KR102064513B1 - Method for purifying alkylene oxide composition - Google Patents

Abstract

An embodiment is a method of purifying an alkylene oxide composition, comprising the following steps: (1) obtaining an alkylene oxide crude composition comprising an ionic component; and (2) mixing the alkylene oxide crude composition with a natural clay adsorbent to obtain a purified alkylene oxide composition suitable for subsequent processing.

Description

Method for purifying alkylene oxide composition {METHOD FOR PURIFYING ALKYLENE OXIDE COMPOSITION}

Embodiments relate to a method for purifying an alkylene oxide composition by removing ionic components that occur during the production of alkylene oxide.

Alkylene oxides are used as important intermediates in the chemical industry, and there are also various methods for preparing such alkylene oxides. By-products may also be produced differently depending on which reactants, catalysts, solvents and the like are used.

For example, a method for producing propylene oxide has been mainly used a hydrochlorine route method and a combination process (a process for producing styrene monomer or methyl tertiary butyl ether together with propylene oxide). However, the hydrochlorin route method has been increasingly avoided due to contamination problems, and the addition process has also been difficult due to the limited use of by-products. Therefore, in recent years, a new method for producing propylene oxide has been studied.

According to a new process, propylene is epoxidized with hydrogen peroxide, an oxidizing agent, under the action of a titanium compound catalyst to produce a propylene oxide composition. This manufacturing method is advantageous in that the process is simple, low energy consumption is possible, and environmentally friendly.

However, in the case of the propylene oxide composition prepared according to such a manufacturing method, there is a disadvantage in that an impurity exists that may affect a subsequent process of preparing a polyol. Therefore, research on what impurities are included and how to selectively remove the impurities continues.

Embodiments seek to provide a purified alkylene oxide composition suitable for application to subsequent processes by selectively removing ionic components that are unnecessary for subsequent processing of by-products of alkylene oxide prepared by the new method.

According to one embodiment, a method for purifying an alkylene oxide composition includes: (1) obtaining an alkylene oxide crude composition containing an ionic component; (2) mixing the alkylene oxide crude composition with a natural clay adsorbent; And (3) obtaining a purified alkylene oxide composition.

According to the method for purifying the alkylene oxide composition according to the embodiment, it is possible to obtain a purified alkylene oxide composition suitable for application in subsequent processes.

Furthermore, alkylene oxide compositions with improved purity and quality can be obtained.

Hereinafter, the present invention will be described in detail through embodiments. The embodiments are not limited to the contents disclosed below and may be modified in various forms as long as the gist of the invention is not changed.

"Including" in the present specification means that it may further include other components unless otherwise specified.

In addition, all numbers and expressions indicating amounts of components, reaction conditions, and the like described herein are to be understood as being modified in all instances by the term "about" unless otherwise specified.

Embodiments provide a purified alkylene oxide composition suitable for application in subsequent processes.

According to one embodiment, a method for purifying an alkylene oxide composition includes: (1) obtaining an alkylene oxide crude composition containing an ionic component; (2) mixing the alkylene oxide crude composition with a natural clay adsorbent; And (3) obtaining a purified alkylene oxide composition.

First, in order to purify the alkylene oxide composition according to the embodiment, an alkylene oxide crude composition containing an ionic component is obtained (step (1)).

The alkylene oxide crude composition is a composition immediately produced by the alkylene oxide production process, and means a composition containing an unnecessary ionic component or the like in a subsequent process.

According to one embodiment, the alkylene oxide crude composition may comprise an alkylene oxide, an ionic component, a nonionic component and a solvent.

The ionic component may include a cationic component and an anionic component.

Specifically, the cationic component may be at least one selected from the group consisting of NH ₂ ⁺ , NH ₄ ^+, and molecular sieves having the functional group. For example, the cationic component may include NH ₄ ⁺ . As another example, the cationic component may include NH ₂ ⁺ and NH ₄ ⁺ . For example, the cationic component may be composed of NH ₄ ⁺ , but is not limited thereto.

