WO2021172898A1

WO2021172898A1 - Apparatus and method for manufacturing propylene glycol methyl ether acetate

Info

Publication number: WO2021172898A1
Application number: PCT/KR2021/002387
Authority: WO
Inventors: 이문용; 차니아고유스도널드
Original assignee: 영남대학교 산학협력단
Priority date: 2020-02-26
Filing date: 2021-02-25
Publication date: 2021-09-02
Also published as: KR20210108901A; KR102533952B1

Abstract

The present invention relates to an apparatus for manufacturing propylene glycol methyl ether acetate (PGMEA). The present invention can provide a manufacturing apparatus comprising: a reaction distiller in which propylene glycol methyl ether (PGME) and methyl acetate (MA) are introduced to prepare propylene glycol methyl ether acetate (PGMEA) and methanol; and a distillation column in which unreacted methyl acetate (MA) and methanol which are introduced from the reaction distiller are separated in a pressurization or decompression condition, wherein propylene glycol methyl ether acetate (PGMEA) is generated and separated in the reaction distiller and unreacted methyl acetate (MA) and methanol are separated from each other by using pressure swing distillation.

Description

Propylene glycol methyl ether acetate manufacturing apparatus and manufacturing method

The present invention relates to an apparatus and method for preparing propylene glycol methyl ether acetate.

Propylene glycol methyl ether acetate (PGMEA) is a solvent used in a wide range of industrial applications due to its high dissolution capacity, good thermal stability, low toxicity and corrosiveness. In particular, since propylene glycol methyl ether acetate (PGMEA) contains both ether bonds and carbonyl groups in its molecular structure, it can be used as an ideal solvent for industrial semiconductors to dissolve polar and non-polar substances. In particular, due to the characteristics of semiconductors that require ultra-fine technology according to the flow of the fourth industrial revolution, it is required to produce propylene glycol methyl ether acetate (PGMEA) having ultra-high purity and extremely low acidity.

Therefore, the problem to be solved by the present invention is to produce propylene glycol methyl ether acetate with ultra-high purity and extremely low acidity, while at the same time, dramatically improving separation efficiency and energy efficiency through process integration (Process Intensification) To provide a manufacturing apparatus and method that can be performed.

The technical problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

Since the present invention can have various changes and can have various embodiments, specific embodiments are illustrated in the drawings and described in detail. However, this is not intended to limit the present invention to specific embodiments, and it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

When a component is referred to as being “connected” or “connected” to another component, it is understood that the other component may be directly connected or connected to the other component, but other components may exist in between. it should be

On the other hand, in the present specification, when it is mentioned that a reactive distiller or a distillation column is "directly connected", it will be understood that a separate column such as another reactive distiller or a distillation column is not additionally interposed therebetween. That is, even if the reactive distiller or the distillation column is directly connected, the reactive distiller or the distillation column does not exist in the middle, and a reboiler, a condenser, or a compressor may be interposed therebetween.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the accompanying drawings.

In order to achieve the above technical problem, an embodiment of the present invention provides a manufacturing apparatus for manufacturing propylene glycol methyl ether acetate (PGMEA; Propylene Glycol Methyl Ether Acetate). 1 shows a configuration of a manufacturing apparatus according to an embodiment, which will be described below with reference to FIG. 1 .

Reaction Distiller (RD)

In one embodiment, the manufacturing apparatus according to the present invention introduces propylene glycol methyl ether (PGME, 1) and methyl acetate (MA, 2) to produce propylene glycol methyl ether acetate (PGMEA, 3) and methanol, and the catalyst is It may include an equipped reactive distiller (RD).

Specifically, the trans-esterification reaction of Chemical Formula 1 below may be performed in the reaction distiller (RD), and propylene glycol methyl ether acetate (PGMEA, 3) may be prepared.

[Formula 1]

In one example, in order to prepare propylene glycol methyl ether acetate (PGMEA, 3), propylene glycol methyl ether (PGME, 1) and methyl acetate (MA, 2) as reactants are introduced into the reaction distiller (RD) from the outside. , propylene glycol methyl ether (PGME, 1) may be introduced into the upper portion of the reactive distiller (RD), and methyl acetate (MA, 2) may be introduced into the lower portion of the reactive distiller (RD).

