KR20130089050A - Process for purification of 2,6-dimethylphenol by circulating azeotropic distillation - Google Patents

Process for purification of 2,6-dimethylphenol by circulating azeotropic distillation Download PDF

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KR20130089050A
KR20130089050A KR1020120010397A KR20120010397A KR20130089050A KR 20130089050 A KR20130089050 A KR 20130089050A KR 1020120010397 A KR1020120010397 A KR 1020120010397A KR 20120010397 A KR20120010397 A KR 20120010397A KR 20130089050 A KR20130089050 A KR 20130089050A
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dimethylphenol
distillation
azeotrope
hydrocarbon
azeotropic
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KR101863104B1 (en
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김정곤
이종화
신철
송재욱
이호창
문민식
김수한
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애경유화주식회사
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C07C37/78—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation by azeotropic distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
    • B01D3/36—Azeotropic distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/88—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
    • C07C39/06—Alkylated phenols
    • C07C39/07—Alkylated phenols containing only methyl groups, e.g. cresols, xylenols

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

PURPOSE: A refinement process of 2,6-dimethyl phenol is provided. The refinement process can completely inhibit the loss of 2,6-dimethyl phenol, while cutting the usage amount of an azeotrope former in half and minimizing the energy consumption, in order to obtain high-yield 2,6-dimethyl phenol. CONSTITUTION: A refinement process of 2,6-dimethyl phenol comprises the steps of: refining 2,6-dimethyl phenols by azeotropic evaporation separating 2,6-dimethyl phenols from a mixture of crude 2,6-dimethyl phenol having o-cresol while using a hydrocarbon azeotrope former with 155-170°C of boiling point, and condensing the azeotrope mixture by using a condenser (40), and collecting the condensed azeotrope mixture in a distillation bath (40) full of water and methanol and circulating the azeotrope former from a segregation bath to the distillation bath to discharge o-cresol. The weight ratio of methanol and water is 1:1-2:1.

Description

순환식 공비증류를 이용한 2,6-디메틸페놀의 정제방법{Process for purification of 2,6-dimethylphenol by circulating azeotropic distillation}Process for purification of 2,6-dimethylphenol by circulating azeotropic distillation

본 발명은 o-크레졸을 포함하는 조 2,6-디메틸페놀의 혼합물로부터 공비제를 사용하여 공비증류를 통해 2,6-디메틸페놀을 정제하는 방법으로서, 상기 공비제로 끓는점 155 내지 170℃의 탄화수소 공비제를 사용하고, 공비혼합물은 응축기에 의해 응축되고 응축된 공비혼합물은 메탄올과 물이 채워진 분리조에 수집되어 공비제가 분리조로부터 층분리 후 증류조로 순환되고, o-크레졸은 외부로 배출되는 과정으로 이루어진 2,6-디메틸페놀을 정제하는 방법에 관한 것이다.
The present invention is a method for purifying 2,6-dimethylphenol through azeotropic distillation from a mixture of crude 2,6-dimethylphenol containing o-cresol by azeotropic distillation, wherein the hydrocarbon has a boiling point of 155 to 170 ° C. The azeotrope is used, and the azeotrope is condensed by the condenser and the condensed azeotrope is collected in a separation tank filled with methanol and water so that the azeotrope is circulated from the separation tank to the distillation tank and the o-cresol is discharged to the outside. It relates to a method for purifying 2,6-dimethylphenol consisting of.

크레졸 아이소머의 혼합물, 크레졸과 2,6-디메틸페놀의 혼합물, 및 이들을 포함한 알킬페놀의 혼합물을 분리하기 위하여 증류, 결정화, 추출, 흡착 또는 이들의 조합 등 다양한 방법이 제안되었다.Various methods have been proposed, such as distillation, crystallization, extraction, adsorption, or a combination thereof, to separate a mixture of cresol isomers, a mixture of cresol and 2,6-dimethylphenol, and a mixture of alkylphenols including them.

