KR20210076239A - High-selective separation method of indole containing in fraction of coal tar wash oil by o/w/o emulsion - Google Patents

Abstract

The present invention relates to a method for selectively separating indole contained in coal tar absorption oil fraction (outflow temperature range: 240 to 265℃) using an O/W/O emulsion. More particularly, the present invention disperses an O/W emulsion emulsified by using an aqueous saponin solution as a liquid film and coal tar absorption oil as an internal oil phase, in an external oil phase (normal-heptane), thereby selectively separating indole contained in the internal oil phase.

Description

High-selective separation method of indole contained in coal tar absorption oil fraction by O/W/O emulsion {HIGH-SELECTIVE SEPARATION METHOD OF INDOLE CONTAINING IN FRACTION OF COAL TAR WASH OIL BY O/W/O EMULSION}

In the present invention, an O/W emulsion emulsified using coal tar absorption oil as an internal oil phase and an aqueous saponin solution as a liquid film as a liquid film is dispersed in an external oil phase (normal-heptane) to selectively permeate indole in the internal oil phase. it's about

In general, coal tar absorption oil is a hydrocarbon of relatively high molecular weight and is used for refining or recovering heavy hydrocarbons such as aromatic organic compounds contained in coke oven gas generated in the dry distillation process for producing coke. It is called coal tar absorption oil because it is manufactured by distilling coal tar.

Such coal tar absorption oil contains impurities such as, for example, ash and quinoline insolubles in petroleum or coal-based tar and pitch for carbon materials. Therefore, various methods for removing it have been tried.

For example, there are solvent extraction methods and filtering methods that filter out insoluble components by dissolving in a specific solvent, but in such a technology, the solvent's dissolving power is not sufficient, so an excess amount of solvent must be added, followed by complicated addition to recover the solvent. There is a problem that requires the process of

The present invention relates to a method for selectively permeating the indole contained in the coal tar absorption oil fraction (outflow temperature range: 240 to 265 ° C.), and more particularly, to the coal tar absorption oil fraction as the internal oil phase and the aqueous saponin solution as the liquid film phase. It is to selectively permeate the indole contained in the internal oil phase by dispersing the O/W emulsion emulsified by using it in the external oil phase (normal-heptane).

1): Republic of Korea Patent Publication No. 10-1423512 2): Korean Patent Publication No. 10-2014-0092435 3): Republic of Korea Patent Publication No. 10-0906563

The present invention is to solve the above problems, and it is possible to separate the indole contained in the coal tar absorption oil fraction with high selectivity and yield. It is an object of the present invention to provide a permeation method using the saponin concentration in the liquid film phase and O/W emulsion. .

The present invention is to solve the above problems, in a method for separating indole contained in coal tar absorption oil fraction using an O/W/O emulsion, permeation rate using n-heptane as an external oil phase (solvent) A highly selective separation method of indole contained in coal tar absorption oil fraction is provided, characterized in that the initial volume fraction of the O/W emulsion with respect to the entire liquid phase in the stirring tank is extracted at 0.1 at 450 rpm to 750 rpm.

Preferably, the O/W emulsion is a highly selective separation method of indole contained in the coal tar absorption oil fraction, characterized in that the initial mass fraction of saponin in the liquid film phase (saponin aqueous solution) is 0.015 to 0.03.

As described above, as a result of liquid membrane permeation according to the present invention, the indole contained in the coal tar absorption oil fraction can be easily classified with high selectivity and yield.

1 is a schematic diagram of highly selective separation of indole and nitrogen ring compounds contained in a coal tar absorption oil fraction according to the present invention.

The terms used in the present invention have been selected as widely used general terms as possible, but in certain cases, there are also terms arbitrarily selected by the applicant. In this case, it is not the name of a simple term, but the meaning described or used in the specific content for practicing the invention should be taken into account to understand its meaning.

Hereinafter, the technical configuration of the present invention with respect to a method of permeating the indole contained in the internal oil phase (coal tar absorption oil fraction) of the O/W emulsion through liquid-liquid contact of the O/W emulsion-solvent (normal-heptane) will be described. .

