KR102427811B1 - Surface modified ceramic hollow fiber membrane, membrane contactor comprising same and method of preparing same - Google Patents

Abstract

Disclosed are a surface-modified ceramic hollow fiber membrane, a membrane contactor comprising the same, and a method for manufacturing the same. The surface-modified ceramic hollow fiber membrane may include: a hydrophilic ceramic hollow fiber membrane containing a hydrophilic inorganic material; and a hydrophobic surface modification layer formed on the surface of the hydrophilic ceramic hollow fiber membrane and including a hydrophobic material. The surface-modified ceramic hollow fiber membrane of the present invention has the effect of minimizing membrane wetting and improving the replacement cycle by imparting hydrophobicity through surface modification. In addition, the membrane contactor including the surface-modified ceramic hollow fiber membrane of the present invention uses a ceramic material with excellent thermal and physical properties to allow direct input without additional equipment for lowering the exhaust gas temperature, and can handle a large amount of high temperature exhaust gas. there is an effect In addition, the membrane contactor including the surface-modified ceramic hollow fiber membrane of the present invention has the effect of remarkably reducing the equipment volume and the installation site.

Description

Surface-modified ceramic hollow fiber membrane, membrane contactor comprising same, and method for manufacturing the same

The present invention relates to a ceramic hollow fiber membrane, a membrane contactor comprising the same, and a manufacturing method thereof, and more particularly, to a surface-modified ceramic hollow fiber membrane, a membrane contactor comprising the same, and a manufacturing method thereof.

As the consumption of fossil fuels increases due to industrial development and improvement of living standards, nitrogen oxides (NO _X ), sulfur oxides (SO _X ) and carbon dioxide (CO ₂ ) in the exhaust gas emitted after fuel combustion have caused air pollution, acid rain, and the atmosphere. The general public is suffering from extreme fine dust and global warming that are secondary to photochemical reactions. Existing general exhaust gas scrubber methods include a packed tower, a spray tower, a venturi scrubber, a bubble column, and the like. However, even if the above conventional techniques are advanced, it is difficult to expect improvement in removal efficiency and size reduction of the device, and furthermore, there are many problems such as flooding and channeling of fluid in the device.

As a means to solve these problems, research on a gas separation process using a membrane contactor is being actively conducted. However, due to the polymer material, it is not suitable for high temperature, and there is a problem in that there are many difficulties in demonstrating it due to the film wetting phenomenon that causes a decrease in the gas removal performance.

Currently, a method of removing sulfur oxides (SO _X ) from exhaust gas is mainly a process of producing gypsum (CaSO ₄ ) using slaked lime (CaO). However, high-quality limestone (CaCO ₃ ) and slaked lime, which are sulfur oxide absorbers, are being depleted by continuous mining, so it is expected that it will be difficult to obtain high-quality gypsum any more. In addition, most of the exhaust gas is emitted at a high temperature, so there is a problem that a large amount of sulfur oxide (SO _X ) suffers a lot of difficulties.

An object of the present invention is to provide a surface-modified ceramic hollow fiber membrane capable of minimizing membrane wetting and improving the replacement cycle by imparting hydrophobicity through surface modification.

It is also an object of the present invention to use a ceramic material having excellent thermal and physical properties so that it can be directly injected without additional equipment for lowering the exhaust gas temperature, and a surface-modified ceramic hollow fiber membrane capable of treating a large amount of high-temperature exhaust gas, including the same It is to provide a membrane contactor that

It is also an object of the present invention to provide a membrane contactor that can dramatically reduce a facility volume and an installation site.

According to an aspect of the present invention, a hydrophilic ceramic hollow fiber membrane including a hydrophilic inorganic material; and a hydrophobic surface modification layer formed on the surface of the hydrophilic ceramic hollow fiber membrane and including a hydrophobic material.

In addition, the hydrophobic surface modification layer may be formed on one or more surfaces selected from an outer surface not in contact with the hollow and an inner surface contacting the hollow of the hydrophilic ceramic hollow fiber membrane.

In addition, the hydrophobic surface modification layer may be formed on the outer surface of the hydrophilic ceramic hollow fiber membrane not in contact with the hollow.

In addition, the hydrophobic material may be formed by coating an organosilane compound on the surface of the hydrophilic ceramic hollow fiber membrane.

In addition, the organosilane compound may be a compound represented by Structural Formula 1 below.

[Structural Formula 1]

In Structural Formula 1,

R ¹ is a C1 to C5 alkyl group,

이고,R ² is a C1 to C5 alkyl group or

ego,

t is any one of an integer from 0 to 5,

u is any one of an integer from 1 to 10,

R ³ is a hydrogen atom (H), a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I),

이고,R ⁴ is

ego,

m is any one of integers from 0 to 4,

n is any one of integers from 0 to 4,

q is any one of integers from 0 to 4,

r is 0 or 1,

m + n + q + r = 4.

