KR101981994B1 - Process for purifying of acetone - Google Patents

Abstract

The present invention relates to a method for purifying recovered acetone containing chlorine, chlorine ions, or chlorine compounds as a chlorine-based impurity, comprising the steps of charging triethylamine (TEA), which is highly reactive with chlorine or chloride ions, Producing a hydrochloride salt; And flocculating the triethylamine hydrochloride by adding the flocculant composition to a process for purifying acetone.
The method of purifying acetone of the present invention can purify recovered acetone containing chlorine-based impurities into high purity acetone, and purify acetone to high purity by a simple process, thereby reducing purification time and processing cost.

Description

{PROCESS FOR PURIFICATION OF ACETONE}

The present invention relates to a method for purifying acetone, and more particularly, to a method for purifying acetone for the purpose of obtaining a high purity acetone from recovered acetone containing impurities such as residual chlorine.

In general, high purity acetone can be used as a mobile phase solvent for the analysis of the mixture in high pressure liquid chromatography. Since it has a very strong polarity, it easily dissolves organic matter and dissolves well and is generally used. Since the UV detector is used as a detector, Should be very high. In addition, acetone, which is used as a cleaning agent for cleaning semiconductors and LCDs in semiconductor and liquid crystal display (LCD) industries, is used in various kinds of fine electronic equipment, and it is required to clean foreign substances contained in the surface, Purity must be very high. Therefore, the analysis results of high purity acetone suitable for this purpose show that organic impurities analyzed by ultraviolet spectroscopy have organic impurities having a maximum of 1.0 at a wavelength of 330 nm to 400 nm and a maximum of 1.0 at a wavelength of 330 nm and a maximum of 0.01 at a wavelength of 350 nm and 400 nm And it is an inorganic metal impurity. By ICP-MS analysis, Ca 10 ppb or less, Fe 20 ppb or less, K 10 ppb or less, Mg 20 ppb or less, Mn 10 ppb or less, Co 10 ppb or less, Cd 25 ppb or less, Sn 20 ppb or less, Cu 10 ppb or less and Al 50 ppb or less, and the concentration of water should be 0.3% or less by the moisture measurement method by Karl-fischer titration.

As a known purification method for purifying acetone at high purity, US Pat. No. 5,897,750 (1999) discloses a method for separating acetone from a mixture of isopropanol and water having a boiling point similar to acetone An extractive distillation method was used. Distillation was performed by addition of 1-nitropropane, 3-carene, dimethylsulfoxide and 3-pentanone as extractants to remove acetone by extractive distillation Isopropyl alcohol and water, and then separating the acetone from the high-boiling-point extractant again by distillation. This method is advantageous when the impurities of a specific component are composed of components that can be easily separated by extractive distillation, but is not applicable when the undesirable organic component is mixed with acetone as in the present invention. U.S. Patent No. 5,788,818 (1998) describes a process for separating cumene, water, aldehyde and methyl alcohol impurities from the process for the production of phenol and acetone. Respectively. Two consecutive distillation columns and a decanter were applied. In the first distillation column, acetone, water and cumene were separated from the distillation column into which about 2% aqueous sodium hydroxide solution was injected, and the second distillation column The mixture containing triethylene glycol, water, cumene and acetone was sent to the third layer separator at the top of the column to separate the acetone from the top of the column by extractive distillation using triethyleneglycol in the distillation column. and separating the water forming the azeotropic mixture and the cumene into acetone layers.

U.S. Patent No. 6,303,826 B1 (2001) describes an oxidation reaction using a heterogeneous catalyst to remove methyl alcohol and acetaldehyde, which are oxidative impurities contained in acetone, and to convert these oxides into liquid or vapor phase It can be separated. That is, by carrying palladium (Pd) or the like, which is a noble metal catalyst, on a carrier and injecting air and the like under high temperature and high pressure conditions, the oxidizing substance can be removed by selective oxidation reaction in acetone, There is a problem in that acetone is separated again from such an oxide after the oxidation reaction.

