown in FIG. 2 was maintained at 2.0.
  • the product was analyzed using gas chromatography, and as a result, even though the ratio of the raw materials was decreased in the fixed bed reactor (FBR), a conversion rate of propylene glycol monomethyl ether (PM) into propylene glycol monomethyl ether acetate (PMA) was 99.9% or more.
  • FBR fixed bed reactor
  • Propylene glycol monomethyl ether (PM) and acetic acid (AA) were mixed at a molar ratio of 1.4:1 and continuously injected into a first reactor in Example 3.
  • the product of the first reactor was injected into a first distillation column, and in the product passing through the first reactor and the first distillation column, a total conversion rate based on acetic acid (AA) was 98% or more.
  • the operation conditions of the first distillation column were the same as in Example 3.
  • compositions in upper and lower portions of the first distillation column were analyzed using gas chromatography, and as a result, as shown in Table 2, it was confirmed that a rate of propylene glycol monomethyl ether acetate (PMA) lost toward the upper portion was 7.0wt%, a purity of propylene glycol monomethyl ether acetate (PMA) separated toward the lower portion was 96.1wt%, and the remaining components were acetic acid (AA, 1.4wt%), propylene glycol monomethyl ether (PM, 0.1wt%) and impurities (2.4wt%).
  • PMA propylene glycol monomethyl ether acetate
  • a raw material in which propylene glycol monomethyl ether acetate (PMA) and acetic acid (AA) were mixed at a molar ratio of 95:5 was separated under a pressurized condition of 1.1bar.
  • a temperature of a lower portion of the third distillation column was maintained at 150°C, and a reflux ratio in an upper portion thereof was maintained at 65.0.
  • a composition in the lower portion of the column was analyzed using gas chromatography, and as a result, it was confirmed that a content of acetic acid (AA) in propylene glycol monomethyl ether acetate (PMA) was 20wtppm.
  • a raw material in which propylene glycol monomethyl ether acetate (PMA) and acetic acid (AA) were mixed at a molar ratio of 95:5 was separated under a pressurized condition of 2.0bar. At this time, a temperature of a lower portion of the column was maintained at 172°C, and a reflux ratio in an upper portion thereof was maintained at 33.0.
  • a composition in the lower portion of the column was analyzed using gas chromatography, and as a result, a content of acetic acid (AA) in propylene glycol monomethyl ether acetate (PMA) was not observed.
  • a raw material in which propylene glycol monomethyl ether acetate (PMA) and acetic acid (AA) were mixed at a molar ratio of 95:5 was separated under a pressurized condition of 4.0bar. At this time, a temperature of a lower portion of the column was maintained at 200°C, and a reflux ratio in an upper portion thereof was maintained at 30.0.
  • a composition in the lower portion of the column was analyzed using gas chromatography, and as a result, a content of acetic acid (AA) in propylene glycol monomethyl ether acetate (PMA) was not observed.
  • a raw material in which propylene glycol monomethyl ether acetate (PMA) and acetic acid (AA) were mixed at a molar ratio of 95:5 was separated under 0.5bar. At this time, a temperature of a lower portion of the column was maintained at 128°C, and a reflux ratio in an upper portion thereof was maintained at 85.0. A composition in the lower portion of the column was analyzed using gas chromatography, and as a result, it was confirmed that a content of acetic acid (AA) in propylene glycol monomethyl ether acetate (PMA) was 95wtppm.
  • a raw material in which propylene glycol monomethyl ether acetate (PMA) and acetic acid (AA) were mixed at a molar ratio of 95:5 was separated under 0.3bar.
  • a temperature of a lower portion of the column was maintained at 116°C, and a reflux ratio in an upper portion thereof was maintained at 120.0.
  • a composition in the lower portion of the column was analyzed using gas chromatography, and as a result, it was confirmed that a content of acetic acid (AA) in propylene glycol monomethyl ether acetate (PMA) was 323wtppm.
  • the loss rate of propylene glycol monomethyl ether acetate (PMA) may be minimized under a more acidic atmosphere, and the content of the impurities may be decreased as compared to the existing process using an excess amount of a glycol ether. Even though the molar ratio of the excessively injected reactant is low, the total conversion rate may be increased, the content of unconverted propylene glycol monomethyl ether (PM) may be minimized, and a usage rate of expensive propylene glycol monomethyl ether (PM) may be maximized, such that economical operation conditions may be set.
  • AA acetic acid
  • the content of acetic acid (AA) in propylene glycol monomethyl ether acetate (PMA) in the lower portion of the column may sufficiently satisfy limited conditions for preparing PMA for electronics according to the present invention due to the pressurized separation conditions of the third distillation column.
  • the conversion rate of the reactant at the low operation temperature and pressure may be increased, the reflux amount may be significantly decreased, and the production amount of the impurities may be decreased even under mild reaction conditions.
  • the separation process at the subsequent separation process may be simplified by injecting an excess amount of carboxylic acid so that the azeotrope of the glycol ether and the produced water does not exist, and the high purity glycol ester for electronics may be provided by easily separating the carboxylic acid through the column operated under the pressurized condition.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé pour préparer un ester de glycol, ledit procédé étant susceptible d'augmenter le taux de conversion d'un éther de glycol dans des conditions de basse température et de basse pression, de minimiser la quantité de matériaux n'ayant pas réagi recyclée au moyen d'une colonne de distillation réactive, et de diminuer la quantité d'impuretés produites, lors de la préparation de l'ester de glycol à partir de l'éther de glycol et d'un acide carboxylique. L'invention concerne en outre un procédé pour préparer un ester de glycol pour l'électronique, ledit procédé permettant de réduire une perte d'ester de glycol vers une partie supérieure d'une colonne de distillation réactive en injectant un excès d'un acide carboxylique par rapport à un nombre de moles d'un éther de glycol et de séparer facilement l'ester de glycol et l'acide carboxylique l'un de l'autre dans des conditions sous pression, et de simplifier un processus subséquent de séparation sur colonne sans appareil de distillation azéotropique distinct.
PCT/KR2014/006912 2013-08-20 2014-07-29 Procédé de préparation d'ester de glycol par distillation réactive WO2015026073A1 (fr)