In addition, according to another embodiment, R ¹ is a C1 to C2 alkyl group,

이고,R ² is a C1 to C2 alkyl group or

ego,

t is any one of integers from 1 to 3,

u is any one of an integer from 3 to 8,

R ³ is a hydrogen atom (H) or a chlorine atom (Cl),

이고,R ⁴ is

ego,

m is any one of integers from 0 to 4,

n is any one of integers from 0 to 4,

q is any one of integers from 0 to 4,

r is 0 or 1,

m + n + q + r = 4.

In addition, the organosilane compound is trimethoxysilane, trimethoxymethylsilane, hexamethyl disilane, trimethyl chlorosilane, and trichloro (1H, 1H, 2H, 2H). -Perfluorooctyl) silane (Trichloro(1H, 1H, 2H, 2H-perfluorooctyl) silane) may include at least one selected from the group consisting of.

In addition, the hydrophilic inorganic material may include at least one selected from the group consisting of silica (SiO ₂ ), titanium dioxide (TiO ₂ ), zirconia (ZrO ₂ ), aluminum oxide (Al ₂ O ₃ ), and composites thereof.

In addition, the hydrophilic ceramic hollow fiber membrane may have a hollow diameter of 1 to 50 mm.

In addition, the hydrophilic ceramic hollow fiber membrane may be used for at least one separation process selected from the group consisting of sulfur oxides (SOx), nitric oxides (NOx), and carbon dioxide (CO ₂ ).

According to another aspect of the present invention, there is provided a membrane contactor including the surface-modified ceramic hollow fiber membrane.

According to another aspect of the present invention, the method comprising: (a) coating a hydrophobic material on the surface of a hydrophilic ceramic hollow fiber membrane including a hydrophilic inorganic material; and (b) drying the hydrophilic ceramic hollow fiber membrane coated with the hydrophobic material to form a hydrophobic surface modification layer on the surface of the hydrophilic ceramic hollow fiber membrane; .

In addition, the step (a) comprises the steps of (a-1) preparing a hydrophobic material solution containing a hydrophobic material and an organic solvent; and (a-2) positioning the hydrophilic ceramic hollow fiber membrane so that at least one surface selected from an outer surface not in contact with the hollow and an inner surface contacting the hollow of the hydrophilic ceramic hollow fiber membrane is in contact with the hydrophobic material solution. ; may be included.

In addition, the step (a-2) may be a step (a-2') of positioning the hydrophilic ceramic hollow fiber membrane so that an outer surface of the hydrophilic ceramic hollow fiber membrane that is not in contact with the hydrophobic material solution is in contact with the hydrophobic material solution.

In addition, in step (a) after step (a-2'), (a-3) rolling the hydrophilic ceramic hollow fiber membrane 1 to 20 times to coat the hydrophobic material on the outer surface of the hydrophilic ceramic hollow fiber membrane ; may be additionally included.

In addition, the organic solvent may include at least one selected from the group consisting of ethanol, toluene, hexane, acetone, and ethyl acetate.

In addition, in the method for producing the ceramic hollow fiber membrane, before step (a), (a') pre-treating the hydrophilic ceramic hollow fiber membrane by immersing the hydrophilic ceramic hollow fiber membrane in a solvent, irradiating ultrasonic waves to wash and drying the hydrophilic ceramic hollow fiber membrane; may include

In addition, the hydrophobic material may be formed by coating an organosilane compound on the surface of the hydrophilic ceramic hollow fiber membrane.

In addition, the organosilane compound may be a compound represented by Structural Formula 1 below.

[Structural Formula 1]

In Structural Formula 1,

R ¹ is a C1 to C5 alkyl group,

이고,R ² is a C1 to C5 alkyl group or

ego,

t is any one of an integer from 0 to 5,

u is an integer from 1 to 10,

R ³ is a hydrogen atom (H), a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I),

이고,R ⁴ is

ego,

m is any one of integers from 0 to 4,

n is any one of integers from 0 to 4,

q is any one of integers from 0 to 4,

r is 0 or 1,

m + n + q + r = 4.

In addition, the organosilane compound is trimethoxysilane, trimethoxymethylsilane, hexamethyl disilane, trimethyl chlorosilane, and trichloro (1H, 1H, 2H, 2H). -Perfluorooctyl) silane (Trichloro(1H, 1H, 2H, 2H-perfluorooctyl) silane) may include at least one selected from the group consisting of.

The surface-modified ceramic hollow fiber membrane of the present invention has the effect of minimizing membrane wetting and improving the replacement cycle by imparting hydrophobicity through surface modification.