The object of the present invention is to provide a method for purifying recovered acetone containing chlorine-based impurities into high purity acetone.

Another object to be solved by the present invention is to provide a method for purifying acetone which can purify acetone to a high purity by a simple process and reduce purification time and processing cost.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention is a method for purifying recovered acetone comprising chlorine, chlorine ion, or chlorine compound as a chlorine-based impurity, comprising the steps of adding triethylamine (TEA), which is highly reactive with chlorine or chloride ions, To give triethylamine hydrochloride; And flocculating the triethylamine hydrochloride by adding the flocculant composition to a process for purifying acetone.

Another aspect of the present invention is a method for purifying recovered acetone comprising chlorine, chlorine ion, or chlorine compound as a chlorine-based impurity, wherein triethylamine (TEA) having high reactivity with chlorine or chloride ion is added to recovered acetone To form triethylamine hydrochloride; Adsorbing a chlorine compound by injecting zinc oxide (ZnO); And coagulating the zinc oxide to which the triethylamine hydrochloride or the chlorine compound adsorbed by charging the flocculating composition.

The zinc oxide (ZnO) may have a specific surface area of 20 m ² / g to 100 m ² / g.

Also, the flocculant composition is a mixture of an aluminum flocculant and an iron chloride flocculant, and the aluminum flocculant is aluminum sulfate or polychlorinated aluminum, and the iron salt flocculant is selected from the group consisting of ferrous chloride, ferric chloride, 1 iron, ferric sulfate, and polysulfide iron.

Also, the flocculant composition may be an aluminum flocculant and an iron salt flocculant mixed at a weight ratio of 1: 1 to 5: 1.

Also, the method for purifying acetone may include: 0.1 to 3 parts by weight of the triethylamine (TEA) to 100 parts by weight of recovered acetone containing 20 to 100 ppm of chlorine-based impurities; 1 to 5 parts by weight of zinc oxide (ZnO); And 3 to 7 parts by weight of the flocculant composition may be added

The method of purifying acetone of the present invention can purify recovered acetone containing chlorine-based impurities into high purity acetone, and purify acetone to high purity by a simple process, thereby reducing purification time and processing cost.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

The term " recovered acetone " in the present invention means acetone which has undergone ordinary refining processes such as conventional fractional distillation, but which requires high purification, including impurities such as organic impurities and inorganic impurities.

"Chlorinated impurities" are oxychlorination (oxychlorination) desorbed chlorine in the chlorine compound or the decomposition process generated by the process (CI) or chloride ion (CI ^-) are performed for the regeneration of catalytic reforming catalysts used in the refining process in the present invention And the like.

The method for purifying acetone according to an embodiment of the present invention includes the steps of: (S10) generating triethylamine hydrochloride by adding triethylamine (TEA) having high reactivity with chlorine or chloride ion to recover acetone; An adsorption step (S20) of adsorbing the chlorine compound by injecting zinc oxide (ZnO); And a flocculating step (S30) for flocculating the zinc oxide adsorbed by the triethylamine hydrochloride or the chlorine compound by injecting the flocculating composition.

In step (S10), triethylamine (TEA) is used to produce triethylamine hydrochloride, which is an insoluble chlorine compound, in combination with chlorine or chloride ions contained in the recovered acetone. The specific reaction mechanism by which triethylamine hydrochloride is formed can be illustrated by the following chemical reaction formula 1.

[Chemical reaction formula 1]

The triethylamine hydrochloride formed in step (S10) has a high solubility in an aqueous solution, but is present as an insoluble chlorine compound in acetone, so that chlorine or chloride ion can be selectively captured and removed.

In the adsorption step (S20), zinc oxide (ZnO) is injected to adsorb and remove a chlorine compound contained as an impurity in the recovered acetone.

