KR101765802B1 - Method of deodorizing 1,2-alkane diols - Google Patents

Abstract

The present invention relates to a method for deodorizing 1,2-alkanediol, comprising the following steps: (a) a primary 1,2-alkanediol treatment step including at least one unit process selected from the group consisting of a reduction agent treatment process, an activated carbon treatment process, and an organic solvent treatment process; and (b) a secondary 1,2-alkanediol treatment step using white clay.

Description

METHOD OF DEODORIZING 1,2-ALKANE DIOLS [0002]

The present invention relates to a process for the treatment of 1,2-alkanediol comprising: (a) at least one unit process selected from the group consisting of a reducing agent treatment process, an activated carbon treatment process, and an organic solvent treatment process; And (b) a second treatment step of 1,2-alkanediol with clay.

Most of the 1,2-alkanediol has a surfactant effect and a moisturizing power, and has antimicrobial activity against fungi, bacteria and yeast, and can also serve as a preservative for cosmetics. In particular, 1,2-hexanediol is a kind of 1,2-alkanediol and is used as a solvent in cosmetic raw materials. The importance of 1,2-hexanediol has become more and more important as human harmfulness to parabens compounds, which have been widely used as preservatives in cosmetics, has come to the fore.

On the other hand, although 1,2-hexanediol requires odorless 1,2-hexanediol in order to be used in cosmetics, 1,2-hexanediol is industrially synthesized and deodorized before it is decomposed, , Herbal medicine boiling odor, or solvent odor. Therefore, it is very important to deodorize such odor in using 1,2-hexanediol as a cosmetic raw material.

The 1,2-alkane diol may be prepared in various ways. The 1,2-epoxyalkane may be prepared by reacting 1-alkene with hydrogen peroxide under a metal catalyst, A method of obtaining a 2-alkanediol; And hydrolyzing the hydroxyalkyl organic acid ester with an acid or base after reacting the hydroxyalkyl organic acid ester with a 1-alkene, an organic acid, and hydrogen peroxide, or a method in which the hydroxyalkyl organic acid ester is reacted with an alcohol To obtain 1,2-alkanediol as a result of the transesterification reaction, and the like are widely known.

Depending on which of the various manufacturing methods listed above is used, unreacted alkenes, organic acids, and organic acid esters; Aldehydes, ketones, and ether compounds that are side reaction materials; And impurities having an odor of organic solvents and catalysts used in the production are various. In this connection, there has been a constant demand for a process for completely treating all the undecalted alkanediols with 1,2-alkanediols produced by certain production methods.

Several methods for removing the odor of the 1,2-alkanediol are known. In Japanese Patent Application Laid-Open No. 2008-007463 A, after the 1,2-alkanediol is mixed with water and any one of a hydrophobic solvent, for example, normal hexane, cyclohexane, and 2-methylhexane, The 1,2-alkanediol is present in the water layer, but odorous impurities are transferred to the organic layer to reduce the odor of the 1,2-alkanediol. However, the deodorization method is limited to the 1,2-alkanediol produced by the method of reacting the alkene with hydrogen peroxide in the presence of formic acid and reacting the obtained reaction product with alcohol, and the deodorizing effect is insufficient.

In WO 1998/002513 A1, odorous impurities with a low boiling point were distilled off using nitrogen or water vapor. Non-polar odor impurities having high boiling point were treated with activated carbon after mixing with water, but they did not show complete deodorization .

Korean Patent Publication No. 10-1268554 B1 discloses a method for deodorizing 1,2-alkanediol by adding propylene glycol and water to 1,2-alkanediol and completely removing propylene glycol under reduced pressure. However, when the number of carbon atoms is 7 And the 1,2-alkanediol used in the production example is only those having 8 or more carbon atoms. Further, the deodorizing operation such as washing with hot water or removing odor impurities with hexane prior to deodorization with propylene glycol was pre-treated. In particular, in the case of 1,2-hexanediol in which the number of carbon atoms is 6 and the product is well soluble in water, It is not possible to apply the process of washing with the hot water exemplified. In addition, propylene glycol has a very high boiling point and requires a large amount of heat for distillation, and it is industrially very difficult to completely remove 1,2-hexanediol.

Korean Patent Publication No. 10-1540842 B1 discloses a process for producing a polyurethane foam by mixing an organic solvent selected in consideration of polarity, solubility, boiling point, and density with 1,2-hexane diol, In this case, the non-polar odor impurities can be easily removed by the organic solvent, but relatively polar odor impurities are not removed by the organic solvent and are present in the water layer like 1,2-hexanediol, It was not.