In one example, methyl acetate (MA, 2) may be introduced into the reaction distiller in excess of the number of moles of propylene glycol methyl ether (PGME, 1). Considering the reaction formula of Formula 1, theoretically, it can be expected that the yield of the product should be increased when the molar ratio of the reactants is 1:1. , it may be desirable to introduce methyl acetate (MA, 2) in excess relative to propylene glycol methyl ether (PGME, 1).

As an example, methyl acetate (MA, 2) and propylene glycol methyl ether (PGME, 1) are introduced into the reactive distiller (RD) in a molar ratio of 2:1 to 5:1 or 2:1 to 4:1. can be That is, since the molar ratio of the reactants satisfies the above range, the conversion of propylene glycol methyl ether (PGME, 1) introduced into the reactive distiller (RD) is improved to approximately 100%, and unreacted propylene glycol methyl ether (PGME, 1) You can control that it doesn't exist.

In one example, the pressure of the reaction distiller (RD) may be 3 atm or less, 2 atm or less, or 1 atm or less, 0 atm or less, and as will be described below, lower than the pressure of the first distillation column (D1) can

Also, in one example, the catalyst provided in the reactive distiller (RD) may be a basic catalyst. That is, the reaction of Formula 1 may be promoted by a basic catalyst, and specifically, the reaction of Formula 1 may exhibit high selectivity to propylene glycol methyl ether acetate (PGMEA, 3) by using a basic catalyst.

The basic catalyst provided in the reactive distiller (RD) may be a basic homogeneous catalyst. That is, the acid catalyst may not be provided in the reactive distiller (RD). That is, in the case of preparing propylene glycol methyl ether acetate (PGMEA) through the transesterification reaction as shown in Formula 1, propylene glycol methyl ether acetate (PGMEA, 3) obtained from the reactive distillation unit (RD) because an acidic catalyst is not involved. may indicate extremely low acidity. Accordingly, propylene glycol methyl ether acetate (PGMEA, 3) prepared according to the present invention may be particularly suitable for solvents used in semiconductor processing. As an example, since the present invention does not contain acidic substances in the catalyst or product, it does not contain acidic impurity components, so that the propylene glycol methyl ether acetate (PGMEA) obtained according to the present invention has a pH of 4 or more and pH 8 or less at 25°C. may, but is not limited thereto, the basic catalyst may include solid sodium methoxide (CH ₃ ONa).

As an example, the hold-up in the reaction distillation stage in the reaction distiller R may be large enough to achieve an appropriate reaction conversion rate.

In addition, in one example, the reaction distillation unit (RD) may perform a reaction for preparing propylene glycol methyl ether acetate (PGMEA, 3) and at the same time perform separation and purification of the product. Accordingly, propylene glycol methyl ether acetate (PGMEA, 3) can be obtained from the reactive distiller (RD), and more specifically, it can be obtained from the lower portion of the reactive distillation unit (RD).

In one example, the yield of propylene glycol methyl ether acetate (PGMEA, 3) obtained from the reactive distillation unit (RD) may be 99% or more, specifically, 99.95% or more, 99.96% or more, 99.97% or more, 99.98% or more , 99.99% or more, or 99.999% or more. Propylene glycol methyl ether acetate (PGMEA, 3) obtained according to the present invention may be particularly suitable as a solvent for semiconductors because it can be obtained in ultra-high purity.

In addition, methanol (7) as a by-product generated from Formula 1 is separated and obtained by the manufacturing apparatus of the present invention as described in detail in FIG. It can be used as a reactant in the propylene glycol methyl ether (PGME) preparation reaction. Therefore, according to the present invention, the amount of raw material required for the reaction can be reduced.

On the other hand, methanol, the product of Formula 1, and unreacted methyl acetate (MA) introduced in excess as a reactant may form a mixture and exist above the reaction distiller (RD). The methanol and methyl acetate (MA) mixture may be an azeotrope.

In general, the liquid mixture can be separated using a distillation process using a difference in volatility between the mixtures, but in the case of an azeotrope forming an azeotrope, it is impossible to separate each substance by a general distillation process.