In addition, the membrane contactor including the surface-modified ceramic hollow fiber membrane of the present invention uses a ceramic material with excellent thermal and physical properties to allow direct input without additional equipment for lowering the exhaust gas temperature, and can handle a large amount of high temperature exhaust gas. there is an effect

In addition, the membrane contactor including the surface-modified ceramic hollow fiber membrane of the present invention has the effect of remarkably reducing the equipment volume and the installation site.

1 (a) is a ceramic hollow fiber membrane that is not surface-modified, (b) is a surface-modified ceramic hollow fiber membrane according to an embodiment of the present invention, (c) is a surface according to another embodiment of the present invention It is a schematic diagram showing the structure of the modified ceramic hollow fiber membrane, and (d) is an image of the ceramic hollow fiber membrane that is not surface-modified.
2 is an image showing a step of coating a hydrophobic material on the outer surface of the hydrophilic ceramic hollow fiber membrane in the method of manufacturing the surface-modified ceramic hollow fiber membrane of the present invention.
Figure 3 is a schematic diagram schematically showing the minimum penetration pressure measuring equipment.
4 shows Examples 1-1, 1-5, 1-6, 1-8 to 1-10, 2-1, 2-5, 2-6 when the liquid ratio (L/G) is 4 ml/L and 2-10 using the hydrophobically surface-modified ceramic hollow fiber membrane prepared according to Comparative Example 1 and the ceramic hollow fiber membrane prepared according to Comparative Example 1 in a membrane contactor, and is a graph showing the removal rate according to time when SO ₂ is separated.
5 shows Examples 1-1, 1-5, 1-6, 1-8 to 1-10, 2-1, 2-5, 2-6 when the liquid ratio (L/G) is 1 ml/L and 2-10 using the hydrophobically surface-modified ceramic hollow fiber membrane prepared according to Comparative Example 1 and the ceramic hollow fiber membrane prepared according to Comparative Example 1 in a membrane contactor, and is a graph showing the removal rate according to time when SO ₂ is separated.
6 (a) to (c) are SEM images of the ceramic hollow fiber membrane prepared according to Comparative Example 1 and the hydrophobically surface-modified ceramic hollow fiber membrane prepared according to Examples 1-10 and 2-10, respectively. .
7A to 7D are SEM images of the hydrophobically surface-modified ceramic hollow fiber membranes prepared according to Examples 1-1, 1-5, 1-6, and 1-10, respectively.
8 (a) to (d) are SEM images of the hydrophobically surface-modified ceramic hollow fiber membranes prepared according to Examples 2-1, 2-5, 2-6 and 2-10, respectively.
9 (a) and (b) are side SEM images of the ceramic hollow fiber membrane prepared according to Comparative Example 1 and the hydrophobically surface-modified ceramic hollow fiber membrane prepared according to Examples 2-5, respectively.

Since the present invention can apply various transformations and can have various embodiments, specific embodiments are illustrated and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention. In describing the present invention, if it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, terms including ordinal numbers such as first, second, etc. to be used hereinafter may be used to describe various elements, but the elements are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

In addition, when it is mentioned that a component is “on another component,” “formed on another component,” “located on another component,” or “stacked on another component,” the It may be formed, positioned, or laminated by being directly attached to the front surface or one surface on the surface of other components, but it will be understood that other components may be further present in the middle.

The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

1 (a) is a ceramic hollow fiber membrane that is not surface-modified, (b) is a surface-modified ceramic hollow fiber membrane according to an embodiment of the present invention, (c) is a surface according to another embodiment of the present invention It is a schematic diagram showing the structure of the modified ceramic hollow fiber membrane, and (d) is an image of the ceramic hollow fiber membrane that is not surface-modified.

Hereinafter, the surface-modified ceramic hollow fiber membrane of the present invention will be described with reference to FIG. 1 .

The present invention relates to a hydrophilic ceramic hollow fiber membrane containing a hydrophilic inorganic material; and a hydrophobic surface modification layer formed on the surface of the hydrophilic ceramic hollow fiber membrane and including a hydrophobic material.

The hydrophobic surface modification layer may be formed on one or more surfaces selected from an outer surface not in contact with the hollow of the hydrophilic ceramic hollow fiber membrane and an inner surface contacting the hollow of the hydrophilic ceramic hollow fiber membrane. It may be formed on an outer surface that is not in contact with the .

The hydrophobic material may be formed by coating an organosilane compound on the surface of the hydrophilic ceramic hollow fiber membrane.

The organosilane compound may be coated on the surface of the hydrophilic ceramic hollow fiber membrane through a sol-gel reaction.

The organosilane compound may be a compound represented by Structural Formula 1 below.