예시된 방법 중, 결정화, 추출 및 흡착은 분리과정이 복합하고, 분리된 크레졸의 효율이 낮아 상업적으로 효과적이지 않다. o-크레졸, m-크레졸 및 p-크레졸의 혼합물과 같이 유사비점을 가지는 적어도 두 개의 알킬페놀의 혼합물 또는 페놀, o-크레졸, p-크레졸, 2,4-디메틸페놀 및 2,6-디메틸페놀을 포함하는 페놀 또는 크레졸의 메틸화 생성물의 혼합물로부터 끓는점이 높은 알킬페놀과 끓는점이 낮은 알킬페놀을 분리하는데 있어서, 다수의 이론단수를 갖는 정류탑이 요구되고, 증류는 높은 환류비에서 수행되어야 한다. 게다가, 이러한 단점 이외에도 이러한 분리 과정은 필요로 한 열의 양 및 증류 속도에 대하여 단점도 가지고 있다.
In the illustrated method, crystallization, extraction and adsorption are not commercially effective due to the complex separation process and low efficiency of the separated cresol. mixtures of at least two alkylphenols with similar boiling points or mixtures of phenols, o-cresols, p-cresols, 2,4-dimethylphenols and 2,6-dimethylphenols, such as mixtures of o-cresols, m-cresols and p-cresols In order to separate a high boiling point alkylphenol and a low boiling point alkylphenol from a mixture of a methylation product of phenol or cresol containing a distillation column, a distillation must be performed at a high reflux ratio. In addition to these disadvantages, this separation process also has disadvantages with respect to the amount of heat required and the rate of distillation.

본 발명의 목적은 o-크레졸을 포함하는 조 2,6-디메틸페놀의 혼합물로부터 공비제로 끓는점이 155 내지 170℃의 탄화수소 공비제를 사용하고, 공비혼합물은 응축기에 의해 응축되고 응축된 공비혼합물은 메탄올과 물이 채워진 분리조에 수집되어 공비제가 분리조로부터 증류조로 순환되고, o-크레졸은 외부로 배출되는 과정으로 이루어진 2,6-디메틸페놀을 정제하는 방법을 제공하는 것이다.
It is an object of the invention to use a hydrocarbon azeotropic boiling point of 155 to 170 ° C. from a mixture of crude 2,6-dimethylphenol containing o-cresol, the azeotrope is condensed by a condenser and the azeotropic mixture Collected in a separation tank filled with methanol and water, the azeotrope is circulated from the separation tank to the distillation tank, o-cresol is to provide a method for purifying the 2,6-dimethyl phenol consisting of the process is discharged to the outside.

본 발명은o-크레졸을 포함하는 조 2,6-디메틸페놀의 혼합물로부터 공비제를 사용하여 공비증류를 통해 2,6-디메틸페놀을 정제하는 방법으로서, 상기 공비제로 끓는점 155 내지 170℃의 탄화수소 공비제를 사용하고, 공비혼합물은 응축기(40)에 의해 응축되고 응축된 공비혼합물은 메탄올과 물이 채워진 분리조(30)에 수집되어 공비제가 분리조(30)로부터 증류조(10)로 순환되고, o-크레졸은 외부로 배출되는 과정으로 이루어진 2,6-디메틸페놀을 정제하는 방법에 관한 것이다.The present invention is a method for purifying 2,6-dimethylphenol through azeotropic distillation from a mixture of crude 2,6-dimethylphenol containing o-cresol by azeotropic distillation, comprising a hydrocarbon having a boiling point of 155 to 170 ° C. with the azeotropic agent. An azeotrope is used, and the azeotrope is condensed by the condenser 40 and the condensed azeotrope is collected in a separation tank 30 filled with methanol and water so that the azeotrope is circulated from the separation tank 30 to the distillation tank 10. And, o-cresol relates to a method for purifying 2,6-dimethylphenol consisting of a process that is discharged to the outside.