According to one embodiment, the ionic component comprises NH ₄ ⁺ , and the content of NH ₄ ⁺ contained in the alkylene oxide crude composition is 0.1 to 5 ppm. Specifically, the ionic component comprises NH ₄ ⁺ , the content of the NH ₄ ⁺ contained in the alkylene oxide crude composition is 0.1 to 3 ppm, 0.1 to 2.5 ppm, 0.3 to 2 ppm or 0.5 to 1.5 ppm It may be, but is not limited thereto.

In addition, the anionic component may be one or more selected from the group consisting of NO ₂ ⁻ , NO ₃ ⁻ and molecular sieves having a functional group thereof. For example, the anionic component may include NO ₂ ⁻ . As another example, the anionic component may include NO ₂ ⁻ and NO ₃ ⁻ . For example, the anionic component may be made of NO ₂ ⁻ , but is not limited thereto.

According to one embodiment, the ionic component comprises NO ₂ ⁻ , and the content of the NO ₂ ⁻ contained in the alkylene oxide crude composition is 0.1 to 5 ppm. Specifically, the ionic component includes NO ₂ ⁻ , and the content of the NO ₂ ⁻ included in the alkylene oxide crude composition may be 0.1 to 3 ppm, 0.1 to 1 ppm or 0.25 to 0.75 ppm, but It is not limited.

According to one embodiment, the ionic component may include a nitrogen-containing ionic component. For example, the ionic component may include one or more selected from the group consisting of NH ₂ ⁺ , NH ₄ ⁺ , NO ₂ ^−, and NO ₃ ⁻ . Alternatively, the ionic component may be one or more selected from the group consisting of NH ₂ ⁺ , NH ₄ ⁺ , NO ₂ ^−, and NO ₃ ⁻ .

According to one embodiment, the ionic component may include 30 to 90% by weight of the cationic component based on the total weight of the ionic component. Specifically, the ionic component may include 40 to 90% by weight, 50 to 90% by weight or 50 to 80% by weight of the cationic component based on the total weight of the ionic component. More specifically, the ionic component may include 60 to 80% by weight of the cationic component based on the total weight of the ionic component, but is not limited thereto.

According to one embodiment, the alkylene oxide crude composition may include a nonionic component in addition to the ionic component. For example, the nonionic component may include an amine component.

Specifically, the amine-based component is diisopropylamine (diisopropylamine), diethylamine (diethylamine), triethylamine (trimethylamine), diethanolamine (diethanolamine), dimethylethylamine (dimethylethylamine), methyl diethanolamine (methyldiethanolamine ), Trimethylamine, and monoisopropylamine may include one or more selected from the group consisting of monoisopropylamine.

In addition, the alkylene oxide crude composition may include a solvent.

Specifically, the solvent may include one or more selected from the group consisting of water, methanol, acetaldehyde, propionaldehyde, methyl formate, and dimethoxymethane.

For example, the alkylene oxide crude composition may comprise dimethoxymethane (DMM) and methyl formate (MF), the content of dimethoxymethane (DMM) and methyl formate (MF) is 10 to 3,000 ppm, 10 to 1,000 ppm, 10 to 500 ppm or 20 to 100 ppm, but is not limited thereto.

According to one embodiment, the controlled polymerization rate (CPR) of the crude alkylene oxide composition of step (1) may be 0.2 to 20. Specifically, the CPR of the alkylene oxide crude composition may be 0.2 to 10, 0.2 to 5, 0.2 to 2, 0.5 to 3, 0.5 to 2 or 0.8 to 1.5, but is not limited thereto.

The CPR (Controlled Polymerization Rate) is an indicator indicating the amount of basic substances in the alkylene oxide composition, and neutralized appropriate hydrochloric acid (concentration: 0.001) after mixing 30 g of the alkylene oxide composition with 100 ml of methanol according to the ASTM D6437 test method. It is the result of quantifying the quantity of N).