[Structural Formula 1]

In Structural Formula 1,

R ¹ is a C1 to C5 alkyl group, preferably a C1 to C2 alkyl group,

, 바람직하게는 C1 내지 C2 알킬기 또는

이고,R ² is a C1 to C5 alkyl group or

, preferably a C1 to C2 alkyl group or

ego,

t is an integer from 0 to 5, preferably an integer from 1 to 3,

u is any one of integers from 1 to 10, preferably any one of integers from 3 to 8,

R ³ is a hydrogen atom (H), a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I), preferably a hydrogen atom (H) or a chlorine atom (Cl),

이고,R ⁴ is

ego,

m is any one of integers from 0 to 4,

n is any one of integers from 0 to 4,

q is any one of integers from 0 to 4,

r is 0 or 1,

m + n + q + r = 4.

The organosilane compound is trimethoxysilane, trimethoxymethylsilane, hexamethyl disilane, trimethyl chlorosilane, and trichloro (1H,1H,2H,2H- It may include at least one selected from the group consisting of perfluorooctyl)silane (Trichloro(1H,1H,2H,2H-perfluorooctyl)silane).

The hydrophilic inorganic material may include at least one selected from the group consisting of silica (SiO ₂ ), titanium dioxide (TiO ₂ ), zirconia (ZrO ₂ ), aluminum oxide (Al ₂ O ₃ ), and composites thereof.

The hydrophilic ceramic hollow fiber membrane may have a hollow diameter of 1 to 50 mm. If the diameter is less than 1 mm, it is not preferable because it is difficult to form a hollow fiber membrane, and if it exceeds 50 mm, it is not preferable because it is difficult to downsize, which is an advantage of the membrane contactor.

The hydrophilic ceramic hollow fiber membrane may be porous.

The hydrophilic ceramic hollow fiber membrane may be used in one or more separation processes selected from the group consisting of sulfur oxides (SOx), nitric oxides (NOx), and carbon dioxide (CO ₂ ).

The present invention also provides a membrane contactor comprising the surface-modified ceramic hollow fiber membrane.

Hereinafter, a method for manufacturing the surface-modified ceramic hollow fiber membrane of the present invention will be described.

First, the hydrophilic ceramic hollow fiber membrane containing the hydrophilic inorganic material on the surface A hydrophobic material is coated (step a).

The step (a) comprises the steps of (a-1) preparing a hydrophobic material solution containing a hydrophobic material and an organic solvent; and (a-2) positioning the hydrophilic ceramic hollow fiber membrane so that at least one surface selected from an outer surface not in contact with the hollow and an inner surface contacting the hollow of the hydrophilic ceramic hollow fiber membrane is in contact with the hydrophobic material solution. ; may be included.

The step (a-2) may be a step (a-2') of positioning the hydrophilic ceramic hollow fiber membrane so that an outer surface of the hydrophilic ceramic hollow fiber membrane not in contact with the hollow is in contact with the hydrophobic material solution.

2 is an image showing a step of coating a hydrophobic material on the outer surface of the hydrophilic ceramic hollow fiber membrane in the method of manufacturing the surface-modified ceramic hollow fiber membrane of the present invention. Referring to FIG. 2 , the step (a) is performed 1 to 20 times, preferably 5 to 15 times, more preferably 8 to (a-3) the hydrophilic ceramic hollow fiber membrane after step (a-2') The method may further include a step of coating the hydrophobic material on the outer surface of the hydrophilic ceramic hollow fiber membrane by rolling 12 times. At this time, the inner surface in contact with the hollow is not to be coated.

The organic solvent may include at least one selected from the group consisting of ethanol, toluene, hexane, acetone, and ethyl acetate.

The method of manufacturing the ceramic hollow fiber membrane includes the steps of (a') pretreating the hydrophilic ceramic hollow fiber membrane by immersing the hydrophilic ceramic hollow fiber membrane in a solvent, washing and drying by irradiating ultrasonic waves before the step (a); can do.

Next, the hydrophilic ceramic hollow fiber membrane coated with the hydrophobic material is dried to form the hydrophilic ceramic hollow fiber membrane. on the surface hydrophobic surface modification layer form (step b).

[Example]

Hereinafter, the present invention will be described in more detail by way of examples. However, this is for illustrative purposes, and the scope of the present invention is not limited thereto.

Example 1: Preparation of surface-modified ceramic hollow fiber membrane through immersion

Example 1-1

A hollow fiber membrane [Pervaporation Membrane module] coated with zirconia (ZrO ₂ ) on the hydrophilic alumina (Al ₂ O ₃ ) ceramic surface was immersed in ethanol, and then cleaned by irradiating ultrasonic waves for 15 minutes using an ultrasonic cleaner, and then 90 It was dried at ℃ and pre-treated.

The pretreated ceramic hollow fiber membrane was immersed for 1 hour in a solution of a mixture of trimethoxysilane, a surface modification material, and ethanol, a solvent, and then dried at 90° C. for 1 hour to surface-modify. Thereafter, it was washed with ethanol and acetone, and dried at 100° C. for 30 minutes to prepare a hydrophobically modified ceramic hollow fiber membrane.