구체적으로 상기 공비혼합물은 증류컬럼(20)의 상부에 연결된 관을 통하여 응축기(40)로 이동하여 응축되어 분리조(30)에 수집되며, 응축된 공비혼합물은 중력에 의해 메탄올과 물의 혼합용매 층 하부까지 연결된 관을 통해 분리조의 하부로 이동하고, 상기 관을 통과한 공비혼합물 중 o-크레졸은 메탄올과 물의 혼합용매에 용해되며 공비제는 메탄올과 물의 혼합용매와는 상 분리되어 정치된다. 메탄올, 물 및 o-크레졸의 혼합용매 층의 수위가 높아지면 상분리된 공비제는 증류조(10)로 순환되고, o-크레졸은 메탄올과 물의 혼합용매에 용해되어 외부로 배출된다.Specifically, the azeotrope is moved to the condenser 40 through a tube connected to the upper portion of the distillation column 20 to condense and collected in the separation tank 30, the condensed azeotrope is a mixed solvent layer of methanol and water by gravity The o-cresol in the azeotrope passed through the tube connected to the bottom and passed through the tube is dissolved in a mixed solvent of methanol and water, and the azeotropic agent is allowed to stand in phase separation from the mixed solvent of methanol and water. When the level of the mixed solvent layer of methanol, water, and o-cresol increases, the phase-separated azeotropic agent is circulated to the distillation tank 10, and the o-cresol is dissolved in the mixed solvent of methanol and water and discharged to the outside.

이하 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명의 분리조(30)는 메탄올과 물이 1:1 ~ 2:1의 중량비로 혼합되어 있으며, 가장 바람직하게는 3:2의 중량비로 혼합되어 있다. In the separation tank 30 of the present invention, methanol and water are mixed at a weight ratio of 1: 1 to 2: 1, and most preferably at a weight ratio of 3: 2.

공비증류된 공비혼합물은 기체상으로 응축기(40)에 도입되어 액상으로 응축되며, 액상으로 응축된 공비혼합물은 메탄올과 물이 혼합되어 있는 분리조(30)로 수집되어 o-크레졸은 메탄올과 물의 혼합용매에 용해되는 반면, 공비제는 메탄올과 물의 혼합용매에 용해되지 않으며, 메탄올, 물 및 o-크레졸의 혼합용액은 아래층으로, 공비제는 위층으로 층분리가 일어난다. 공비제층은 다시 증류조(10)로 재도입되어 조 2,6-디메틸페놀의 공비제로 순환되며, o-크레졸이 용해되어 있는 메탄올과 물의 혼합용매층은 외부로 배출시켜 o-크레졸을 제거한다. 또한, o-크레졸을 외부로 배출시킨 다음, 분리조(30)에 다시 메탄올과 물의 혼합용매를 주입하는 과정을 조 2,6-디메틸페닐 내 o-크레졸이 모두 제거될 때까지 반복적으로 수행하고, 공비제는 최초로 투입된 것 이외에는 추가로 더 투입하지는 않고 분리조(30)로부터 수집된 공비제를 계속적으로 재사용한다.The azeotropic distilled azeotrope is introduced into the condenser 40 in the gas phase and condensed in the liquid phase. The azeotropic mixture condensed in the liquid phase is collected in a separation tank 30 in which methanol and water are mixed. While dissolved in the mixed solvent, the azeotropic agent is not dissolved in the mixed solvent of methanol and water, and the mixed solution of methanol, water and o-cresol is the lower layer, the azeotropic agent is separated into the upper layer. The azeotrope layer is reintroduced into the distillation tank 10 and circulated to the azeotrope of crude 2,6-dimethylphenol, and the mixed solvent layer of methanol and water in which o-cresol is dissolved is discharged to the outside to remove o-cresol. . In addition, the o-cresol was discharged to the outside, and then a process of injecting a mixed solvent of methanol and water again into the separation tank 30 was repeatedly performed until all of the o-cresol in the crude 2,6-dimethylphenyl was removed. In addition, the azeotropic agent is continuously added to the azeotropic agent collected from the separation tank 30 without further addition other than the first azeotropic agent.