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CN201480000762.XA CN104640836B (zh) 2013-08-20 2014-07-29 使用反应精馏制备乙二醇酯的方法
MYPI2016000302A MY179699A (en) 2013-08-20 2014-07-29 Method for preparing glycol ester using reactive distillation

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KR1020130098551A KR101349106B1 (ko) 2013-08-20 2013-08-20 반응증류를 이용한 글리콜 에스테르의 제조방법
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CN110423197A (zh) * 2019-09-17 2019-11-08 凯瑞环保科技股份有限公司 一种利用低浓度乙二醇生产乙二醇双乙酸酯的装置和方法
CN115443263A (zh) * 2020-04-22 2022-12-06 帝斯曼知识产权资产管理有限公司 酰化α,ω-烷二醇的方法

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CN110305012A (zh) * 2019-08-16 2019-10-08 南通百川新材料有限公司 一种半导体级丙二醇甲醚乙酸酯的合成工艺
WO2021172898A1 (fr) * 2020-02-26 2021-09-02 영남대학교 산학협력단 Appareil et procédé de production d'acétate de propylèneglycolméthyléther
CN112194580B (zh) * 2020-11-04 2021-09-14 中建安装集团有限公司 一种反应精馏耦合渗透汽化生产丙二醇单甲醚醋酸酯的装置及工艺
KR102399263B1 (ko) * 2021-08-09 2022-05-17 에스케이머티리얼즈퍼포먼스 주식회사 프로필렌 글리콜 모노메틸 에테르 아세테이트의 제조방법
KR102498772B1 (ko) * 2021-11-29 2023-02-10 주식회사 켐트로닉스 초고순도 pgmea의 제조방법

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CN105693514A (zh) * 2016-03-18 2016-06-22 江苏雷蒙化工科技有限公司 一种多元醇的低碳羧酸酯的连续化生产系统及其生产方法
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CN115443263A (zh) * 2020-04-22 2022-12-06 帝斯曼知识产权资产管理有限公司 酰化α,ω-烷二醇的方法

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