Accordingly, the present invention proposes a deodorization method of 1,2-alkanediol which has excellent deodorizing effect and does not require excessive apparatus or energy, regardless of the method of producing 1,2-alkanediol.

Accordingly, the present invention provides a process for producing 1,2-alkanediol comprising: (a) a first treatment step of a 1,2-alkanediol comprising at least one unit process selected from the group consisting of a reducing agent treatment process, an activated carbon treatment process, and an organic solvent treatment process; And (b) a second step of treating the 1,2-alkanediol with clay.

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

According to a first aspect of the present invention, there is provided a process for producing a 1,2-alkanediol comprising: (a) a first treatment step of a 1,2-alkanediol comprising at least one unit process selected from the group consisting of a reducing agent treatment process, an activated carbon treatment process, and an organic solvent treatment process; And (b) a second treatment step of 1,2-alkanediol with clay.

The method of deodorizing 1,2-alkanediol according to one embodiment of the present invention is for producing odorless 1,2-hexanediol which can be used for cosmetic applications, It is possible to provide a deodorizing method that overcomes the limitations of the prior art which are not commonly used in all 1,2-hexanediol because of differences in degree of odor and cause thereof.

The method for deodorizing a 1,2-alkanediol according to an embodiment of the present invention is characterized in that a 1,2-alkanediol containing at least one unit process selected from the group consisting of a reducing agent treatment process, an activated carbon treatment process, And the second treatment step of 1,2-alkanediol using clay, which is more effective than the conventional method of deodorizing 1,2-alkanediol.

In the deodorization method of a 1,2-alkanediol according to an embodiment of the present invention, in the second treatment step, the clay may act as a catalyst for decomposition or conversion of an impurity contained in the 1,2- It acts as an adsorbent for the impurities contained in the 2-alkanediol, and is more effective in removing polar odorous substances, and decomposes materials containing alkenes and carbonyl groups, such as aldehydes, or converts them to high boiling point materials Thereby making it easier to remove in the subsequent process.

1 is a flowchart showing one type of deodorization process of 1,2-alkanediol performed according to one embodiment of the present invention.
FIG. 2 is a flowchart showing another type of deodorization process of 1,2-alkanediol performed according to one embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is "on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

Throughout this specification, the term "combination (s) thereof " included in the expression of the machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, Quot; means at least one selected from the group consisting of the above-mentioned elements.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B".

Throughout this specification, the term "alkyl" refers to an alkyl group having from 1 to 12 carbon atoms, from 1 to 10 carbon atoms, from 1 to 8 carbon atoms, from 1 to 5 carbon atoms, from 1 to 3 carbon atoms, from 3 to 8 Carbon atoms, or linear or branched alkyl groups having from 3 to 5 carbon atoms. For example, the methyl group is in the group, ethyl group, n- propyl group ⁽ⁿ Pr), iso- propyl ⁽ⁱ Pr), n- butyl group ⁽ⁿ Bu), tert- butyl ^(t Bu), iso- butyl ⁽ⁱ Bu), sec- butyl ^(s Bu), pentyl, hexyl, iso-hexyl, heptyl, 4,4-dimethyl pentyl, octyl, 2,2,4-trimethyl pentyl group, Nonyl group, decyl group, undecyl group, dodecyl group, isomers thereof, and the like, but the present invention is not limited thereto.

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to these embodiments and examples and drawings.

According to a first aspect of the present invention, there is provided a process for producing a 1,2-alkanediol comprising: (a) a first treatment step of a 1,2-alkanediol comprising at least one unit process selected from the group consisting of a reducing agent treatment process, an activated carbon treatment process, and an organic solvent treatment process; And (b) a second step of treating the 1,2-alkanediol with clay.

In one embodiment of the present invention, the 1,2-alkanediol may include those having 5 to 10 carbon atoms. For example, the 1,2-alkanediol may be 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, - decanediol, and all possible isomers thereof.

In one embodiment of the invention, the alkanediol may comprise 1,2-hexanediol.

In one embodiment of the invention, as shown in Figures 1 and 2, the first processing step and the second processing step may be performed simultaneously or sequentially. Alkanediol is carried out simultaneously or sequentially, in each case in which each unit process of the first treatment step is carried out individually or in combination, with the second treatment step of treating the 1,2-alkanediol by clay But is not limited thereto.