On the other hand, since the methanol and methyl acetate (MA) mixture formed in the reactive distiller (RD) shows the shift of the azeotrope sensitively to the pressure change, the operating pressure of the distillation column is controlled using this behavior to control the relative volatility and the azeotropic point of the mixture. , that is, each component can be separated into pure components by controlling the azeotropic composition. Hereinafter, a distillation column, which is a configuration for separating an azeotrope of methanol and methyl acetate (MA) into pure components, will be described in detail.

Distillation column (D1, D2)

In one embodiment, unreacted methyl acetate (MA) and methanol may be separated by pressure swing distillation.

An azeotrope of methyl acetate (MA) and methanol can also be separated using extractive distillation. However, in this case, as an entrainer, which is an additional solvent, is essentially required to change the relative volatility of the composition, there is a problem in that economical efficiency is lowered, and furthermore, there is a fatal disadvantage in that the product is contaminated.

Accordingly, the present invention can produce propylene glycol methyl ether acetate (PGMEA) in a more environmentally friendly, high yield and energy-efficient manner using pressure swing distillation that does not require a third component such as an additional solvent. In addition, when pressure swing distillation is used, as will be described in more detail below, pure methyl acetate (MA) finally separated and obtained is recycled to the reaction distiller (RD) to produce propylene glycol methyl ether acetate (PGMEA). It can be reused as a reactant, and pure methanol finally separated and obtained can be recycled to the reactor (R) and reused as a reactant of a propylene glycol methyl ether (PGME) production reaction. Therefore, the manufacturing apparatus of the present invention can reduce the amount of use of reactants and energy consumption through a sustainable process, and furthermore, as will be described later, energy exchange between the condenser and the reboiler is possible, so that energy is introduced from the outside can be minimized.

In one example, the manufacturing apparatus may include a distillation column (D) for separating unreacted methyl acetate and methanol introduced from the reaction distiller (RD) under pressure or reduced pressure. Specifically, the distillation column (D) is directly connected to the reaction distiller (RD), the methanol and methyl acetate (MA) mixture (4) can be introduced into the distillation column (D) from the top of the reaction distiller (RD).

In one example, the distillation column (D) may include a first distillation column (D1) directly connected to the reactive distiller (RD) and a second distillation column (D2) directly connected to the first distillation column (D1) (that is, the reactive distiller) (RD), the first distillation column (D1), the second distillation column (D2) are sequentially arranged), the pressure swing distillation is a second distillation column operated at a different pressure from the first distillation column (D1) and the first distillation column (D1) (D2) can be carried out.

In one example, the pressure of the first distillation column (D1) may be higher than the pressure of the second distillation column (D2). That is, the first distillation column (D1) may be operated at a higher pressure than the second distillation column (D2).

The methanol and methyl acetate (MA) mixture (4) introduced from the reactive distiller (RD) may contain an excess of methyl acetate (MA) compared to methanol. That is, since the mixture (4) is introduced into the first distillation column (D1) including methyl acetate (MA) in a larger mole fraction compared to methanol, the first distillation column (D1) is at a lower pressure than the second distillation column (D2) The mixture (4) cannot be separated into its individual pure components.

In one example, the pressure of the first distillation column (D1) may be less than or equal to the pressure causing the ignition point of the compound present in the first distillation column (D1) or decomposition of the catalyst provided in the reaction distiller (RD) starts.

Specifically, in one example, the pressure of the first distillation column (D1) may be 4 atm or more and 12 atm or less, and specifically, the lower limit of the pressure of the first distillation column (D1) is 5 atm or more, 6 atm or more, 7 atm or more , may be 8 atm or more, and the upper limit thereof may be 11 atm or less or 10 atm or less. In addition, the pressure of the second distillation column (D2) may be greater than 0 atm and less than 4 atm, specifically, 3 atm or less, 2 atm or less, or 1.5 atm or less. By controlling the pressure of the first distillation column (D1), the yield of propylene glycol methyl ether acetate (PGMEA, 3) is determined, that is, by satisfying the above range with the operating pressure of the first distillation column (D1), the present invention is a reaction Propylene glycol methyl ether acetate (PGMEA, 3) obtained from the still (RD) can exhibit a yield of 99% or more.

As an example, the pressure difference between the first distillation column D1 and the second distillation column D2 may be 5 atm or more, 6 atm or more, 7 atm or more, or 8 atm or more, and the upper limit may be 10 atm or less.