When the CPR of the alkylene oxide crude composition of step (1) does not satisfy the appropriate range, it is difficult to control the reactivity in the manufacturing process of the latter product using the raw material, as well as the CPR value of the latter product using the raw material It is outside of the CPR specification. Therefore, when the CPR value of the alkylene oxide crude composition satisfies an appropriate range, the quality of the product can be improved. In particular, it is more advantageous to maintain the CPR value of the alkylene oxide crude composition up to 2.0 or less.

Specifically, as the cationic impurities among the ionic impurities mentioned above are more than the anionic impurities, the cationic impurities remaining after the impurities are neutralized become a factor for raising the CPR value of the alkylene oxide crude composition.

According to one embodiment, the basicity of the crude alkylene oxide composition of step (1) may be 1 to 40. Specifically, the basicity of the alkylene oxide crude composition may be 2 to 40, 2 to 20, 0.4 to 10 or 0.4 to 7, but is not limited thereto.

Specifically, as the cationic impurities among the ionic impurities mentioned above are more than the anionic impurities, the cationic impurities remaining after the impurities are neutralized may be a factor for increasing the basicity of the crude alkylene oxide composition.

According to one embodiment, the nitrogen content of the crude alkylene oxide composition of step (1) is 0.2 to 10 ppm. Specifically, the nitrogen content of the alkylene oxide crude composition may be 0.2 to 7 ppm, 0.2 to 5 ppm, 0.2 to 3 ppm, 0.2 to 1.8 ppm, 0.3 to 1.5 ppm, 0.2 to 1.5 ppm or 0.3 to 0.8 ppm It is not limited to this.

When the nitrogen content of the alkylene oxide crude composition of step (1) is maintained at a high level, the nitrogen content of the alkylene oxide crude composition is kept as low as possible in that it causes a odor in the latter product using the raw material. Good to do.

The factor which raises the nitrogen content of the said alkylene oxide crude composition is because of the components containing nitrogen contained in the above-mentioned ionic component, nonionic component, and a solvent.

According to one embodiment, the alkylene oxide may be ethylene oxide, propylene oxide or butylene oxide. Specifically, the alkylene oxide may be propylene oxide.

The alkylene oxide crude composition is then mixed with a natural clay adsorbent (step (2)).

According to one embodiment, the natural clay adsorbent may be a series of aluminosilicate (aluminosilicate).

Specifically, the natural clay adsorbent may be montmorillonite, kaolinite, kapilite, sepiolite, bentonite, diatomite, or a combination thereof, and bentonite is preferred, but is not limited thereto. It is not.

The natural clay adsorbent is a functional group of OH ₂ ⁺ and O ^- is formed on the surface through the process as shown in the following figure, the OH ₂ ⁺ and O ^- is a cationic component and anionic component and ions in the alkylene oxide crude composition By bonding, the cationic component and the anionic component in the alkylene oxide crude composition can be effectively removed.

In addition, by using the natural clay adsorbent, only ionic components can be effectively removed without generating impurities due to side reactions in the alkylene oxide crude composition. Furthermore, by adsorbing the cationic component and the anionic component in the alkylene oxide crude composition to the dispersed natural clay adsorbent, it is possible to effectively remove both the cationic component and the anionic component from the alkylene oxide crude composition.

Specifically, molecular sieves such as zeolites have the advantage of selectively removing the cationic component NH ₄ ⁺ through physical adsorption, but when using such molecular sieves, the anionic component NO ₂ ⁻ is not adsorbed. Difficult to remove, the NH ₄ ⁺ is not completely removed, but also because the water (H ₂ O) is adsorbed there is a disadvantage that the service life can be shortened.

On the other hand, the natural clay adsorbent can effectively remove not only cationic components such as NH ₄ ^{+ in the} alkylene oxide crude composition, but also anionic components such as NO ₂ ⁻ , and similar levels to the molecular sieve. The basicity can be lowered. In addition, the moisture is not adsorbed together, there is an advantage that can extend the service life.