In one embodiment of the present application, when the first processing step and the second processing step are sequentially performed, if the second processing step is performed after the first processing step, only the impurities But can remove the remaining water in the 1,2-alkanediol. In addition, if the first processing step is performed after the second processing step, the impurities are decomposed or converted by the clay, and then the impurities can be effectively removed during the first processing step.

In one embodiment of the present invention, when the first treatment step and the second treatment step are performed at the same time, the deodorization method of the 1,2-alkanediol can be conveniently performed by performing the filtration treatment at once after deodorization. Particularly, in the case where the activated carbon treatment step and the second treatment step are performed simultaneously in the unit process of the first treatment step, the deodorization method can be easily performed by mixing the activated carbon and the clay and processing them at once and filtering them at a time.

In one embodiment of the present invention, the first processing step includes performing the second processing step between the unit processes when the first processing step includes a plurality of the unit processes, but the present invention is not limited thereto .

In one embodiment of the invention, the reducing agent treatment process comprises adding a reducing agent selected from the group consisting of metal salts of borohydride anions, metal salts of dithionite anions, and combinations thereof to the 1,2-alkanediol Reducing an impurity contained in the 1,2-alkanediol; Wherein the activated carbon treatment step comprises adding activated carbon to the 1,2-alkanediol to adsorb impurities contained in the 1,2-alkanediol on the activated carbon, and then filtering the activated carbon; The organic solvent treatment step may include the step of adding an organic solvent and water to the 1,2-alkanediol to extract the impurities contained in the 1,2-alkanediol by the organic solvent, It is not. For example, one or more of the unit processes of the first treatment step may be performed depending on the degree of odor of the 1,2-alkanediol to be deodorized, and the unit processes may be all performed to enhance the deodorization effect .

In one embodiment of the present invention, the reducing agent used in the reducing agent treatment process is selected from the group consisting of lithium borohydride, sodium borohydride, potassium borohydride, lithium dithionite, sodium dithionite, potassium dithionite, But are not limited to, metal salts selected from the group consisting of combinations of these.

In one embodiment of the present invention, in the reducing agent processing step, the peroxidized impurities contained in the 1,2-alkanediol generated due to the side reaction of hydrogen peroxide used as a raw material in the 1,2-alkanediol production process, But it is not limited thereto. When the impurities are reduced, the impurities may be converted into odorless compounds or converted to materials that can be easily removed in a subsequent deodorization process after the reduction process, but are not limited thereto.

In one embodiment of the present invention, the reducing agent may be used in an amount of about 1 part by weight or less based on 100 parts by weight of the 1,2-alkanediol, but the present invention is not limited thereto. For example, the reducing agent may be present in an amount of up to about 1 part by weight, up to about 0.9 part by weight, up to about 0.8 part by weight, up to about 0.7 part by weight, up to about 0.6 part by weight, About 0.5 part by weight or less, about 0.4 part by weight or less, about 0.3 part by weight or less, about 0.2 part by weight or less, or about 0.1 part by weight or less.

In one embodiment of the present invention, the reducing agent treatment process may be conducted in an alkali aqueous solution environment or in a water-free state, but is not limited thereto.

In one embodiment of the present invention, there is no particular limitation on the pH in the reducing agent treatment process, but the present invention is not limited thereto.

In one embodiment of the invention, the reducing agent treatment process may be performed at a temperature of about 20 < 0 > C to about 90 < 0 > C, but is not limited thereto. For example, the reducing agent treatment process may be performed at a temperature of from about 20 캜 to about 90 캜, from about 20 캜 to about 80 캜, from about 20 캜 to about 70 캜, from about 20 캜 to about 60 캜, From about 20 째 C to about 40 째 C, from about 20 째 C to about 30 째 C, from about 30 째 C to about 90 째 C, from about 40 째 C to about 90 째 C, from about 50 째 C to about 90 째 C, But is not limited to, at a temperature of from about 0 C to about 90 C, from about 80 C to about 90 C, from about 30 C to about 80 C, from about 40 C to about 70 C, or from about 50 C to about 60 C . In one embodiment of the invention, when the reducing agent treatment process proceeds at less than about 20 ° C, the reaction rate may be very slow, but is not limited thereto.

In one embodiment of the present invention, the reducing agent treatment process may be performed for about 1 hour to about 3 hours to complete the reaction, but the present invention is not limited thereto.