In one example, the first distillation column (D1) is operated in a specific pressure range, so that pure methyl acetate (MA, 5) can be separated from the bottom of the first distillation column (D1), and the obtained pure methyl acetate (MA, 5) is recycled to the lower part of the reaction distiller (RD) and can be used as a reactant of the propylene glycol methyl ether acetate (PGMEA) production reaction.

In one example, unreacted methyl acetate (MA) and methanol remaining after separation of methyl acetate (MA, 5) may be introduced into the second distillation column (D2) to form an azeotrope (6). The methanol and methyl acetate (MA) azeotrope 6 introduced from the first distillation column D1 may contain an excess of methanol compared to methyl acetate (MA). That is, the azeotrope 6 may be introduced into the second distillation column D2 including methanol in a larger mole fraction compared to methyl acetate (MA).

As described above, the second distillation column (D2) is operated in a specific pressure range, and thus pure methanol (7) can be separated from the lower part of the second distillation column (D2), and the obtained pure methanol (7) is below As described in detail in FIG. 2, it is separated and obtained by the manufacturing apparatus of the present invention, and can be performed in a step prior to the propylene glycol methyl ether acetate (PGMEA) preparation reaction as a reactant of the propylene glycol methyl ether (PGME) preparation reaction. can be used

In addition, methyl acetate (MA) and methanol, which have not been separated, form an azeotropic mixture (8) and are present in the upper part of the second distillation column (D2), and a mixture of methyl acetate (MA) and methanol is obtained from the upper part of the second distillation column (D2). The mixture of methyl acetate (MA) and methanol obtained from the top of the second distillation column (D2) may be recycled to the first distillation column (D1). The azeotrope 8 may contain an excess of methyl acetate (MA) relative to methanol.

Further, in one example, the first distillation column (D1) may be provided with a condenser at the upper portion, the second distillation column (D2) may be provided with a reboiler at the lower portion. The reboiler provided in the lower part of the second distillation column (D2) may have a temperature difference of at least 10 K or more from the condenser provided in the upper part of the first distillation column (D1), in detail, the reboiler provided in the lower part of the second distillation column (D2) The boiler may have a lower temperature of at least 10 K or more than the condenser provided on the first distillation column (D1).

As such, as the condenser provided in the upper portion of the first distillation column D1 and the reboiler provided in the lower portion of the second distillation column D2 perform heat exchange, the manufacturing apparatus of the present invention can more efficiently save energy. have. That is, the heat to be removed from the condenser provided in the upper part of the first distillation column D1 can be removed without a separate cooler as heat is transferred to the reboiler, and the reboiler provided in the lower part of the second distillation column D2 is Heat can be supplied without separate steam.

In summary, the manufacturing apparatus according to an embodiment of the present invention consists of a reactive distiller, a first distillation column, and a second distillation column, so that propylene glycol methyl ether acetate (PGMEA) can be produced in excellent yield with only three columns in total. and it can be efficiently recovered as each pure component from an azeotrope of methyl acetate and methanol formed in the process of preparing it,

FIG. 2 shows the configuration of a manufacturing apparatus according to another embodiment, which will be described below with reference to FIG. 2 . In describing the present invention, in order to facilitate the overall understanding, the same reference numerals are used for the same components in the drawings, and duplicate descriptions of the same components are omitted.

Prior to this reaction for preparing propylene glycol methyl ether acetate (PGMEA) described above, a preparation reaction for preparing propylene glycol methyl ether (PGME) may be performed as follows.

< Preparation of propylene glycol methyl ether (PGME): preparation reaction >

Reactor (R)

In one example, the manufacturing apparatus according to the present invention may include a reactor (R) in which propylene oxide (PO, 9) and methanol (10) are introduced to produce propylene glycol methyl ether (PGME), which is a reactant of this reaction. have. As an example, methanol (10) and propylene oxide (PO, 9) may be introduced into the reactor (R) in a ratio of 7:1 to 12:1. In addition, the reactor (R) may be carried out at a temperature of 300 K to 370 K and 0.5 atm to 2 atm.

Specifically, the ring opening reaction of Formula 2 below may be performed inside the reactor (R). As an example, a basic catalyst may be provided inside the reactor (R). That is, the reaction of Formula 2 can be minimized from the risk of ultimately producing acidic propylene glycol methyl ether acetate (PGMEA) by using a basic catalyst, and can be advantageous in terms of selectivity of propylene glycol methyl ether (PGME) production.