According to one embodiment, the alkylene oxide crude composition and the natural clay adsorbent may be mixed in a weight ratio of 1: 1 to 50. For example, the weight ratio of the alkylene oxide crude composition and the natural clay adsorbent is 1: 1 to 45, 1: 1 to 40, 1: 1 to 35, 1: 1 to 30, 1: 1 to 25, 1 : 1 to 20, 1: 1 to 18, 1: 1 to 15, or 1: 1 to 10. When the said range is satisfied, since the dispersibility of the said natural clay adsorbent can be improved, the outstanding adsorption effect can be acquired.

According to one embodiment, the method may further include sonicating after step (2) and before step (3). For example, the sound wave treatment may be performed at 20 to 40 kHz or 30 to 40 kHz for 10 to 20 minutes or 10 to 30 minutes. Through the sonic treatment, the natural clay adsorbent can be effectively dispersed in the alkylene oxide crude composition.

Next, a purified alkylene oxide composition is obtained (step (3)).

According to one embodiment, the purified alkylene oxide composition comprises an ionic component comprising a cationic component and an anionic component.

At this time, the description of the type of the ionic component is as described in step (1). In addition, the purified alkylene oxide composition may include a nonionic component and a solvent in addition to the ionic component, a description thereof is also as described in step (1).

According to one embodiment, the purified alkylene oxide composition comprises an ionic component comprising a cationic component and an anionic component, the cationic component 10 to 70 weight based on the total weight of the ionic component May contain%. For example, the ionic component may include 20 to 70% by weight, 30 to 70% by weight, 40 to 60% by weight or 45 to 55% by weight of the cationic component based on the total weight of the ionic component. However, the present invention is not limited thereto.

For example, the purified alkylene oxide composition may include NH ₄ ⁺ , and the content of NH ₄ ⁺ contained in the purified alkylene oxide composition may be 0.05 to 0.5 ppm. Specifically, the content of the NH ₄ ⁺ contained in the purified alkylene oxide composition may be 0.1 to 0.5 ppm, 0.15 to 0.5 ppm, 0.2 to 0.5 ppm, 0.3 to 0.5 ppm or 0.4 to 0.5 ppm, but is not limited thereto. It doesn't happen.

In addition, the purified alkylene oxide composition may include NO ₂ ⁻ , and the content of the NO ₂ ⁻ included in the purified alkylene oxide composition may be 0.05 to 0.5 ppm. Specifically, the content of the NO ₂ ⁻ included in the purified alkylene oxide composition may be 0.1 to 0.5 ppm or 0.2 to 0.5 ppm, but is not limited thereto.

That is, cationic components such as NH ₄ ⁺ and anionic components such as NO ₂ ⁻ contained in the alkylene oxide crude composition may be adsorbed and removed from the natural clay adsorbent.

According to one embodiment, the CPR of the purified alkylene oxide composition of step (3) is 0-2. Specifically, the CPR of the purified alkylene oxide composition may be 0 to 1.5, 0 to 1.2, 0 to 0.8, 0 to 0.5, 0.1 to 0.5, 0.1 to 0.3 or 0.1 to 0.2, but is not limited thereto.

The definition of the CPR is as described in step (1) above.

When the CPR of the purified alkylene oxide composition of step (3) is within the above range, it is not only easy to control the reactivity in the manufacturing process of the latter product using the raw material, but also the lower CPR value of the made product itself, the product CPR specification It is advantageous in that it satisfies.

According to one embodiment, the basicity of the purified alkylene oxide composition of step (3) is 0-4. Specifically, the basicity of the purified alkylene oxide composition may be 0 to 3, 0 to 2.4, 0 to 1.6 or 0 to 1.0, but is not limited thereto.

According to one embodiment, the nitrogen content of the purified alkylene oxide composition of step (3) is from 0.1 to 0.7 ppm. Specifically, the nitrogen content of the purified alkylene oxide composition may be 0.1 to 0.6 ppm, 0.1 to 0.55 ppm, 0.2 to 0.55 ppm or 0.4 to 0.55 ppm, but is not limited thereto.