In one embodiment of the present invention, in the activated carbon treatment process, the activated carbon may include a carbonaceous adsorbent, but is not limited thereto. The active carbon may be granular activated carbon or powder activated carbon. For example, wood activated carbon, coal activated carbon, alkaline activated carbon, neutral activated carbon, and the like may be used, but the present invention is not limited thereto.

In one embodiment of the present invention, the activated carbon may be used in an amount of about 1 part by weight to about 30 parts by weight based on 100 parts by weight of the 1,2-alkanediol, but is not limited thereto. For example, the activated carbon may be present in an amount of from about 1 part by weight to about 30 parts by weight, from about 1 part by weight to about 25 parts by weight, from about 1 part by weight to about 20 parts by weight, From about 1 part to about 10 parts, from about 1 part to about 8 parts, from about 1 part to about 6 parts, from about 1 part to about 5 parts, from about 1 part to about 15 parts, from about 1 part to about 10 parts, From about 1 part to about 3 parts, from about 1 part to about 2 parts, from about 1 part to about 30 parts, from about 2 parts to about 30 parts, from about 1 part to about 4 parts, from about 1 part to about 3 parts, 3 parts by weight to about 30 parts by weight, about 4 parts by weight to about 30 parts by weight, about 5 parts by weight to about 30 parts by weight, about 10 parts by weight to about 30 parts by weight, about 15 parts by weight to about 30 parts by weight, 20 parts by weight to about 30 parts by weight, about 25 parts by weight to about 30 parts by weight, about 5 parts by weight to about 25 parts by weight, about 5 parts by weight to about 20 parts by weight, About 15 parts by weight, about 5 parts by weight to about 10 parts by weight, about 10 parts by weight to about 25 parts by weight, about 10 parts by weight to about 20 parts by weight, or about 10 parts by weight to about 15 parts by weight, But is not limited thereto.

In one embodiment herein, the activated carbon may be diluted with water to lower the viscosity of the 1,2-alkanediol in the activated carbon treatment process, wherein the water is present in an amount of from about 30 parts by weight to about 100 parts by weight relative to 100 parts by weight of the 1,2- 300 parts by weight, about 30 parts by weight to about 250 parts by weight, about 30 parts by weight to about 200 parts by weight, about 30 parts by weight to about 150 parts by weight, about 30 parts by weight to about 100 parts by weight, But it is not limited thereto.

In one embodiment of the present invention, the activated carbon treatment process may be performed at a temperature of about 30 < 0 > C to about 80 < 0 > C, but is not limited thereto. For example, the activated carbon treatment process may be performed at a temperature of from about 30 캜 to about 80 캜, from about 30 캜 to about 70 캜, from about 30 캜 to about 60 캜, from about 30 캜 to about 50 캜, At a temperature from about 40 DEG C to about 80 DEG C, from about 50 DEG C to about 80 DEG C, from about 60 DEG C to about 80 DEG C, from about 70 DEG C to about 80 DEG C, from about 40 DEG C to about 70 DEG C, But is not limited thereto. For example, when the temperature is raised in the activated carbon treatment process, a relatively small amount of water can be used, and when a small amount of water is used, there is an advantage that water can be easily removed by distillation, but the present invention is not limited thereto.

In one embodiment of the present invention, in the organic solvent treatment, water and the organic solvent not mixed with water are added to the 1,2-alkanediol to separate the phases, the 1,2-alkane But the present invention is not limited thereto, and the extraction may be performed by extracting the 1,2-alkanediol in an aqueous solution in which odor impurities contained in the diol are removed and the odor impurities are partially removed.

In one embodiment of the present invention, in the organic solvent treatment, the organic solvent may be a solvent selected from the group consisting of a linear or branched hydrocarbon solvent, a cycloalkane solvent, a dialkyl ketone solvent, But is not limited thereto.

In one embodiment of the invention, the hydrocarbon-based solvent has a total carbon number of from about 5 to about 25, from about 5 to about 20, from about 5 to about 15, from about 10 to 20, from about 15 to about 20, But are not limited to, linear or branched hydrocarbon-based solvents. For example, the linear or branched hydrocarbons may include but are not limited to pentane, hexane, heptane, octane, nonane, decane, or all possible isomers thereof.

In one embodiment of the invention, the cycloalkane-based solvent has a total carbon number of from about 5 to about 25, from about 5 to about 20, from about 5 to about 15, from about 10 to 20, from about 15 to about 20, But is not limited thereto. For example, the cycloalkane can include, but is not limited to, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, or all possible isomers thereof.