본 발명의 탄화수소 공비제는 상압에서 155 내지 170℃의 끓는점을 갖는 탄화수소 화합물 또는 그들의 혼합물로, 고비점의 탄화수소 공비제를 별도의 정제 과정을 거쳐 155 내지 170℃의 끓는점을 가지는 탄화수소 화합물 또는 그들의 혼합물을 분리하여 사용한다. 상기 상업적으로 판매중인 고비점의 탄화수소 공비제는 155 내지 170℃의 끓는점을 갖는 탄화수소 화합물을 30% 이상, 좋게는 60% 이상, 더욱 좋게는 95% 이상 포함하고 있다.Hydrocarbon azeotrope of the present invention is a hydrocarbon compound or a mixture thereof having a boiling point of 155 to 170 ℃ at atmospheric pressure, a hydrocarbon compound or a mixture thereof having a boiling point of 155 to 170 ℃ through a separate purification process of a high boiling point hydrocarbon azeotropic agent Use separately. The commercially available high boiling hydrocarbon azeotrope contains at least 30%, preferably at least 60%, more preferably at least 95% of hydrocarbon compounds having a boiling point of 155 to 170 ° C.

본 발명의 탄화수소 공비제는 조 2,6-디메틸페놀 100 중량부에 대하여 15 내지 50 중량부로 사용되는 것이 바람직하다.The hydrocarbon azeotrope of the present invention is preferably used in an amount of 15 to 50 parts by weight based on 100 parts by weight of crude 2,6-dimethylphenol.

본 발명의 탄화수소 공비제는 o-크레졸과 공비물 또는 공비혼합물을 형성하여 조 2,6-디메틸페놀로부터 o-크레졸을 공비혼합물의 형태로 제거시키는데 효과적이다.The hydrocarbon azeotrope of the present invention is effective in forming an azeotrope or azeotrope with o-cresol to remove o-cresol in the form of an azeotrope from crude 2,6-dimethylphenol.

본 발명에 따른 정제 방법에서 2,6-디메틸페놀은 공비혼합물 형태로 전혀 손실되지 않는다.In the purification process according to the invention 2,6-dimethylphenol is not lost at all in the form of azeotrope.

본 발명의 탄화수소 공비제와 함께 다른 탄화수소 용매를 사용할 수 있으며, 탄화수소 용매는 탄화수소 공비제의 양보다 적게 사용하며, 바람직하게는 공비제의 무게에 비해 50% 미만으로 사용한다. Other hydrocarbon solvents may be used with the hydrocarbon azeotrope of the present invention, the hydrocarbon solvent being used less than the amount of the hydrocarbon azeotrope, preferably less than 50% by weight of the azeotrope.

공비증류는 상압, 저압 또는 고압에서 실시될 수 있으나, 바람직하게는 상압에서 실시한다. Azeotropic distillation may be carried out at atmospheric pressure, low pressure or high pressure, but preferably at atmospheric pressure.

증류는 연속식 또는 회분식으로 실시될 수 있으나, 회분식으로 실시되는 것이 가장 바람직하다.
Distillation may be carried out continuously or batchwise, but is most preferably carried out batchwise.

본 발명에 따른 2,6-디메틸페놀의 정제방법을 사용하면, 기존 공법의 단점인 2,6-디메틸페놀 손실을 완전히 방지함과 동시에 공비제를 순환시켜 재사용함으로서 공비제 사용량을 절반정도로 단축하고, 일반 공비제를 이용한 공비증류에 비해 공정시간을 크게 단축시켜 에너지 소모량을 최소화하여 고순도의 2,6-디메틸페놀을 고수율로 얻을 수 있고 경제성을 더욱 높이는 효과를 기대할 수 있다.
By using the method for purifying 2,6-dimethylphenol according to the present invention, while completely preventing the loss of 2,6-dimethylphenol, which is a disadvantage of the existing method, the azeotropic agent is recycled by circulating and reducing the amount of azeotropic agent to about half. Compared to azeotropic distillation using common azeotropic agents, the process time can be significantly shortened to minimize energy consumption, thereby obtaining high purity 2,6-dimethylphenol in high yield and improving economic efficiency.

도 1 - 본 발명에 따른 2,6-디메틸페놀을 정제하기 위한 실험장치(10:증류조, 20:증류컬럼, 30:분리조, 40:응축기)1-Experimental apparatus for purifying 2,6-dimethylphenol according to the present invention (10: distillation tank, 20: distillation column, 30: separation tank, 40: condenser)

이하에서는, 실시예를 통하여 본 발명을 더욱 상세하게 설명한다. 그러나, 본 발명의 범위가 하기의 실시예로 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to the following examples.