[Formula 2]

In one example, the propylene glycol methyl ether (PGME, 1) produced according to the reaction of Formula 2 is separated into a pure substance in the still (d) and then is directly connected to the still (d) from the lower part of the still (d) Reaction distiller (RD) can be introduced.

In addition, unreacted methanol 11 separated from the distiller (d) may be recycled back to the reactor (R) and reused as a reactant of the propylene glycol methyl ether (PGME) production reaction.

Furthermore, pure methanol (7) obtained as a by-product through this reaction to prepare propylene glycol methyl ether acetate (PGMEA; Propylene Glycol Methyl Ether Acetate) is recycled back to the reactor (R) and propylene glycol methyl ether ( PGME) can be reused as a reactant in the production reaction.

3 and 4 show the configuration of a manufacturing apparatus according to another embodiment, which will be described below with reference to FIGS. 3 and 4 . In describing the present invention, in order to facilitate the overall understanding, the same reference numerals are used for the same components in the drawings, and duplicate descriptions such as the same components and the same effects are omitted.

Reaction Distiller (RD)

In one embodiment, the pressure of the reaction distiller (RD) may be a high pressure compared to the pressure of the distillation column (D). That is, the reaction distiller (RD) may be operated at a higher pressure than the distillation column (D) described below.

In one example, the pressure of the reactive distiller (RD) may be less than or equal to the pressure causing the decomposition of the catalyst provided in the reactive distiller (RD) or the ignition point of the compound present in the distillation column (D).

Specifically, in one example, the pressure of the reactive distiller (RD) may be 4 atm or more and 10 atm or less, and specifically, the lower limit of the reaction distiller (RD) pressure may be 5 atm or more, 6 atm or more, or 7 atm or more. and the upper limit may be 9 atm or less or 8 atm or less. In addition, the pressure of the distillation column (D) may be more than 0 atm and less than 4 atm, specifically, 3 atm or less, 2 atm or less, or 1.5 atm or less.

The transesterification reaction of Chemical Formula 1 performed in the reactive distillation unit (RD) is a reversible endothermic reaction, and the endothermic reaction is a more forward reaction in terms of reaction rate because when the pressure is increased under equivalent conditions, the temperature rises and moves in the product direction. can be advantageous

That is, unlike in FIGS. 1 and 2 described above, the forward reaction proceeds more favorably as the reaction distiller (RD) is operated at high pressure, and a mixture of methanol and methyl acetate (MA) present in the upper portion of the reaction distiller (RD) (6) may include methanol in excess of methyl acetate (MA).

Distillation column (D)

In one embodiment, the distillation column (D) may consist of only one distillation column, and the pressure swing distillation may be performed through the distillation column (D) and the reactive distiller (RD) operated at different pressures.

Unlike in FIGS. 1 and 2 , the azeotrope 6 introduced from the reaction distiller RD is introduced into the distillation column D including methanol in a larger mole fraction compared to methyl acetate (MA), so the distillation column (D) It is possible to separate the azeotrope (6) at a lower pressure than the silver reaction distiller (RD), and specifically, it can be obtained by separating the pure methanol component in the lower part of the distillation column (D), and methyl acetate (MA) in the upper part of the distillation column (D) ) can be obtained in an excess of azeotrope.

As an example, the pressure difference between the reaction distiller (RD) and the distillation column (D) may be 3 atm or more, 4 atm or more, 5 atm or more, or 6 atm or more, and the upper limit may be 10 atm or less.

In one example, the yield of propylene glycol methyl ether acetate (PGMEA, 3) obtained from the reactive distillation unit (RD) may be 99% or more, specifically, 99.95% or more, 99.96% or more, 99.97% or more, 99.98% or more , 99.99% or more, or 99.999% or more. That is, according to the present invention, propylene glycol methyl ether acetate (PGMEA, 3) can be obtained in ultra-high purity, so it can be particularly suitable as a solvent for semiconductors.

In addition, as described above, the distillation column (D) is operated in a specific pressure range, and thus pure methanol (7) can be separated from the lower part of the distillation column (D), and the obtained pure methanol (7) is shown in FIG. As can be seen, separated and obtained by the production apparatus of the present invention, it can be used as a reactant of the propylene glycol methyl ether (PGME) production reaction that can be carried out in the step before the propylene glycol methyl ether acetate (PGMEA) production reaction. .