In one embodiment herein, the dialkyl ketone solvent has a total carbon number of from about 3 to about 15, from about 3 to about 10, from about 3 to about 8, from about 5 to about 15, from about 5 to about 10, from about 5 To about 8, from about 6 to about 8, or from about 3 to about 6, by weight of the dialkyl ketone. The two linear or branched alkyl groups contained in the dialkyl ketone system may be the same or different from each other and each of the alkyl groups may have from about 1 to about 6 carbon atoms, from about 1 to about 5, from about 1 to about 4, from about 1 To about 3, or about 1 or about 2. For example, the linear or branched alkyl group may be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, An isohexyl group, or all possible isomers thereof, but is not limited thereto.

In one embodiment of the present application, in the organic solvent treatment process, the organic solvent includes one selected from the group consisting of hexane, cyclohexane, diethylketone, methylbutylketone, methylisobutylketone, and combinations thereof But is not limited thereto. For example, the organic solvent used in the organic solvent treatment process may be n-hexane, but is not limited thereto.

In one embodiment of the present invention, the organic solvent may include, but is not limited to, a volatile organic solvent in consideration of the ease of removal of the organic solvent after the organic solvent treatment process.

In one embodiment of the present invention, the organic solvent used in the organic solvent treatment step may include about 50 parts by weight to about 200 parts by weight, about 50 parts by weight to about 150 parts by weight based on 100 parts by weight of the 1,2- Or from about 50 parts by weight to about 100 parts by weight, and the water may be used in an amount of about 50 parts by weight to about 100 parts by weight, about 50 parts by weight to about 90 parts by weight based on 100 parts by weight of the 1,2- , From about 50 parts by weight to about 80 parts by weight, from about 50 parts by weight to about 70 parts by weight, or from about 50 parts by weight to 60 parts by weight.

In one embodiment of the invention, the clay in the second treatment step may be one comprising silica-based, alumina-based, or aluminosilicate-based clay.

In one embodiment of the invention, the clay in the second treatment step may comprise one selected from the group consisting of common clay, activated clay, and combinations thereof. The general clay refers to clay present in nature, and the active clay means that the clay is activated with an acid.

In one embodiment of the invention, in the second treatment step, the clay may act as a catalyst for decomposition or conversion of the impurities contained in the 1,2-alkanediol; Or an adsorbent of an impurity contained in the 1,2-alkanediol. Activated carbon can generally be used for the adsorption of impurities, but activated carbon is used for adsorption of relatively nonpolar materials, whereas whitewater differs in that it is effective for adsorption of polar substances. Particularly, clay has a function as a catalyst as well as an adsorbing ability. Particularly, the clay is converted into a substance having alkene or carbonyl group known as odor impurities of 1,2-alkanediol, for example, aldehyde, Making it easier to remove in subsequent processes.

In one embodiment of the present invention, the clay in the second treatment step may be used in an amount of about 0.5 parts by weight to about 10.0 parts by weight based on 100 parts by weight of the 1,2-alkanediol. For example, the clay may be present in an amount of from about 0.5 parts to about 10.0 parts, from about 0.5 parts to about 9.5 parts, from about 0.5 parts to about 9.0 parts, from about 0.5 parts to about 9.0 parts, From about 0.5 parts to about 6.5 parts by weight, from about 0.5 parts by weight to about 6.5 parts by weight, from about 0.5 parts by weight to about 8.5 parts by weight, from about 0.5 to about 8.0 parts by weight, from about 0.5 to about 7.5 parts by weight, from about 0.5 to about 7.0 parts by weight, About 0.5 parts to about 5.0 parts, about 0.5 parts to about 4.5 parts, about 0.5 parts to about 4.0 parts, about 0.5 parts to about 6.0 parts, about 0.5 parts to about 5.5 parts, about 0.5 parts to about 5.0 parts, About 0.5 parts to about 2.5 parts, about 0.5 parts to about 2.0 parts, about 0.5 parts to about 1.5 parts, about 0.5 parts to about 3.5 parts, about 0.5 parts to about 3.0 parts, about 0.5 parts to about 3.0 parts, From about 0.5 parts by weight to about 1.0 part by weight, from about 1.0 part by weight to about 10.0 parts by weight, from about 1.0 part by weight to about 9.5 About 1.0 part to about 9.0 parts by weight, about 1.0 to about 8.5 parts by weight, about 1.0 to about 8.0 parts by weight, about 1.0 to about 7.5 parts by weight, about 1.0 to about 7.0 parts by weight About 1.0 part by weight to about 4.5 parts by weight, about 1.0 part by weight to about 4.5 parts by weight, about 1.0 to about 4.5 parts by weight, about 1.0 to about 6.0 parts by weight, about 1.0 to about 5.5 parts by weight, about 1.0 to about 5.0 parts by weight, About 1.0 to about 3.5 parts by weight, about 1.0 to about 2.5 parts by weight, or about 1.0 to about 2.0 parts by weight, May be used in parts by weight. In one embodiment of the present invention, when the clay is used in an amount of less than about 0.5 part by weight based on 100 parts by weight of the 1,2-alkane diol, the deodorizing effect may not be sufficiently exhibited, but the present invention is not limited thereto.