[실시예1][Example 1]

도 1에 도시된 실험장치를 이용하여 공비증류를 실시하였다. o-크레졸2.7%를 함유하는2,6-디메틸페놀 1100g에 제품명 YK-MD40(SK종합화학) 고비점의 탄화수소 공비제를 끓는점 155 ~ 170 ℃ 범위의 혼합물만 분별 증류하여 공비제로서 200g을 가하였다. 상기 혼합물을 증류조(10)에 넣고 30단 증류컬럼(20)을 설치하였으며, 증류 컬럼 상단에 공비제를 순환시키기 위한 증류 보조장치를 설치하였다. 상기 증류 보조장치는 분리조(30)와 응축기(40)로 이루어져 있으며, 응축되어 수집된 공비혼합물이 메탄올과 물의 혼합용매 하단부까지 연결된 관을 중력에 의해 통과하여 상 분리가 되는 과정에서 추출이 되도록 운영되는 장치로, 도 1에 도시되어 있다. 상기 증류 보조장치의 추출용매 영역(300mL부피의 유리로 만들어진 초자)을 분리조(30)라 하고 상기 분리조(30)에는 메탄올과 정제수를 6:4의 무게비로 혼합한 용액을 250g을 충진하였다. 보조 증류장치 상단의 응축기(40)에 사용된 냉각수는 실온의 수돗물을 순환시켰다. 시료의 가열은 110V 히팅멘틀(heating mentle)을 이용하였으며, 입력 전압을60~70V로 조정하여 운전하였다. 증류 시간의 경과에 따라 증류조 내의 시료와 분리조의 시료를 가스크로마토그래피로 분석하였다. 가스크로마토그래피 분석에는 HP-5컬럼을 이용하였으며, 내부표준법을 이용하여 분석하였다. 증류조 시료 분석 결과 o-크레졸의 함량이 0.2%이하인 경우 증류를 종결하였다. 그 결과를 하기 [표1]에 기재하였다.
The azeotropic distillation was performed using the experimental apparatus shown in FIG. 1,100 g of 2,6-dimethylphenol containing 2.7% of o-cresol, and fractionally distill the mixture of boiling point 155 ~ 170 ℃ into hydrocarbon boiling azeotropy with high boiling point product name YK-MD40 (SK General Chemical). It was. The mixture was placed in a distillation tank (10), and a 30-stage distillation column (20) was installed, and a distillation aid for circulating azeotropic agent was installed at the top of the distillation column. The distillation aid consists of a separation tank 30 and a condenser 40, so that the azeotrope mixed with condensation is extracted by gravity through a tube connected to the lower end of the mixed solvent of methanol and water to be separated in the process of phase separation. Operating device, shown in FIG. 1. The extraction solvent region of the distillation aid (a glass made of 300 mL volume of glass) was called a separation tank 30, and the separation tank 30 was filled with 250 g of a mixture of methanol and purified water at a weight ratio of 6: 4. . Cooling water used in the condenser 40 at the top of the auxiliary distillation unit circulated the tap water at room temperature. The sample was heated using a 110V heating mentle and operated by adjusting the input voltage to 60 to 70V. As the distillation time passed, the samples in the distillation tank and the samples in the separation tank were analyzed by gas chromatography. Gas chromatographic analysis was performed using HP-5 column, and analyzed by the internal standard method. Distillation was terminated when the o-cresol content was 0.2% or less as a result of distillation tank sample analysis. The results are shown in the following [Table 1].