Examples 1-2 to 1-10

Referring to Table 1 below, using the method described in Example 1-1 under the conditions of Table 1, the hydrophobic surface-modified ceramic hollow fiber membranes of Examples 1-2 to 1-10 were prepared.

Example surface modification material menstruum 1-1 Trimethoxysilane ethanol 1-2 Trimethoxymethylsilane ethanol 1-3 Hexamethyl disilane ethanol 1-4 Trimethyl chlorosilane ethanol 1-5 Trichloro(1H,1H,2H,2H-perfluorooctyl)silane ethanol 1-6 Trimethoxysilane toluene 1-7 Trimethoxymethylsilane toluene 1-8 Hexamethyl disilane toluene 1-9 Trimethyl chlorosilane toluene 1-10 Trichloro(1H,1H,2H,2H-perfluorooctyl)silane toluene

Example 2: Through coating surface modified Manufacturing of ceramic hollow fiber membrane

Example 2-1

A hollow fiber membrane [Pervaporation Membrane module] coated with zirconia (ZrO ₂ ) on the hydrophilic alumina (Al ₂ O ₃ ) ceramic surface was immersed in ethanol, and then cleaned by irradiating ultrasonic waves for 15 minutes using an ultrasonic cleaner, and then 90 It was dried at ℃ and pre-treated.

Referring to FIG. 2, the pretreated ceramic hollow fiber membrane was rolled 10 times in 5 mL of a solution of a mixture of trimethoxysilane, a surface modifying material, and ethanol, a solvent, and then dried at 90° C. for 1 hour to surface-modify. . Thereafter, it was washed with ethanol and acetone, and dried at 100° C. for 30 minutes to prepare a hydrophobically modified ceramic hollow fiber membrane.

Examples 2-2 to 2-10

Referring to Table 2 below, using the method described in Example 2-1 under the conditions of Table 2, the hydrophobic surface-modified ceramic hollow fiber membranes of Examples 2-2 to 2-10 were prepared.

Example surface modification material menstruum 2-1 Trimethoxysilane ethanol 2-2 Trimethoxymethylsilane ethanol 2-3 Hexamethyl disilane ethanol 2-4 Trimethyl chlorosilane ethanol 2-5 Trichloro(1H,1H,2H,2H-perfluorooctyl)silane ethanol 2-6 Trimethoxysilane toluene 2-7 Trimethoxymethylsilane toluene 2-8 Hexamethyl disilane toluene 2-9 Trimethyl chlorosilane toluene 2-10 Trichloro(1H,1H,2H,2H-perfluorooctyl)silane toluene

comparative example One: No surface modification Manufacturing of non-porous ceramic hollow fiber membranes

A hollow fiber membrane [Pervaporation Membrane module] coated with zirconia (ZrO ₂ ) on a hydrophilic alumina (Al ₂ O ₃ ) ceramic surface was purchased and used as Comparative Example 1.

[Test Example]

Test Example 1: Contact angle analysis

The contact angle of the surface-modified ceramic hollow fiber membrane was measured using a self-manufactured contact angle measuring device. Table 3 below shows the contact angles of the hydrophobically surface-modified ceramic hollow fiber membranes prepared according to Examples 1-1 to 1-10 and Examples 2-1 to 2-10.

Surface modification method Example surface modification material menstruum contact angle immersion
(immersion) 1-1 Trimethoxysilane ethanol 91.6° 1-2 Trimethoxymethylsilane ethanol 20° 1-3 Hexamethyl disilane ethanol 20° 1-4 Trimethyl chlorosilane ethanol 0° 1-5 Trichloro(1H,1H,2H,2H-perfluorooctyl)silane ethanol 118.4° 1-6 Trimethoxysilane toluene 112.5° 1-7 Trimethoxymethylsilane toluene 103° 1-8 Hexamethyl disilane toluene 81.2° 1-9 Trimethyl chlorosilane toluene 80.8° 1-10 Trichloro(1H,1H,2H,2H-perfluorooctyl)silane toluene 130.9° coating
(coating) 2-1 Trimethoxysilane ethanol 98° 2-2 Trimethoxymethylsilane ethanol 30.8° 2-3 Hexamethyl disilane ethanol 29.8° 2-4 Trimethyl chlorosilane ethanol 0° 2-5 Trichloro(1H,1H,2H,2H-perfluorooctyl)silane ethanol 124.0° 2-6 Trimethoxysilane toluene 90.7° 2-7 Trimethoxymethylsilane toluene 48.5° 2-8 Hexamethyl disilane toluene 45.1° 2-9 Trimethyl chlorosilane toluene 60.1° 2-10 Trichloro(1H,1H,2H,2H-perfluorooctyl)silane toluene 138.9°

Referring to Table 3, it was confirmed that the difference in the contact angle of the surface appeared according to the surface modification method. The contact angle is a measure for determining whether the surface is hydrophobic or hydrophilic. The ceramic hollow fiber membranes prepared according to Examples 1-1 to 1-10 and Examples 2-1 to 2-10 impart hydrophobicity to the surface of the hydrophilic ceramic membrane. was able to confirm that The contact angle of the ceramic hollow fiber membrane surface-modified through immersion and coating shows a similar tendency. Through this, it can be confirmed that surface modification through coating uses a smaller amount of surface modification material as compared to surface modification through immersion, thereby significantly reducing the amount of surface modification material used.