In addition, in one example, methyl acetate (MA) and methanol that has not been separated form an azeotropic mixture (8) and are present in the upper part of the distillation column (D), and a mixture of methyl acetate (MA) and methanol from the upper part of the distillation column (D) can be obtained, and the azeotrope (8) can contain an excess of methyl acetate (MA) relative to methanol. The azeotrope (8) may be recycled from the upper part of the distillation column (D) to the reaction distiller (RD), and specifically, the methyl acetate (MA) and methanol azeotrope (8) obtained from the upper part of the distillation column (D) is a reaction distiller The position at which the propylene glycol methyl ether (PGME, 1) is recycled to the reactive distiller (RD) and recycled to (RD) may be the same as the position at which the propylene glycol methyl ether (PGME, 1) is introduced into the reactive distiller (RD).

In summary, the manufacturing apparatus according to an embodiment of the present invention consists of a reactive distiller and a distillation column, so that only two columns in total can achieve the object of the present invention. That is, unlike in FIGS. 1 and 2, as long as the reactive distiller (RD) is operated at an appropriate high pressure, only one distillation column (D) can obtain high purity propylene glycol methyl ether acetate (PGMEA), and at the same time, Energy efficiency can be dramatically improved by efficiently recovering methanol as a pure component from an azeotrope of methyl acetate and methanol.

Another embodiment of the present invention provides a method for preparing propylene glycol methyl ether acetate (PGMEA; Propylene Glycol Methyl Ether Acetate). In describing the present invention, descriptions overlapping with the manufacturing apparatus will be omitted.

In one embodiment, the preparation method according to the present invention prepares propylene glycol methyl ether acetate (PGMEA) and methanol from propylene glycol methyl ether (PGME; Propylene Glycol Methyl Ether) and methyl acetate (MA; Methyl Acetate), and propylene glycol Reactive distillation step to obtain methyl ether acetate (PGMEA); and a distillation step of separating the unreacted methyl acetate (MA) and methanol mixture obtained from the reactive distillation step under pressure or reduced pressure, wherein the unreacted methyl acetate (MA) and methanol are pressure swing distillation (Pressure Swing). can be separated by distillation).

In one example, the pressure swing distillation may be performed through the first distillation column and the second distillation column operated at a different pressure from the first distillation column. In one example, the pressure of the first distillation column (D1) may be less than or equal to the pressure at which decomposition of the catalyst provided in the reaction distiller (RD) starts or causes the flash point of the compound present in the first distillation column (D1), in detail , the pressure of the first distillation column may be 4 atm or more and 12 atm or less, and the pressure of the second distillation column may be less than 4 atm.

In another example, the pressure swing distillation may be performed through a single distillation column and a distillation column and a reactive distiller operated at different pressures. In one example, the pressure of the reactive distiller (RD) may be less than or equal to the pressure at which the decomposition of the catalyst provided in the reactive distiller (RD) starts or causes the ignition point of the compound present in the distillation column (D), and the pressure of the reactive distiller is 4 atm or more and 10 atm or less, and the pressure of the distillation column may be less than 4 atm.

As described above, the present invention can reduce energy consumption, carbon dioxide emission, waste production, and product consumption through process integration (process intensification). In particular, it is possible to produce propylene glycol methyl ether acetate with extremely low acidity and to have ultra-high purity, and it is possible to provide an apparatus for efficiently recovering as a pure component from an azeotrope of methyl acetate and methanol formed in the process of preparing it. .

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 shows the configuration of a manufacturing apparatus according to an embodiment.

2 shows the configuration of a manufacturing apparatus according to another embodiment.

3 shows the configuration of a manufacturing apparatus according to another embodiment.

4 shows the configuration of a manufacturing apparatus according to another embodiment.

Hereinafter, a preferred experimental example (example) is presented to help the understanding of the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited by the following experimental examples.