[비교예 1]Comparative Example 1

o-크레졸 2.7%를 함유하는 2,6-디메틸페놀 1100g에 제품명 YK-MD40(SK종합화학) 고비점의 탄화수소 공비제를 끓는점 155 ~ 170 ℃ 범위의 혼합물만 분별 증류하여 공비제로서 400g을 가하였다. 상기 혼합물을 증류조에 넣고 30단 증류컬럼으로 상압 하에서 공비증류시켰다. 가열은 110V 히팅멘틀(heating mentle)을 이용하였으며, 입력 전압을 60~70V로 조정하여 운전하였다. 환류비는10:1로 설정하고 상부 증류온도별로 분획한 시료는 가스크로마토그래피로 분석하였다. 가스크로마토그래피 분석에는 HP-5컬럼을 이용하였으며, 내부표준법을 이용하여 분석하였다. 최종적으로는 증류조 내의 잔류 시료를 가스 크로마토그래피로 분석하여 탄화수소 공비제를 제외한 시료 중 o-크레졸의 함량이 0.2%이하인 경우 종료하였다. 그 결과를 하기 [표1]에 기재하였다.
1,100 g of 2,6-dimethylphenol containing 2.7% of o-cresol was separately fractionated by distilling only the mixture having a boiling point of 155-170 ° C from the high boiling point hydrocarbon azeotropic agent YK-MD40 (SK synthesis chemical). It was. The mixture was placed in a distillation tank and azeotropically distilled under atmospheric pressure with a 30-stage distillation column. Heating was performed using a 110V heating mentle, and the input voltage was operated to 60 ~ 70V. The reflux ratio was set to 10: 1 and the samples fractionated by the upper distillation temperature were analyzed by gas chromatography. Gas chromatographic analysis was performed using HP-5 column, and analyzed by the internal standard method. Finally, the residual sample in the distillation tank was analyzed by gas chromatography, and the sample was terminated when the content of o-cresol was 0.2% or less in the sample except for the hydrocarbon azeotrope. The results are shown in the following [Table 1].

[비교예 2]Comparative Example 2

고비점의 탄화수소 공비제(제품명YK-MD40, SK종합화학)를 그대로 사용한 것을 제외하고는 비교예 1과 동일한 방법으로 공비증류를 실시하였다. 그 결과를 하기 [표1]에 기재하였다.
Azeotropic distillation was carried out in the same manner as in Comparative Example 1 except that a high boiling point hydrocarbon azeotropic agent (product name YK-MD40, SK Global Chemical) was used as it was. The results are shown in the following [Table 1].

[비교예 3][Comparative Example 3]

탄화수소 공비제를 사용하지 않는 것을 제외하고는 비교예 1과 동일한 방법으로 증류를 실시하였다. 그 결과를 하기 [표1]에 기재하였다.
Distillation was carried out in the same manner as in Comparative Example 1 except that no hydrocarbon azeotrope was used. The results are shown in the following [Table 1].

[표 1][Table 1]

Figure pat00001

Figure pat00001

상기 표 1의 결과로부터, 동일한 양의 조 2,6-디메틸페놀을 정제하기 위하여 사용되는 공비제의 함량은 공비제로 고비점의 탄화수소 공비제로부터 분별증류된 끓는점 155 ~ 170 ℃ 범위의 탄화수소 공비제를 이용하고 메탄올과 물이 채워진 분리조를 이용한 실시예 1의 경우 비교예 1과 2의 공비제 사용량의 절반으로 매우 적은 양으로 고순도의 2,6-디메틸페놀을 정제할 수 있음을 알 수 있다. From the results of Table 1, the content of the azeotropic agent used to purify the same amount of crude 2,6-dimethylphenol is azeotropic hydrocarbon azeotropic agent in the range of boiling point 155 ~ 170 ℃ fractionated from a high boiling point hydrocarbon azeotropic agent In the case of Example 1 using a separation tank filled with methanol and water, it can be seen that high purity 2,6-dimethylphenol can be purified in a very small amount at half the amount of azeotropic agents of Comparative Examples 1 and 2. .

또한, 실시예 1의 경우 공비증류 후 증류조 내 공비제는 5~7 wt% 잔류하며, 이는 상기 공정 이후 1:10의 환류비에서 분별증류로 완전히 제거가능한 반면, 비교예 2의 경우 공비제를 정제하지 않고 그대로 사용하였기 때문에 잔류 공비제의 완전한 제거가 어렵다.In addition, in the case of Example 1, after the azeotropic distillation, the azeotropic agent in the distillation tank remains 5 to 7 wt%, which can be completely removed by fractional distillation at a reflux ratio of 1:10 after the process, whereas in the case of Comparative Example 2 As it was used without purification, it was difficult to completely remove the residual azeotropic agent.