Test Example 2: Analysis of Minimum Penetration Pressure

Figure 3 is a schematic diagram schematically showing the minimum penetration pressure measuring equipment. Referring to FIG. 3 , the physical pressure of the membrane was measured by adjusting the valve at the rear end after fixing the flow rate of the liquid at 100 mL/min and installing a pressure gauge before and after. Minimum penetration pressure of the hydrophobically surface-modified ceramic hollow fiber membranes prepared according to Examples 1-1 to 1-10 and Examples 2-1 to 2-10 and the non-surface-modified ceramic hollow fiber membranes prepared according to Comparative Example 1 is shown in Table 4 below.

Surface modification method surface modification material menstruum Minimum penetration pressure (bar) before washing test after washing test - Comparative Example 1 - - 0.04 0.04 immersion
(immersion) Example 1-1 Trimethoxysilane ethanol 0.10 0.10 Example 1-2 Trimethoxymethylsilane ethanol - - Examples 1-3 Hexamethyl disilane ethanol - - Examples 1-4 Trimethyl chlorosilane ethanol - - Examples 1-5 Trichloro(1H,1H,2H,2H-perfluorooctyl)silane ethanol 0.85 0.85 Examples 1-6 Trimethoxysilane toluene 0.36 0.35 Examples 1-7 Trimethoxymethylsilane toluene - - Examples 1-8 Hexamethyl disilane toluene 0.18 0.18 Examples 1-9 Trimethyl chlorosilane toluene 0.18 0.18 Examples 1-10 Trichloro(1H,1H,2H,2H-perfluorooctyl)silane toluene 0.90 0.90 coating
(coating) Example 2-1 Trimethoxysilane ethanol 0.22 0.17 Example 2-2 Trimethoxymethylsilane ethanol - - Example 2-3 Hexamethyl disilane ethanol - - Example 2-4 Trimethyl chlorosilane ethanol - - Example 2-5 Trichloro(1H,1H,2H,2H-perfluorooctyl)silane ethanol 0.35 0.41 Example 2-6 Trimethoxysilane toluene 0.26 0.20 Example 2-7 Trimethoxymethylsilane toluene - - Examples 2-8 Hexamethyl disilane toluene - - Examples 2-9 Trimethyl chlorosilane toluene - - Example 2-10 Trichloro(1H,1H,2H,2H-perfluorooctyl)silane toluene 0.52 0.54

Referring to Table 4, it was confirmed that the minimum penetration pressure of the membrane surface-modified through coating was lower than that of surface modification through immersion. It was confirmed that, unlike surface modification through immersion, only the outer surface of the membrane surface-modified through coating was coated, not the entire inner and outer surfaces of the membrane, and the permeation pressure was low.

test example 3: surface modification Way, surface modification SO according to the type and flow rate of substances and solvents ₂ Removal rate analysis

The hydrophobically surface-modified ceramic hollow fiber membranes prepared according to Examples 1-1 to 1-10 and Examples 2-1 to 2-10 and the non-surface-modified ceramic hollow fiber membranes prepared according to Comparative Example 1 were applied to the membrane contactor. was used to analyze the SO ₂ removal rate.

The SO ₂ removal rate (%) after an appropriate time has elapsed from the time the SO ₂ absorbent is introduced into the membrane contactor can be calculated by Equation 1 below.

[Formula 1]

SO ₂ Removal Rate (%)= ((S ₁ -S ₂ )/S ₁ )x100

In Equation 1, S ₁ is the concentration of SO ₂ in the exhaust gas introduced into the membrane contactor, and S ₂ is the concentration of SO ₂ in the exhaust gas discharged from the membrane contactor.

4 shows Examples 1-1, 1-5, 1-6, 1-8 to 1-10, 2-1, 2-5, 2-6 when the liquid ratio (L/G) is 4 ml/L and 2-10 using the hydrophobically surface-modified ceramic hollow fiber membrane prepared according to Comparative Example 1 and the ceramic hollow fiber membrane prepared according to Comparative Example 1 in a membrane contactor, and is a graph showing the removal rate according to time when SO ₂ is separated. Referring to FIG. 4 , the overall SO ₂ removal rate is high, which is the same as a general study result in which the removal rate is high due to an increase in the residence time that can be in contact with the liquid as the flow rate of the gas is lower. In particular, it was confirmed that the removal rate of the film in which only the outer surface of the ceramic film was modified through coating was similar to that of Comparative Example 1 in which the surface was not modified.