In one embodiment of the present application, when the first processing step includes a plurality of the unit processes, between the unit processes; Alternatively, when the first processing step and the second processing step are performed in sequence, the method may further include removing water between the first processing step and the second processing step, but the present invention is not limited thereto .

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are given for the purpose of helping understanding of the present invention, but the present invention is not limited to the following Examples.

[ Example ]

Example  One

100 g of 1,2-hexanediol with severe odor, 0.5 g of NaBH ₄ , and 100 g of water were placed in a condenser-equipped flask and the pH was adjusted to 11 with aqueous sodium hydroxide solution. The mixture was stirred at 50 DEG C for 1 hour and neutralized with a dilute hydrochloric acid solution. Thereafter, 5 g of activated carbon was added to the reaction solution, and the mixture was heated to 80 DEG C, stirred for 1 hour, cooled to room temperature, and filtered. 100 mL of n-hexane was added to the filtrate, and the mixture was stirred at room temperature for 1 hour. The inner solution was transferred to a separatory funnel and allowed to stand for 1 hour to form an upper layer (normal hexane layer) and a lower layer Water layer). The lower layer was put in a distillation apparatus and heated while slowly evacuating the vacuum while heating. 95 g of water was distilled off, and then 1,2-hexanediol was distilled off under a reduced pressure of 10 mmHg at a temperature of 100 to 120 ° C. 3 g of the active white clay was added to 1,2-hexanediol from which water had been removed by distillation, and the mixture was stirred at an internal temperature of 50 ° C for 1 hour. When the active white clay was removed by filtration, 83.6 g of 1,2-hexanediol was obtained.

Comparative Example  One

The operation was carried out in the same manner as in Example 1 except that 1,2-hexanediol was distilled and recovered. Thereafter, no active white clay was treated, and 85.0 g of 1,2-hexanediol was obtained.

Example  2

100 g of 1,2-hexanediol, 0.5 g of NaBH4, and 100 g of water, which had severe odor, were placed in a condenser-equipped flask, the pH was adjusted to 11 with sodium hydroxide, and the mixture was stirred at 50 ° C for 1 hour. Solution. Thereafter, 100 mL of n-hexane was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour to transfer the inner solution to a separatory funnel. The mixture was allowed to stand for 1 hour to form an upper layer (normal hexane layer) and a lower layer Water layer). The lower layer was placed in a distillation apparatus and heated while slowly evacuating while evacuating. 97 g of water was distilled off and 1,2-hexanediol was distilled off under a reduced pressure of 10 mmHg at a temperature of 100 to 120 ° C. 3 g of the active white clay was added to 1,2-hexanediol which had been distilled and the water was removed, stirred at an internal temperature of 50 ° C for 1 hour, filtered to remove the active white clay, and 85.4 g of 1,2- .

Comparative Example  2

The same procedure as in Example 2 was carried out except that 1,2-hexanediol was distilled and recovered, and then an activated clay soil treatment was not carried out, and 86.2 g of 1,2-hexanediol was obtained.

Example  3

100 g of 1,2-hexanediol, 0.5 g of NaBH ₄ and 100 g of water were added to a condenser-equipped flask, the pH was adjusted to 11 with sodium hydroxide, and the mixture was stirred at 50 ° C for 1 hour. Solution. Thereafter, 5 g of activated carbon was added to the reaction solution, and the mixture was heated to 80 캜 and stirred for 1 hour, cooled to room temperature, and filtered. The filtrate was put in a distillation apparatus and heated while slowly evacuating it with heating to distill 95 g of water. Then 1,2-hexanediol was distilled off under a reduced pressure of 10 mmHg at a temperature of 100 to 120 ° C. 3-g of active white clay was added to 1,2-hexanediol which had been distilled to remove moisture, stirred at an internal temperature of 50 ° C for 1 hour, filtered to remove the active white clay, and 84.1 g of 1,2- .