Although it has been described with reference to the above embodiments, it will be understood by those skilled in the art that various modifications and changes can be made to the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. will be able

manufacturing example

Propylene oxide (PO, 9) 10 kmol/h and methanol (10) were introduced into the reactor (R) in excess and passed through the still (d) to obtain pure propylene glycol methyl ether (PGME) from the bottom of the still (d). The unreacted methanol (11) was recycled from the top of the still (d) and reintroduced into the reactor (R).

Example 1

Propylene glycol methyl ether (PGME, 1) 10 kmol/h and methyl acetate (MA, 2) 28 kmol/h produced according to Preparation Example were introduced into a reactive distiller (RD) equipped with solid sodium methoxide, and propylene glycol Methyl ether acetate (PGMEA, 3) was obtained in 99.999%. At this time, the operating pressure of the reaction distiller (RD) was 1 atm. A methanol and methyl acetate (MA) mixture (4) was introduced from the reaction distiller (RD) into the first distillation column (D1), and pure methyl acetate (MA) was separated from the lower portion of the first distillation column (D1), and unseparated methyl An azeotrope of acetate (MA) and methanol (6) was introduced into the second distillation column (D2), and pure methyl acetate (MA) was separated from the bottom of the second distillation column (D2). Here, the unseparated methyl acetate (MA) and methanol azeotrope (8) obtained from the upper part of the second distillation column (D2) was recycled and introduced into the upper part of the first distillation column (D1). At this time, the operating pressure of the first distillation column (D1) was 10 atm, the operating pressure of the second distillation column (D2) was 1 atm.

Example 2

Propylene glycol methyl ether (PGME, 1) 10 kmol/h and methyl acetate (MA, 2) 10 kmol/h produced according to the above preparation example were introduced into a reactive distiller (RD) equipped with solid sodium methoxide, and also As 13 kmol/h of methyl acetate (MA, 8) recycled from the distillation column (D) was introduced, propylene glycol methyl ether acetate (PGMEA, 3) was obtained in 99.999%. At this time, the operating pressure of the reaction distiller (RD) was 7 atm. Methanol and methyl acetate (MA) azeotrope (6) was introduced from the reaction distiller (RD) into the distillation column (D), and pure methanol was separated from the lower part of the distillation column (D), and unseparated methanol and methyl acetate (MA) azeotrope The mixture (8) was recycled to the reaction distiller (RD). At this time, the operating pressure of the distillation column (D) was 1 atm.

Experimental example

Table 1 below summarizes the data according to Examples 1 and 2, and the required amount of methyl acetate (MA) required in the transesterification reaction of the reactive distiller, the yield of glycol methyl ether acetate (PGMEA), the reboiler duty (energy consumption) and carbon dioxide emissions.

	실시예 1Example 1	실시예 2Example 2
MA 요구량(kmol/h)MA demand (kmol/h)	28.4428.44	22.9922.99
PGMEA 수득률(%)PGMEA yield (%)	99.99999.999	99.99999.999
리보일러 듀티(MW)Reboiler Duty (MW)	2.1072.107	0.7820.782
에너지 절감(%)Energy Saving (%)	--	62.8962.89
연간 총 이산화탄소 배출량 (t/year)Total annual carbon dioxide emissions (t/year)	7092.77092.7	4521.334521.33
탄소 배출량 절감(%)Carbon emission reduction (%)	--	36.2536.25

Explanation of symbols

RD: Reactive distiller for propylene glycol methyl ether acetate (PGMEA) production

D (D1, D2) : still

R: Reactor for propylene glycol methyl ether (PGME) production

d: still

1: Propylene glycol methyl ether (PGME)

2: methyl acetate (MA)

3: Propylene glycol methyl ether acetate (PGMEA)

4: A mixture of unreacted methyl acetate and methanol (number of moles of methyl acetate > number of moles of methanol)

5: methyl acetate (MA)

6: unreacted methyl acetate and methanol azeotrope (number of moles of methanol > number of moles of methyl acetate)

7: methanol

8: unreacted methyl acetate and methanol azeotrope (number of moles of methyl acetate > number of moles of methanol)

9: Propylene oxide (PO)

10: methanol

11: methanol

Claims

As an apparatus for producing propylene glycol methyl ether acetate (PGMEA; Propylene Glycol Methyl Ether Acetate),

Propylene glycol methyl ether (PGME; Propylene Glycol Methyl Ether) and methyl acetate (MA; Methyl Acetate) are introduced to produce propylene glycol methyl ether acetate (PGMEA) and methanol, a reaction distiller equipped with a catalyst; and