5 shows Examples 1-1, 1-5, 1-6, 1-8 to 1-10, 2-1, 2-5, 2-6 when the liquid ratio (L/G) is 1 ml/L and 2-10 using the hydrophobically surface-modified ceramic hollow fiber membrane prepared according to Comparative Example 1 and the ceramic hollow fiber membrane prepared according to Comparative Example 1 in a membrane contactor, and is a graph showing the removal rate according to time when SO ₂ is separated. Referring to FIG. 5 , as the flow rate of gas increased, an experiment in the case of membranes (Examples 1-1, 1-5, 1-6, 1-8 to 1-10) whose surface was modified through immersion At the beginning of this process, the SO ₂ removal rate rapidly decreases. In addition, in the case of Comparative Example 1, which showed the most excellent SO ₂ removal rate, the SO ₂ removal rate of Examples 2-1, 2-5 and 2-6, which was a film surface-modified through coating after about 24 hours from the start of the experiment, was higher than It was observed that the performance decreased. As a result of the increase in the flow rate of gas, the residence time for contact with the liquid was reduced, and both the outer surface and the inner pores of the ceramic membrane were covered with the surface-modifying material, thereby reducing the performance of the membrane contactor.

Test Example 4: SEM image analysis

6 (a) to (c) are SEM images of the ceramic hollow fiber membrane prepared according to Comparative Example 1 and the hydrophobically surface-modified ceramic hollow fiber membrane prepared according to Examples 1-10 and 2-10, respectively. . Referring to FIG. 6 , the difference between the surface of Comparative Example 1 without surface modification and the surfaces of Examples 1-10 and 2-10 whose surface was modified through immersion and coating can be clearly observed. do. This was confirmed to be consistent with the results confirmed through the contact angle analysis of Test Example 1.

7A to 7D are SEM images of the hydrophobically surface-modified ceramic hollow fiber membranes prepared according to Examples 1-1, 1-5, 1-6, and 1-10, respectively. Referring to FIG. 7 , it was confirmed that there was a difference in the appearance of the coating on the surface according to the type of the modifying material and the type of the solvent used for the surface modification. In the case of Examples 1-1 and 1-6, some cracks were observed on the modified surface, which is considered to be the effect of trimethoxysilane, which is a surface modification material. In addition, it was confirmed that the evenness of the modified surface was consistent with the experimental results of the contact angle analysis of Test Example 1, and trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane (Trichloro (1H, 1H, 2H) ,2H-perfluorooctyl)silane) showed a more even type of modified surface than trimethoxysilane.

8A to 8D are SEM images of the hydrophobically surface-modified ceramic hollow fiber membranes prepared according to Examples 2-1, 2-5, 2-6, and 2-10, respectively. Referring to FIG. 8 , the surfaces of Examples 2-1, 2-5, 2-6, and 2-10 in which the surface was modified through coating were modified through immersion (FIG. 7). It was confirmed that it was uneven compared to the reference). Although the roughness of the surface was rough compared to surface modification through immersion, it was confirmed that there was no significant difference from the results of the contact angle analysis of Test Example 1.

9 (a) and (b) are side SEM images of the ceramic hollow fiber membrane prepared according to Comparative Example 1 and the hydrophobically surface-modified ceramic hollow fiber membrane prepared according to Examples 2-5, respectively. Referring to FIG. 9 , a modified surface and a thin surface modified layer were confirmed depending on the presence or absence of surface modification.

Test Example 5: Analysis of HTU Value of Ceramic Hollow Fiber Membrane Contactor

When calculating the theoretical facility volume of the gas separation process, the packing height (Z) value is the standard, and the height of transfer unit (HTU) value used in calculating the Z value is the total mass transfer coefficient (K _G a) value is determined by

HTU is used as a measure of general process efficiency, and the theoretical facility volume and efficiency comparison of the gas separation process can be confirmed through the moving unit height (HTU) value.

The formulas and factor values used to calculate the moving unit height (HTU) value are as follows.

(1)

(One)

In Equation (1), K _G a is the overall mass transfer capacity coefficient (kmol/m ³ ·hr·kPa), Q _g is the gas flow rate (Nm ³ /hr), Z is the effective hollow fiber membrane length (M), and P is Operating pressure (kPa), C _SO2,in is 2,000 ppm, C _SO2,out is 10 ppm.

The moving unit height (HTU) can be calculated by substituting K _G a calculated from Equation (1) into Equation (2) below.

(2)

(2)

In the above formula (2), P is the pressure (kPa).