The permeation method of the present invention uses an O/W emulsion composed of 50% by volume of the internal oil phase and 50% by volume of the liquid membrane (saponin aqueous solution: initial mass fraction of saponin: 0.015 to 0.03), and the stirring speed is set to 450 rpm to 900 rpm, and the stirring speed is set in the stirring tank This is a method of permeating the initial volume fraction of the O/W emulsion with respect to the entire liquid in the range of 0.1 to 0.4.

As a result of permeating the indole contained in the absorption oil fraction under the permeation condition using the O/W emulsion formulated under the emulsification conditions, the permeability was very good.

In the present invention, the separation selectivity was calculated in the following manner.

Selectivity of indole (IN) using diethylnaphthalene (DMN) as a reference component β _IN,DMN is the ratio of the partition coefficient m of _DMN to the partition coefficient m _{IN of IN to DMN.}

In this case, x is the mass fraction in the residual phase (internal oil phase in the O/W emulsion phase) collected after an arbitrary permeation time, and y is the mass fraction in the extracted phase (external oil phase, solvent phase) separated after an arbitrary permeation time.

In addition, in the present invention, the yield of indole (IN) was expressed as _{Y IN .}

In this case, E is the mass (g) of the extracted phase separated after an arbitrary permeation time, and R ₀ is the mass (g) of the raw material (coal tar absorption oil) before permeation operation.

Hereinafter, the technical configuration of the present invention will be described in more detail through the following examples.

[Example 1] Composition of the initial internal oil coal tar absorption oil fraction (outflow temperature range: 240 to 265 ℃) used in the permeation experiment

As a result of analyzing the internal oil phase (coal tar absorption oil fraction) used in the experiment using GC, it had the composition shown in Table 1 below. Referring to Table 1, the composition of indole in the absorption oil fraction was 4.66 wt%.

[Table 1]

Composition of indole contained in coal tar absorption oil fraction

_{[Example 2] Effect of initial mass fraction (C sap,0} ) of saponin in liquid membrane (saponin aqueous solution) on permeation of indole

100 ml of the raw material (internal oil phase) and 100 ml of an aqueous saponin solution (liquid film) maintained at a constant concentration were put into a stirring tank, and emulsified for 10 minutes only with a stirrer (stirring speed 600 rpm). Thereafter, while circulating and circulating this with an attached pump, it was emulsified for 10 minutes using a high-speed homogenizer (stirring speed 20,000 rpm) and the above-mentioned stirrer to prepare a further atomized O/W emulsion.

A glass batch stirring tank with an inner diameter of 8 cm and a height of 8 cm was used as a permeation device for the O/W emulsion and the external oil phase (solvent: n-heptane). The impeller is a six-flatblade turbine type, and its position is installed at the mid-height of the liquid core on the central axis. In addition, four baffle plates were inserted into the tank so that a free interface was not formed.

A certain amount of O/W emulsion was put into a stirring tank to reach the experimental temperature, and then a predetermined amount of a solvent (normal-heptane) maintained at the experimental temperature was added to start stirring. After a certain period of time had elapsed, stirring was stopped and allowed to stand to separate the residual phase (emulsion) and the extraction phase (solvent), and then the mass of each phase was measured. A small amount of fractional residual phase and a sample to which acetone was added to the extracted phase were analyzed by GC to determine the concentration of the separation target component (indole) contained in the second phase.

_O,0=0.5로 일정하게 유지)을 사용하여 교반조내 전체 액상(320 ml)에 대한 O/W 에멀젼의 초기 체적분율

_OW,0를 0.1, 투과온도 T를 30 ^oC, 교반속도를 600 rpm으로 일정하게 유지한 상태에서 40초 동안 투과실험(t=40s)를 행해 인돌의 투과성능을 측정했다. 그 결과를 다음 표 2에 제시했다. Five types of O/W emulsions (initial volume fraction of internal oil in O/W emulsion) prepared by changing the _{initial mass fraction C sap,0} of saponin in the liquid film (saponin aqueous solution) from 0.010 to 0.03

_{O, 0} = 0.5), the initial volume fraction of the O/W emulsion with respect to the total liquid phase (320 ml) in the stirring bath

The permeation performance of indole was measured by conducting a permeation experiment (t=40s) for 40 seconds while maintaining _OW,0 at 0.1, permeation temperature T at 30 ^{o C, and stirring speed at 600 rpm.} The results are presented in Table 2 below.