A distillation column for separating the unreacted methyl acetate (MA) and methanol mixture introduced from the reaction distiller under pressure or reduced pressure,

The propylene glycol methyl ether acetate (PGMEA) is obtained from the reactive distiller,

The unreacted methyl acetate (MA) and methanol are separated by pressure swing distillation (Pressure Swing Distillation) manufacturing apparatus.
The method of claim 1,

Methyl acetate (MA) is introduced into the reaction distiller in excess (excess) than the number of moles of propylene glycol methyl ether (PGME).
The method of claim 1,

The catalyst provided in the reactive distillation apparatus is a basic catalyst.
The method of claim 1,

A production apparatus in which the yield of propylene glycol methyl ether acetate (PGMEA) obtained from a reactive distiller is 99% or more.
The method of claim 1,

The distillation column includes a first distillation column connected to a reactive distillation unit and a second distillation column connected to the first distillation column,

Pressure swing distillation is a manufacturing apparatus that is performed through a first distillation column and a second distillation column operated at a different pressure from the first distillation column.
6. The method of claim 5,

A manufacturing apparatus in which the pressure of the first distillation column is higher than that of the second distillation column.
6. The method of claim 5,

The pressure of the first distillation column is below the pressure at which the decomposition of the catalyst starts or causes the flash point of the compound in the distillation column.
6. The method of claim 5,

The pressure of the first distillation column is 4 atm or more and 12 atm or less,

The pressure of the second distillation column is less than 4 atm.
6. The method of claim 5,

A mixture of methyl acetate (MA) and methanol is obtained from the top of the second distillation column (D2),

A production apparatus in which a mixture of methyl acetate (MA) and methanol obtained from the upper portion of the second distillation column (D2) is recycled to the upper portion of the first distillation column (D1).
6. The method of claim 5,

A manufacturing apparatus comprising a reactive distiller, a first distillation column, and a second distillation column.
The method of claim 1,

The distillation column consists of one distillation column,

Pressure swing distillation is a distillation column and a distillation column and a production device that is performed through a reactive distiller operating at different pressures.
12. The method of claim 11,

A manufacturing device in which the pressure of the reaction distiller is higher than that of the distillation column.
12. The method of claim 11,

The pressure of the reaction distiller is below the pressure at which the decomposition of the catalyst starts or causes the ignition point of the compound in the distillation column.
12. The method of claim 11,

The pressure of the reaction distiller is 4 atm or more and 10 atm or less,

A production device in which the pressure of the distillation column is less than 4 atm.
12. The method of claim 11,

A mixture of methyl acetate (MA) and methanol is obtained from the top of the distillation column,

A production device in which a mixture of methyl acetate (MA) and methanol obtained from the top of the distillation column is recycled to the reaction distillation unit.
12. The method of claim 11,

A manufacturing apparatus comprising a reactive distiller and a distillation column.
A method for preparing propylene glycol methyl ether acetate (PGMEA; Propylene Glycol Methyl Ether Acetate), comprising:

Reaction distillation step to prepare propylene glycol methyl ether acetate (PGMEA) and methanol from propylene glycol methyl ether (PGME; Propylene Glycol Methyl Ether) and methyl acetate (MA; Methyl Acetate), and to obtain propylene glycol methyl ether acetate (PGMEA) ; and

A distillation step of separating the unreacted methyl acetate (MA) and methanol mixture obtained from the reaction distillation step under pressure or reduced pressure,

The method for producing the unreacted methyl acetate (MA) and methanol is separated by pressure swing distillation (Pressure Swing Distillation).
18. The method of claim 17,

Pressure swing distillation is a manufacturing method performed through a first distillation column and a second distillation column operated at a different pressure from the first distillation column.
19. The method of claim 18,

The pressure of the first distillation column is 4 atm or more and 12 atm or less,

The pressure of the second distillation column is less than 4 atm.
18. The method of claim 17,

Pressure swing distillation is a manufacturing method performed through one distillation column and a distillation column and a reactive distiller operating at different pressures.
21. The method of claim 20,

The pressure of the reaction distiller is 4 atm or more and 10 atm or less,

A production method wherein the pressure of the distillation column is less than 4 atm.