또한, 공비제로 고비점의 탄화수소 공비제로부터 분별증류된 끓는점 155 ~ 170 ℃ 범위의 탄화수소 공비제를 이용하고 메탄올과 물이 채워진 분리조를 이용한 실시예 1의 경우 증류조 내의 탄화수소 공비제를 제외한 나머지 시료 중 o-크레졸의 함량이 0.2%이하가 되기까지 10시간이 걸렸으나, 메탄올과 물이 채워진 분리조를 이용하지 않고 단지 실시예 1과 동일한 공비제를 사용한 비교예 1의 경우 증류조 내의 탄화수소 공비제를 제외한 나머지 시료 중 o-크레졸의 함량이 0.2%이하가 되기까지 24시간이 걸렸고, 고비점의 탄화수소 공비제만 이용한 비교예 2의 경우 17시간이 걸렸고, 공비제를 사용하지 않고 일반 증류를 실시한 비교예 3의 경우 공비증류가 일어나지 않았다. In addition, in the case of Example 1 using a hydrocarbon azeotropic agent of boiling point 155 ~ 170 ℃ range fractionated from a high boiling point hydrocarbon azeotropic agent and a separation tank filled with methanol and water as the azeotropic agent except the hydrocarbon azeotropic agent in the distillation tank It took 10 hours until the o-cresol content in the sample was 0.2% or less, but in Comparative Example 1 using the same azeotropic agent as in Example 1 without using a separation tank filled with methanol and water, the hydrocarbon in the distillation tank was It took 24 hours for the o-cresol content to be 0.2% or less in the remaining samples except for the azeotropic agent, and in Comparative Example 2 using only a high boiling point hydrocarbon azeotropic agent, it took 17 hours. In the case of Comparative Example 3, the azeotropic distillation did not occur.

또한, 실시예 1의 공비증류 시간에 따른 분리조 내 메탄올과 물의 혼합용매층에 용해된 o-크레졸과 2,6-디메틸페놀의 함량을 살펴보면 o-크레졸만 분리조 내 메탄올과 물의 혼합용매층에 용해되어 있을 뿐, 2,6-디메틸페놀은 전혀 존재하지 않음을 알 수 있다. 이로부터 실시예 1의 방법을 통하여 2,6-디메틸페놀을 정제함에 있어 2,6-디메틸페놀은 전혀 손실되지 않고 단지 o-크레졸만 선택적으로 제거되어 고수율로 고순도의 2,6-디메틸페놀을 수득할 수 있음을 알 수 있다.In addition, the contents of o-cresol and 2,6-dimethylphenol dissolved in the mixed solvent layer of methanol and water in the separation tank according to the azeotropic distillation time of Example 1 were mixed solvent layers of methanol and water in the o-cresol-only separation tank. It is found that only 2,6-dimethylphenol does not exist at all. From this, in the purification of 2,6-dimethylphenol through the method of Example 1, 2,6-dimethylphenol was not lost at all, and only o-cresol was selectively removed to obtain high purity 2,6-dimethylphenol in high yield. It can be seen that can be obtained.

또한, 탄화수소 공비제를 사용하지 않은 비교예 3의 일반적인 증류로는 30단 증류컬럼으로 고순도의 2,6-디메틸페놀을 수득하는 것이 불가능하였다. In addition, it was not possible to obtain high purity 2,6-dimethylphenol in a 30-stage distillation column in the general distillation of Comparative Example 3 without using a hydrocarbon azeotropic agent.

즉, 본 발명에서와 같이 공비제로 고비점의 탄화수소 공비제로부터 분별증류된 끓는점 155 ~ 170 ℃ 범위의 탄화수소 공비제를 이용하고 메탄올과 물이 채워진 분리조를 이용하는 경우 공비제의 순환으로 인하여 공정시간이 획기적으로 단축되었으며 또한, 공비제의 사용량이 절반으로 감소하였을 뿐만 아니라 2,6-디메틸페놀의 손실이 전혀 발생하지 않았다.That is, as in the present invention, when using a boiling point 155 ~ 170 ℃ hydrocarbon azeotropic agent fractionated from a high boiling point azeotropic azeotropic agent and using a separation tank filled with methanol and water process time due to the circulation of azeotropic agent This drastic shortening also reduced the use of azeotropic agents in half and no loss of 2,6-dimethylphenol.