The zinc oxide (ZnO) is not particularly limited, but it has a specific surface area (bet) of 20 to 100 m ² / g, preferably 3 to 80 m ² / g, more preferably 40 to 100 m ² / 70 m ² / g can be used. Here, the specific surface area means the average specific surface area obtained based on the adsorption isotherm of BET (Brunauer, Emmett, Teller).

The zinc oxide can be obtained by baking zinc hydroxide, zinc carbonate, basic zinc carbonate or the like at 350 to 400 ° C. The zinc hydroxide, zinc carbonate, basic zinc carbonate and the like are preferably crystallized in an aqueous solution. For example, zinc carbonate precipitated in an aqueous ammonium zinc carbonate solution and zinc hydroxide obtained by a uniform precipitation method can be preferably used.

The reaction mechanism by which zinc oxide adsorbs a chlorine compound in the present invention can be illustrated by the following chemical reaction formula 2.

[Chemical reaction formula 2]

The flocculation step (S30) is a step of injecting the flocculant composition to flocculate the zinc oxide particles adsorbed by the triethylamine hydrochloride or the chlorine compound produced in the step (S10), thereby enlarging the flocculated zinc oxide particles.

In one embodiment, the flocculant composition may be a mixture of an aluminum flocculant and an iron chloride flocculant.

Specifically, the aluminum-based flocculant may comprise aluminum sulfate or polychlorinated aluminum and the iron salt-based flocculant may be selected from the group consisting of ferrous chloride, ferric chloride, ferric chloride, ferrous sulfate, ferric sulfate, and poly And sulfuric acid iron.

Also, the flocculant composition may be an aluminum flocculant and an iron salt flocculant mixed at a weight ratio of 1: 1 to 5: 1. It is possible to exhibit excellent flocculation speed and flocculation effect in the above range.

In step (S30), the chlorine compound particles agglomerated by the agglomerate composition can be easily removed because they grow into gravity-settable particles of 25 to 40 mu m.

The chlorine compound particles precipitated by the gravity precipitation can be removed by a reduced pressure, a pressure filtration method, or a natural sedimentation method.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Example

Example  One

3 parts by weight of triethylamine (TEA) was added to 100 parts by weight of recovered acetone containing a polychlorinated biphenyl (PCBs) as a chlorine compound at a concentration of 20 ppm to produce triethylamine hydrochloride in the recovered acetone. 2 parts by weight of aluminum sulfate as an aggregating agent and 1 part by weight of polychloride were added to the recovered acetone in which the triethylamine hydrochloride was formed, and then left to stand for about 1 hour so that the resulting aggregates naturally precipitated by gravity. The precipitated acetone was filtered using a filter to obtain acetone from which the chlorine compound had been removed.

Example  2

3 parts by weight of triethylamine (TEA) was added to 100 parts by weight of recovered acetone containing a polychlorinated biphenyl (PCBs) as a chlorine compound at a concentration of 20 ppm to produce triethylamine hydrochloride in the recovered acetone. Thereafter, 3 parts by weight of zinc oxide (ZnO) having a specific surface area of 45 m ² / g was added to adsorb the chlorine compound contained in the recovered acetone, and then triethylamine hydrochloride and the number of times the zinc oxide particles adsorbed with the chlorine compound 3 parts by weight of aluminum sulfate as an aggregating agent and 1.5 parts by weight of poly-iron chloride were added to acetone, and the resulting aggregates were allowed to stand for about one hour to precipitate naturally by gravity. The precipitated acetone was filtered using a filter to obtain acetone from which the chlorine compound had been removed.

Comparative Example  One

3 parts by weight of triethylamine (TEA) was added to 100 parts by weight of recovered acetone containing a polychlorinated biphenyl (PCBs) as a chlorine compound at a concentration of 20 ppm to produce triethylamine hydrochloride in the recovered acetone. 2 parts by weight of aluminum sulfate as an aggregating agent and 4 parts by weight of poly (iron chloride) were added to the recovered acetone in which triethylamine hydrochloride was formed, and then left to stand for about 1 hour so that the resulting aggregates naturally precipitated by gravity. The precipitated acetone was filtered using a filter to obtain acetone from which the chlorine compound had been removed.