[Table 2]

Change in selectivity and yield according to _{the initial mass fraction (C sap,0} ) of saponin in the liquid film (saponin aqueous solution)

Regardless of C _{sap,0 , Y IN} and β _IN,DMN showed almost constant values _{, so the influence of C sap,0} on yield and selectivity could not be recognized. At C _sap < 0.01, the liquid film was unstable and emulsification was impossible.

In the _{range 0.015≤C sap,0} ≤0.03, Y _IN and β _IN,DMN showed high values of 29% and over 15.8, respectively.

[Example 3] Effect of stirring speed (N) on permeation of indole

100 ml of the raw material (internal oil phase) and 100 ml of an aqueous saponin solution (liquid film) maintained at a constant concentration were put into a stirring tank, and emulsified for 10 minutes only with a stirrer (stirring speed 600 rpm). Thereafter, while circulating and circulating this with an attached pump, it was emulsified for 10 minutes using a high-speed homogenizer (stirring speed 20,000 rpm) and the above-mentioned stirrer to prepare a further atomized O/W emulsion.

A glass batch stirring tank with an inner diameter of 8 cm and a height of 8 cm was used as a permeation device for the O/W emulsion and the external oil phase (solvent: n-heptane). The impeller is a six-flatblade turbine type, and its position is installed at the mid-height of the liquid core on the central axis. In addition, four baffle plates were inserted into the tank so that a free interface was not formed.

A certain amount of O/W emulsion was put into a stirring tank to reach the experimental temperature, and then a predetermined amount of a solvent (normal-heptane) maintained at the experimental temperature was added to start stirring. After a certain period of time had elapsed, stirring was stopped and allowed to stand to separate the residual phase (emulsion) and the extraction phase (solvent), and then the mass of each phase was measured. The concentration of indole contained in phase 2 was determined by GC analysis of a small amount of the fractional residual phase and a sample in which acetone was added to the extraction phase.

_O,0=0.5로 일정하게 유지)을 사용하여 교반조내 전체 액상(320 ml)에 대한 O/W 에멀젼의 초기 체적분율

_OW,0를 0.1, 투과온도 T를 30 ^oC를 일정하게 유지한 상태에서 교반속도 N을 변화시켜 40초 동안 투과실험(t=40s)를 행해 인돌의 투과성능을 측정했다. 그 결과를 다음 표 3에 제시했다. O/W emulsion (initial volume fraction of internal oil phase in O/W emulsion _{) prepared with an initial mass fraction C sap,0} of saponin in the liquid film (saponin aqueous solution) of 0.02

_{O, 0} = 0.5), the initial volume fraction of the O/W emulsion with respect to the total liquid phase (320 ml) in the stirring bath

The permeation performance of indole was measured by conducting a permeation experiment (t=40s) for 40 seconds by changing the stirring speed N while maintaining the _OW,0 at 0.1 and the permeation temperature T at 30 ^{o C.} The results are presented in Table 3 below.

[Table 3]

Change of selectivity and yield according to stirring speed (N)

N

900의 범위에서 Y_IN은 29 ～ 38의 범위를, β_IN,DMN은 12.5 ～ 22.3의 범위를 보였다. The increase in N decreased the average diameter of the O/W emulsion, resulting in an increase in the liquid-liquid contact area, _{thereby increasing Y IN} , but β _{IN and DMN} decreased inversely due to increased membrane breakage as N increased. 450

N

In the range of 900, Y _IN showed a range of 29 ~ 38, and β _{IN, DMN} showed a range of 12.5 ~ 22.3.

_OW,0)이 인돌의 투과에 미치는 영향[Example 4] Initial volume fraction of O/W emulsion with respect to the entire liquid phase in the stirring tank (

_{Effect of OW,0} ) on permeation of indole

100 ml of the raw material (internal oil phase) and 100 ml of an aqueous saponin solution (liquid film) maintained at a constant concentration were put into a stirring tank, and emulsified for 10 minutes only with a stirrer (stirring speed 600 rpm). Thereafter, while circulating and circulating this with an attached pump, it was emulsified for 10 minutes using a high-speed homogenizer (stirring speed 20,000 rpm) and the above-mentioned stirrer to prepare a further atomized O/W emulsion.