Comparative Example  3

The same procedure as in Example 3 was carried out except that 1,2-hexanediol was distilled and recovered, and thereafter, no active white clay was treated, and 85.5 g of 1,2-hexanediol was obtained.

Example  4

100 g of 1,2-hexanediol with severe odor, 5 g of activated carbon and 100 g of water were placed in a flask equipped with a condenser, heated to 80 DEG C, stirred for 1 hour, cooled to room temperature and filtered. To the filtrate was added 100 mL of n-hexane and the mixture was stirred at room temperature for 1 hour. The inner solution was transferred to a separatory funnel and allowed to stand for 1 hour to obtain an upper layer (normal hexane layer) and a lower layer (a water layer containing 1,2- ). The lower layer was put in a distillation apparatus and heated while slowly evacuating the vacuum while heating. 95 g of water was distilled off, and then 1,2-hexanediol was distilled off under a reduced pressure of 10 mmHg at a temperature of 100 to 120 ° C. 3-g of active white clay was added to 1,2-hexanediol from which water had been removed by distillation, stirred at an internal temperature of 50 ° C for 1 hour, and filtered to remove active clay to obtain 83.9 g of 1,2-hexanediol.

Comparative Example  4

The operation was carried out in the same manner as in Example 4 except that 1,2-hexanediol was distilled and recovered, and thereafter, no active white clay was treated, and 86.7 g of 1,2-hexanediol was obtained.

Example  5

100 g of 1,2-hexanediol with severe odor, 5 g of activated carbon and 3 g of active white clay were added, and the mixture was heated to 80 DEG C, stirred for 1 hour, cooled to room temperature and filtered. 82.8 g of 1,2- .

Comparative Example  5

100 g of 1,2-hexanediol with severe odor and 5 g of activated carbon were charged and heated to 80 DEG C, stirred for 1 hour, cooled to room temperature and filtered to obtain 83.3 g of 1,2-hexanediol.

Example  6

 To 100 g of 1,2-hexanediol with severe odor, 100 g of water and 100 mL of n-hexane were added. The mixture was stirred at room temperature for 1 hour, the internal solution was transferred to a separatory funnel, and the mixture was allowed to stand for 1 hour, ) And a lower layer (a water layer containing 1,2-hexanediol). The lower layer was placed in a distillation apparatus and heated while slowly evacuating the vacuum while heating. 98 g of water was distilled off, and then 1,2-hexanediol was distilled off under a reduced pressure of 10 mmHg at a temperature of 100 to 120 ° C. 3 g of active white clay was added to 1,2-hexanediol from which water had been removed by distillation, stirred at an internal temperature of 50 ° C for 1 hour, and filtered to remove active clay to obtain 88.8 g of 1,2-hexanediol.

Comparative Example  6

The operation was carried out in the same manner as in Example 6 except that 1,2-hexanediol was distilled and recovered. Thereafter, an active white clay was not treated, and 89.6 g of 1,2-hexanediol was obtained.

Example  7

100 g of 1,2-hexanediol with severe odor, 0.5 g of NaBH ₄ , and 100 g of water were placed in a condenser-equipped flask and the pH was adjusted to 11 with aqueous sodium hydroxide solution. After stirring at 50 DEG C for 1 hour, the solution was neutralized with a dilute hydrochloric acid solution. Then, 100 g of water and 100 mL of n-hexane were added, and the mixture was stirred at room temperature for 1 hour. The inner solution was transferred to a separatory funnel, and the mixture was allowed to stand for 1 hour to form an upper layer (normal hexane layer) Containing water layer). The lower layer was placed in a distillation apparatus and heated while slowly evacuating the vacuum while heating. 98 g of water was distilled off, and 1,2-hexanediol was distilled off under a reduced pressure of 10 mmHg at a temperature of 100 to 120 ° C. 5 g of activated carbon and 3 g of active white clay were added to 1,2-hexanediol in which water was removed by distillation, and the mixture was stirred at an internal temperature of 60 ° C for 1 hour and filtered to remove activated carbon and activated clay. 82.8 g of hexanediol was obtained.