When the nitrogen content of the purified alkylene oxide composition of step (3) is within the above range, the rear end of the product having the same as the raw material is a rear end of the alkylene oxide produced by other methods such as chlorohydrin and combined acid method. It is advantageous in that it is reduced to the odor level of the product.

The above content is described in more detail by the following examples. However, the following examples are only for illustrating the present invention, and the scope of the examples is not limited thereto.

EXAMPLE

Example 1-1

Through the process of preparing the alkylene oxide, an alkylene oxide crude composition was obtained. At this time, the obtained alkylene oxide crude composition contained NH ₄ ⁺ , NO ₂ ^−, and alkylene oxide.

20 mg of montmorillonite (Aldrich Chemical Company. Inc) as a natural clay adsorbent was added to 1 ml of the crude alkylene oxide composition, and sonicated to obtain a purified alkylene oxide composition.

Example 1-2

The experiment was performed in the same manner as in Example 1-1, except that kaolinite (Aldrich Chemical Company. Inc) was used as the natural clay adsorbent.

Example 1-3

The same experiment as in Example 1-1 was performed except that Sepiolite (Aldrich Chemical Company. Inc) was used as the natural clay adsorbent.

Example 1-4

The experiment was the same as in Example 1-1 except that bentonite (Aldrich Chemical Company. Inc) was used as the natural clay adsorbent.

Example 1-5

Experiment was carried out in the same manner as in Example 1-1, except that diatomaceous earth (Aldrich Chemical Company. Inc) was used as the natural clay adsorbent.

Comparative Example 1-1

The alkylene oxide crude composition was used without purification.

Evaluation Example 1: Determination of Nitrogen Content

Based on the test method of ASTM D 6437 (Standard Test Method for Polyurethane Raw materials), each composition was diluted in 3 g of toluene and then quantitatively analyzed by detecting the wavelength emitted by nitrogen dioxide generated by burning in oxygen and argon.

The results of Evaluation Example 1 are shown in Table 1 below.

Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1-5 Comparative Example 1-1 Nitrogen content (ppm) of alkylene oxide crude composition 0.78 0.78 0.78 0.78 0.78 0.78 Refined
Nitrogen Content (ppm) of Alkylene Oxide Crude Composition 0.72 0.63 0.65 0.39 0.66 0.78 No purification step

As shown in Table 1, the nitrogen content of the alkylene oxide composition after the purification step of the alkylene oxide composition of Examples 1-1 to 1-5, the alkylene of Comparative Example 1-1 did not perform the purification step It can be seen that it is lower than the nitrogen content of the oxide crude composition. Specifically, Examples 1-1 to 1-5 showed a nitrogen content reduction rate of 8%, 19%, 17%, 50% and 15%, respectively, compared to Comparative Example 1-1 without performing the purification step.

Example 2-1

Through the process of preparing the alkylene oxide, an alkylene oxide crude composition was obtained. At this time, the obtained alkylene oxide crude composition contained NH ₄ ⁺ , NO ₂ ^−, and alkylene oxide.

20 mg of bentonite (Aldrich Chemical Company. Inc) as a natural clay adsorbent was added to 1 ml of the crude alkylene oxide composition, and sonicated to obtain a purified alkylene oxide composition.

Example 2-2

The same experiment as in Example 2-1 was conducted except that 40 mg of the natural clay adsorbent was used.

Example 2-3

The same experiment as in Example 2-1 was conducted except that 60 mg of the natural clay adsorbent was used.

Example 2-4

The same experiment as in Example 2-1 was conducted except that 80 mg of the natural clay adsorbent was used.

Comparative Example 2-1

The alkylene oxide crude composition was used without purification.

Evaluation Example 2: Determination of Nitrogen Content

Based on the test method of ASTM D 6437 (Standard Test Method for Polyurethane Raw materials), each composition was diluted in 3 g of toluene and then quantitatively analyzed by detecting the wavelength emitted by nitrogen dioxide generated by burning in oxygen and argon.

The results of Evaluation Example 2 are shown in Table 2 below.