A glass batch stirring tank with an inner diameter of 8 cm and a height of 8 cm was used as a permeation device for the O/W emulsion and the external oil phase (solvent: n-heptane). The impeller is a six-flatblade turbine type, and its position is installed at the mid-height of the liquid core on the central axis. In addition, four baffle plates were inserted into the tank so that a free interface was not formed.

A certain amount of O/W emulsion was put into a stirring tank to reach the experimental temperature, and then a predetermined amount of a solvent (normal-heptane) maintained at the experimental temperature was added to start stirring. After a certain period of time had elapsed, stirring was stopped and allowed to stand to separate the residual phase (emulsion) and the extraction phase (solvent), and then the mass of each phase was measured. The concentration of indole contained in phase 2 was determined by GC analysis of a small amount of the fractional residual phase and a sample in which acetone was added to the extraction phase.

_O,0=0.5로 일정하게 유지)을 사용하여 교반속도 N을 600 rpm, 투과온도 T를 30 ^oC를 일정하게 유지한 상태에서 교반조내 전체 액상(320 ml)에 대한 O/W 에멀젼의 초기 체적분율

_OW,0를 변화시켜 40초 동안 투과실험(t=40s)를 행해 인돌의 투과성능을 측정했다. 그 결과를 다음 표 4에 제시했다. O/W emulsion (initial volume fraction of internal oil phase in O/W emulsion _{) prepared with an initial mass fraction C sap,0} of saponin in the liquid film (saponin aqueous solution) of 0.02

O/W emulsion for the entire liquid phase (320 ml) in the stirring tank while maintaining the stirring speed N of 600 rpm and the permeation temperature T of 30 ^o _{C constant using O, 0 = 0.5)} volume fraction

_{The permeation performance of indole was measured by changing OW,0} and conducting a permeation experiment (t=40s) for 40 seconds. The results are presented in Table 4 below.

[Table 4]

_OW,0)에 따른 선택도와 수율의 변화Initial volume fraction of O/W emulsion with respect to the entire liquid phase in the stirring tank (

Changes in selectivity and yield according to _{OW,0 )}

_OW,0가 증가함에 따라 수율 및 선택도가 급격히 감소했다. 0.1

_OW,0

0.4의 범위에서 Y_IN은 11 ～ 34의 범위를, β_IN,DMN은 3.7 ～ 19의 범위를 보였다.

The yield and selectivity decreased sharply with increasing _OW,0. 0.1

_OW,0

In the range of 0.4, Y _IN showed a range of 11 ~ 34, and β _{IN, DMN} showed a range of 3.7 ~ 19.

The above description is illustrative of the present invention, and the embodiments published in the specification are intended to explain, not to limit the technical idea of the present invention, so those of ordinary skill in the art to which the present invention pertains. Various modifications and variations will be possible without departing from the technical idea of Therefore, the protection scope of the present invention is to be interpreted by the matters described in the claims, and technical matters within the scope equivalent thereto should be construed as being included in the scope of the present invention.

_OW,0 : 초기 체적분율

_O,0 : 초기 부피분율
E : 임의의 투과시간 후 분취한 추출상의 질량(g)
R₀ : 투과조작 전의 원료(콜타르 흡수유)의 질량(g)C _sap,0 : initial mass fraction

_OW,0 : initial volume fraction

_O,0 : initial volume fraction
E: Mass (g) of the extracted phase collected after any permeation time
R ₀ : Mass (g) of raw material (coal tar absorption oil) before permeation operation

Claims (2)

In the method of separating indole contained in coal tar absorption oil fraction using O/W/O emulsion,
Contained in coal tar absorption oil fraction, characterized in that by using n-heptane as an external oil phase (solvent), the permeation rate is 450 rpm to 750 rpm, and the initial volume fraction of the O/W emulsion with respect to the entire liquid phase in the stirring tank is extracted to 0.1 A method for highly selective isolation of indoles. According to claim 1,
O/W emulsion is a highly selective separation method of indole contained in coal tar absorption oil fraction, characterized in that the initial mass fraction of saponin in the liquid film phase (saponin aqueous solution) is 0.015 ~ 0.03.

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