Example  8

100 g of 1,2-hexanediol with severe odor and 3 g of active white clay were placed in a condenser-equipped flask and stirred for 2 hours while heating to 100 DEG C in a weak vacuum. After cooling, 5 g of activated carbon and 100 g of water were added and the mixture was heated to 80 DEG C and stirred for 1 hour, cooled to room temperature and filtered. To the filtrate, 100 mL of n-hexane was added and the mixture was stirred at room temperature for 1 hour. The inner solution was transferred to a separatory funnel and allowed to stand for 1 hour to form an upper layer (normal hexane layer) and a lower layer (containing 1,2-hexanediol Water layer). The lower layer was placed in a distillation apparatus and heated while slowly evacuating the vacuum while heating to distill off about 95 g of water. The 1,2-hexanediol was then distilled and recovered under a reduced pressure of 10 mmHg at a temperature of 100 ° C to 120 ° C to obtain 1,2- 83.0 g of hexanediol was obtained.

The deodorized 1,2- Hexanediol  Evaluation of deodorizing effect

A total of 15 samples, such as 1,2-hexanediol and untreated 1,2-hexanediol from Examples 1 to 8 and Comparative Examples 1 to 6, were evaluated by five external panels. For the evaluation, 50 mL of warm water at 50 ° C was added to a 100 mL beaker, and 1 drop of each sample was dropped on the beaker with a syringe and immediately smelled.

 The evaluation results are shown in the following Table 1, and the score of each panel is expressed as an integer from 0 to 5, and when a different score is given, a unit of 0.5 is inserted between them. The evaluation score for non-deodorized 1,2-hexanediol is 4, and the evaluation criteria are as follows:

<Evaluation scale and scoring>

0 point: There is no odor.

1 point: There is a very weak odor.

2 points: I am weak but I can detect it immediately.

3 points: There is almost no objection even if it continues to carry out with usual odor.

4 points: It is difficult to keep going because it is strong.

Score 5: Strong and stimulating, so stop acting as soon as you take it.

For reference, the respective stages of the deodorization process in the following [Table 1] are expressed as follows:

a1: Reducing agent treatment process

a2: Activated carbon treatment process

a3: Organic solvent treatment process

b: Clay treatment process

 [Table 1]

It was confirmed that the deodorizing effect of the example accompanied with the clay treatment was better by about 0.5 to 1 than that of the comparative example without the clay treatment under the same conditions, It was confirmed that the deodorizing effect of hexanediol was improved.

The foregoing description of the disclosure is exemplary, It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present invention .

Claims (12)

(a) a first treatment step of a 1,2-alkanediol, including a reducing agent treatment process, an activated carbon treatment process, and an organic solvent treatment process; And
(b) Second treatment step of 1,2-alkanediol using clay
A method for deodorizing a 1,2-alkanediol,
In the second treatment step, the clay acts as a catalyst for decomposing or converting impurities contained in the 1,2-alkanediol,
Wherein the 1,2-alkanediol has from 5 to 10 carbon atoms.
A method for deodorization of 1,2-alkanediol.
delete The method according to claim 1,
Wherein the 1,2-alkanediol comprises 1,2-hexanediol.
The method according to claim 1,
Wherein the first treatment step and the second treatment step are carried out simultaneously or sequentially.
The method according to claim 1,
And performing the second treatment step between the unit processes of the first treatment step.
The method according to claim 1,
The reducing agent treatment step may include adding a reducing agent selected from the group consisting of a metal salt of borohydride anion, a metal salt of dithionite anion, and a combination thereof to the 1,2-alkanediol, Reducing impurities contained therein;
Wherein the activated carbon treatment step comprises adding activated carbon to the 1,2-alkanediol to adsorb impurities contained in the 1,2-alkanediol on the activated carbon, and then filtering the activated carbon;
Wherein the organic solvent treatment step comprises adding an organic solvent and water to the 1,2-alkanediol to extract the impurities contained in the 1,2-alkanediol by the organic solvent. - deodorization method of alkanediol.
The method according to claim 1,
Wherein the activated carbon in the activated carbon treatment step comprises a carbonaceous adsorbent.
The method according to claim 1,
Wherein the clay in the second treatment step comprises a silica-based, alumina-based, or aluminosilicate-based one.
The method according to claim 1,
Wherein said clay in said second treatment step comprises one selected from the group consisting of common clay, activated clay, and combinations thereof.
delete The method according to claim 1,
Wherein the white clay is used in an amount of 0.5 to 10.0 parts by weight based on 100 parts by weight of the 1,2-alkanediol in the second treatment step.
The method according to claim 1,
When the first processing step includes a plurality of the unit processes, between the unit processes; Or removing the water between the first treatment step and the second treatment step when the first treatment step and the second treatment step are performed in sequence, the deodorization of the 1,2-alkanediol Way.

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