In Table 5 below, a hollow fiber membrane (Ceramic) coated with zirconia (ZrO ₂ ) on the alumina (Al ₂ O ₃ ) ceramic surface used in a packed column and an embodiment of the present invention used in a conventional exhaust gas scrubber The effective module length of the membrane contactor, the SO ₂ removal rate, the moving unit height (HTU) value, and the reactor volume were numerically expressed.

Packed column ceramic membrane contactor Module effective length (m) 1 - 3.2 0.250 SO ₂ Removal Rate (%) > 99 HTU ^* value (m) 0.5 - 1.6 1.2 x 10 ^-1 Reactor volume One 1 / 4.1 - 13.3

Referring to Table 5 above, the moving unit height (HTU) value in literature of the packed column is 0.5-1.6 m, and when inversely calculated by applying the experimental value of the membrane contactor, the effective module length (m) of the lab-scale packed column is 3.2 is estimated to be m. When the module size and experimental value of the ceramic membrane contactor used for surface modification are applied in the example, the moving unit height (HTU) value is calculated as 1.2 x 10 ^-1 m.

Based on the calculation results, it is determined that the volume is reduced by 1/13 times when the ceramic hollow fiber membrane contactor is applied compared to the existing packed column. has the effect of reducing

In the above, although preferred embodiments of the present invention have been described, those of ordinary skill in the art can add, change, delete or The present invention may be variously modified and changed by addition and the like, and this will also be included within the scope of the present invention. For example, each component described as a single type may be implemented in a distributed manner, and likewise components described as distributed may also be implemented in a combined form. The scope of the present invention is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention. do.

Claims (20)

A hydrophilic ceramic hollow fiber membrane containing a hydrophilic inorganic material; and
and a hydrophobic surface modification layer formed on the surface of the hydrophilic ceramic hollow fiber membrane and including a hydrophobic material;
The hydrophobic surface modification layer is formed on the outer surface of the hydrophilic ceramic hollow fiber membrane not in contact with the hollow,
The hydrophobic material is formed by coating an organosilane compound on the surface of the hydrophilic ceramic hollow fiber membrane,
The organosilane compound is at least one selected from the group consisting of trimethoxysilane, trimethoxymethylsilane, hexamethyl disilane, and trimethyl chlorosilane. including,
The hydrophilic inorganic material is a hydrophobic ceramic hollow fiber membrane containing zirconia (ZrO ₂ ). delete delete delete delete delete delete delete According to claim 1,
The hydrophilic ceramic hollow fiber membrane is a surface-modified ceramic hollow fiber membrane, characterized in that the hollow diameter of 1 to 50 mm. According to claim 1,
The hydrophilic ceramic hollow fiber membrane is a surface-modified ceramic hollow fiber membrane, characterized in that it is used for at least one separation process selected from the group consisting of sulfur oxide (SOx), nitric oxide (NOx), and carbon dioxide (CO ₂ ). A membrane contactor comprising the surface-modified ceramic hollow fiber membrane according to claim 1 . (a-1) preparing a hydrophobic material solution containing a hydrophobic material and an organic solvent;
(a-2) positioning the hydrophilic ceramic hollow fiber membrane so that the outer surface of the hydrophilic ceramic hollow fiber membrane containing a hydrophilic inorganic material, which is not in contact with the hollow, is in contact with the hydrophobic material solution, a hydrophobic material on the surface of the hydrophilic ceramic hollow fiber membrane coating the; and
(b) drying the hydrophilic ceramic hollow fiber membrane coated with the hydrophobic material to form a hydrophobic surface modification layer on the surface of the hydrophilic ceramic hollow fiber membrane;
The hydrophobic material is formed by coating an organosilane compound on the surface of the hydrophilic ceramic hollow fiber membrane,
The organosilane compound comprises at least one selected from the group consisting of trimethoxysilane, trimethoxymethylsilane, hexamethyldisilane, and trimethyl chlorosilane,
The hydrophilic inorganic material is a method of manufacturing a surface-modified ceramic hollow fiber membrane comprising zirconia (ZrO ₂ ). delete delete 13. The method of claim 12,
After step (a-2) above
(a-3) rolling the hydrophilic ceramic hollow fiber membrane 1 to 20 times to coat the hydrophobic material on the outer surface of the hydrophilic ceramic hollow fiber membrane; Desert manufacturing method. 13. The method of claim 12,
The organic solvent comprises at least one selected from the group consisting of ethanol, toluene, hexane, acetone, and ethyl acetate. Desert manufacturing method. 13. The method of claim 12,
Before the step (a-1), the method for manufacturing the ceramic hollow fiber membrane
(a') pretreatment of the hydrophilic ceramic hollow fiber membrane by immersing the hydrophilic ceramic hollow fiber membrane in a solvent, washing and drying by irradiating ultrasonic waves; . delete delete delete

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