Example 2-1 Example 2-2 Example 2-3 Example 2-4 Comparative Example 2-1 Nitrogen content (ppm) of alkylene oxide crude composition 0.61 0.61 0.61 0.61 0.61 Refined
Of alkylene oxide crude compositions
Nitrogen content (ppm) 0.15 0.43 0 0 0.61 No purification step

As shown in Table 2, the nitrogen content of the alkylene oxide composition after the purification step of the alkylene oxide composition of Examples 2-1 to 2-4, the alkylene of Comparative Example 2-1 did not perform the purification step It can be seen that it is lower than the nitrogen content of the oxide crude composition. Specifically, Examples 2-1 to 2-4 showed a nitrogen content reduction rate of 75%, 30%, 100% and 100%, respectively, compared to Comparative Example 2-1 without performing the purification step.

Claims (19)

(1) obtaining an alkylene oxide crude composition containing an ionic component;
(2) a weight ratio of the alkylene oxide crude composition with a natural clay adsorbent including montmorillonite, kaolinite, sepiolite, bentonite, or a combination thereof, in a weight ratio of 1: 1 to 50; Mixing with; And
(3) A method for purifying an alkylene oxide composition, comprising obtaining a purified alkylene oxide composition. The method of claim 1,
Further comprising sonicating after step (2) and before step (3). The method of claim 1,
A method for purifying an alkylene oxide composition, wherein the ionic component comprises a cationic component and an anionic component. The method of claim 3,
The ionic component comprises 30 to 90% by weight of the cationic component based on the total weight of the ionic component, alkylene oxide composition purification method. The method of claim 1,
The method of purifying an alkylene oxide composition, wherein the ionic component comprises a nitrogen-containing ionic component. The method of claim 5,
The nitrogen-containing ionic component comprises at least one member selected from the group consisting of NH ₂ ⁺ , NH ₄ ⁺ , NO ₂ ^−, and NO ₃ ⁻ , alkylene oxide composition purification method. The method of claim 1,
Process for purifying alkylene oxide composition, wherein the nitrogen content of the alkylene oxide crude composition of step (1) is 0.2 to 10 ppm. The method of claim 1,
The ionic component comprises NH ₄ ⁺ ,
A method for purifying an alkylene oxide composition, wherein the content of NH ₄ ⁺ contained in the alkylene oxide crude composition of step (1) is 0.1 to 5 ppm. The method of claim 1,
The natural clay adsorbent is an aluminosilicate series, alkylene oxide composition purification method. delete delete The method of claim 1,
The alkylene oxide composition purification method, wherein the alkylene oxide is propylene oxide. The method of claim 1,
Wherein said purified alkylene oxide composition comprises an ionic component comprising a cationic component and an anionic component, wherein said cationic component comprises 10 to 70 weight percent based on the total weight of said ionic component Method for Purifying Wylene Oxide Composition. The method of claim 1,
The nitrogen content of the purified alkylene oxide composition is 0.1 to 0.7 ppm, alkylene oxide composition purification method. The method of claim 1,
The purified alkylene oxide composition comprises NH ₄ ⁺ , wherein the content of NH ₄ ⁺ contained in the purified alkylene oxide composition is 0.05 to 0.5 ppm. The method of claim 1,
The purified alkylene oxide composition comprises NO ₂ ⁻ , wherein the content of NO ₂ ⁻ contained in the purified alkylene oxide composition is 0.05 to 0.5 ppm. Alkylene oxide composition prepared by the method of claim 1, the nitrogen content of 0.1 to 0.7 ppm. The method of claim 17,
The alkylene oxide composition comprises NH ₄ ⁺ , wherein the content of NH ₄ ⁺ contained in the alkylene oxide composition is 0.05 to 0.5 ppm, alkylene oxide composition. The method of claim 17,
The alkylene oxide composition comprises NO ₂ ⁻ , wherein the content of NO ₂ ⁻ contained in the alkylene oxide composition is 0.05 to 0.5 ppm.