How to measure physical properties

1. Determination of the concentration of residual chlorine or chloride ion in the oil from which chlorine or chlorine ions have been removed

In order to examine the effect of the removing method according to the present invention, the residual chlorine concentration of the chlorine-free oil was measured in Example 1-2 and Comparative Example 1. In order to determine the residual chlorine concentration, ion chromatography (ICS-3000, manufactured by Dionex) was used as an analyzing machine.

Initial chlorine concentration measurement

To determine the concentration of the initial chlorine or chloride ion in the recovered acetone in Example 1-2 and Comparative Example 1, the recovered acetone from which triethylamine hydrochloride was formed in Step 1 of each Example was washed with 0.05 M sodium hydroxide solution Recovery Chlorine was extracted from acetone and its concentration was determined. The results of washing the recovered acetone with sodium hydroxide solution can be judged by the initial chlorine concentration contained in the recovered acetone because the chlorine desorbed by the electron beam irradiation binds to the total amount of triethylamine and is present as insoluble particles in the oil , And when it is extracted with water such as an aqueous solution of sodium hydroxide, the whole amount can be extracted from the oil due to high solubility of triethylamine hydrochloride in water.

As a result of measurement, the initial chlorine concentration of the recovered acetone containing 20 ppm of polychlorinated biphenyl of Example 1 - 2 and Comparative Example 1 was measured to be 39 ppm.

Determination of chlorine concentration in acetone with chlorine compound removed

In Example 1-2 and Comparative Example 1, the supernatant of the recovered acetone in which the aggregates precipitated was taken to determine the residual chlorine concentration.

The residual chlorine concentration of Example 1 was 0.310 ppm, the residual chlorine concentration of Example 2 was 0.234 ppm, and the residual chlorine concentration of Comparative Example 1 was 4.254 ppm after spontaneous precipitation of the agglomerates.

From the experimental results, it can be seen that the acetone refining method of the present invention can purify recovered acetone containing chlorine-based impurities into high purity acetone, and purify acetone to a high purity by a simple process, thereby reducing purification time and processing cost .

Claims (6)

delete A method for purifying recovered acetone comprising chlorine, chlorine ions, or a chlorine compound as a chlorine-based impurity,
Adding triethylamine (TEA), which is highly reactive with chlorine or chloride ions, to the recovered acetone to produce triethylamine hydrochloride;
Adsorbing a chlorine compound by injecting zinc oxide (ZnO); And
And agglomerating the zinc oxide adsorbed with the triethylamine hydrochloride or the chlorine compound by adding the aggregating composition.
3. The method of claim 2,
Wherein the zinc oxide (ZnO) has a specific surface area of 20 m ² / g to 100 m ² / g.
3. The method of claim 2,
The flocculant composition is a mixture of an aluminum flocculant and an iron salt flocculant,
The aluminum-based flocculant is aluminum sulfate or aluminum chloride,
The iron salt type flocculant includes at least one selected from the group consisting of ferrous chloride, ferric chloride, ferric chloride, ferrous sulfate, ferric sulfate, and polysulfate. .
The method of claim 3,
Wherein the flocculant composition is a mixture of an aluminum flocculant and an iron chloride flocculant at a weight ratio of 1: 1 to 5: 1.
3. The method of claim 2,
Based on 100 parts by weight of recovered acetone containing 20 to 100 ppm of chlorine-based impurities,
0.1 to 3 parts by weight of triethylamine (TEA);
1 to 5 parts by weight of zinc oxide (ZnO); And
Wherein 3 to 7 parts by weight of the flocculant composition is added.