Claims (6)

o-크레졸을 포함하는 조 2,6-디메틸페놀의 혼합물로부터 공비제를 사용하여 공비증류를 통해 2,6-디메틸페놀을 정제하는 방법으로서,
상기 공비제로 끓는점 155 내지 170℃의 탄화수소 공비제를 사용하고, 공비혼합물은 응축기에 의해 응축되고 응축된 공비혼합물은 메탄올과 물이 채워진 분리조에 수집되어 공비제가 분리조로부터 증류조로 순환되고, o-크레졸은 외부로 배출되는 2,6-디메틸페놀의 정제 방법.
A process for purifying 2,6-dimethylphenol via azeotropic distillation using an azeotropic agent from a mixture of crude 2,6-dimethylphenol comprising o-cresol,
As the azeotropic agent, a hydrocarbon azeotropic agent having a boiling point of 155 to 170 ° C. is used, the azeotrope is condensed by a condenser and the condensed azeotrope is collected in a separation tank filled with methanol and water so that the azeotrope is circulated from the separation tank to a distillation tank, o- Cresol is a method for purifying 2,6-dimethylphenol that is discharged to the outside.
제 1항에 있어서,
상기 메탄올과 물은 1:1 ~ 2:1의 중량비로 혼합되는 2,6-디메틸페놀의 정제 방법.
The method of claim 1,
The methanol and water is a purification method of 2,6-dimethylphenol is mixed in a weight ratio of 1: 1 ~ 2: 1.
제 1항에 있어서,
상기 탄화수소 공비제는 고비점의 탄화수소 공비제를 분별증류하여 분리된 끓는점 155 내지 170℃의 탄화수소 화합물 또는 그들의 혼합물인 2,6-디메틸페놀의 정제 방법.
The method of claim 1,
The hydrocarbon azeotropic agent is a method for purifying 2,6-dimethylphenol, which is a hydrocarbon compound having a boiling point of 155 to 170 ° C. or a mixture thereof separated by distillation of a high boiling point hydrocarbon azeotropic agent.
제 3항에 있어서,
상기 고비점의 탄화수소 공비제는 끓는점 155 내지 170℃의 탄화수소 화합물 또는 그들의 혼합물을 30% 이상 포함하는 것인 2,6-디메틸페놀의 정제 방법.
The method of claim 3,
The high boiling point hydrocarbon azeotropic agent is a boiling point of 155 to 170 ℃ a hydrocarbon compound or a mixture thereof containing 30% or more of the purification method of 2,6-dimethylphenol.
제 1항에 있어서,
상기 탄화수소 공비제는 조 2,6-디메틸페놀 100 중량부에 대하여 15 내지 50 중량부로 사용되는 2,6-디메틸페놀의 정제 방법.
The method of claim 1,
The hydrocarbon azeotropic agent is used in the amount of 15 to 50 parts by weight based on 100 parts by weight of crude 2,6-dimethylphenol.
제 1항에 있어서,
상기 공비증류는 상압에서 수행되는 2,6-디메틸페놀의 정제 방법.The method of claim 1,
The azeotropic distillation is carried out at atmospheric pressure.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2789146A (en) * 1954-08-10 1957-04-16 Consolidation Coal Co Separation of 2, 6-xylenols from cresols
US4349419A (en) * 1978-12-25 1982-09-14 Mitsui Petrochemical Industries Ltd. Process for separation of alkyl phenols by azeotropic distillation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2789146A (en) * 1954-08-10 1957-04-16 Consolidation Coal Co Separation of 2, 6-xylenols from cresols
US4349419A (en) * 1978-12-25 1982-09-14 Mitsui Petrochemical Industries Ltd. Process for separation of alkyl phenols by azeotropic distillation

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