Untitled record

The full row

Background of the invention

This invention relates to an apparatus for separating carbon dioxide from an exhaust gas, and, in particular, to an apparatus for separating carbon dioxide using a separator, which is made of a ceramic-coated porous silicone membrane and method 5 of manufacturing such apparatus.

The phenomenon of global warming (global warming) is a phenomenon of concern all over the world, and the greenhouse effect that occurs due to carbon dioxide and methane gases plays an essential role in the phenomenon of global warming. The phenomenon of global warming not only destroys the ecosystem but also has a great impact on human social life. In this context, many efforts have been implemented to reduce emissions of carbon dioxide and methane into the atmosphere.

In sewage treatment plants, wastewater treatment plants, sanitary landfills, etc., the organic materials contained in these wastes generate gas when they decompose. This gas is called landfill gas. In the primary stage of landfills, landfill gas decomposes in the presence of oxygen. However, as the amount of oxygen gradually decreases, the landfill gas essentially decomposes under anaerobic conditions. Most of the landfill gas generated in the aerobic decomposition process contains a percentage ranging from 0.4% to 0.6% carbon dioxide, and from 4% to . 6% of methane, and very small amounts of other components such as nitrogen and ammonia. Methane and carbon dioxide, the main components of landfill gas, are the cause of global warming.

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In order for landfill gas to be made usable for industrial use, methane must be separated from carbon dioxide.

The phenomenon of global warming caused by the increase in the amount of carbon dioxide in the air is one of the important environmental problems that must be solved by humans. Carbon dioxide is released from sewage treatment plants, wastewater treatment plants, sanitary landfills, etc., when that waste is burned. Carbon dioxide is especially a problem when it is released from thermal power plants or from Metal foundries. Accordingly, technologies have been developed to separate and remove carbon dioxide from exhaust gas. Some carbon dioxide separation techniques have already been developed, including absorption methods, adsorption methods, and separation methods from

Air cooling and membrane separation method.

The absorption method is a method for selectively separating carbon dioxide by absorbing carbon dioxide. In this absorption method, the gas resulting from combustion or the process gas, which contains carbon dioxide 5 1, is brought into contact with a solution, so that the carbon dioxide Carbon dioxide can be absorbed by a chemical reaction. Among the well-known absorption methods, the wet amine method is a commercially available technique. In this wet amine method, carbon dioxide is collected from the combustion exhaust gas with an amine-based absorber.

The adsorption method is a method for separating carbon dioxide by physically adsorbing carbon dioxide onto the surface of an adsorbent that has the ability to attract carbon dioxide.

·carbon dioxide

Cold air separation is a traditional gas-liquid separation method to separate carbon dioxide liquefied at a low temperature from other gases that have not been liquefied. This method is preferable because it can produce a large amount of liquefied carbon dioxide, but its disadvantage is that it requires a large amount of energy for cooling.

In the membrane separation method, a solid membrane is used that has a separation function. And the membrane separation method

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It is widely used from the molecular level to the particle level depending on the type of membrane used. In addition, since the material is usually separated using pressure, which is mechanical energy, less energy is consumed in the membrane separation method than in the thermal energy distillation method. Examples of applied membrane separation methods include reverse osmosis, ultrafiltration, microfiltration, dialysis, and gas separation. In particular,

The gas separation method is of interest as a way to separate and collect carbon dioxide in a way that conserves energy from sources that produce it in large quantities, such as thermal power plants, cement factories, and metal foundry furnaces.

In particular, a gas separation membrane, which can be used in the membrane separation method to separate and collect a particular gas from, for example, natural gas, can

It is an aromatic polyimide membrane, which is obtained by polymerizing and imidizing it to an aromatic tetracarboxylic acid component.

The aromatic diamine component and the aromatic diamine component tetracarboxylic acid are implemented

Actively reacts on the aromatic polyimide membrane. However, the gas separation membrane composed of 5 1 aromatic polyimide can only be manufactured at high temperatures of 5350°C or higher and suffers from problems including thermal resistance, durability, and chemical resistance. Therefore, solutions to these problems must be sought.

Other conventional techniques for separating and collecting carbon dioxide are described in Korean Patent Publication No. 0734926-1 and Japanese Open Patent Publication No. HEI 180062-10. Korean Patent Bulletin No. 20 No. 0734926-10 describes a device for removing sulfur compounds and separating methane 5%100 and dioxide.

Carbon dioxide 001 Hb using a liquid catalyst that is chelated with iron. The device can handle the sulfur compound found in a foul-smelling gas generated from landfills or from anaerobic decomposition and separate and treat the methane and carbon dioxide in the gas. In addition, Japanese Open Patent No. HEI 180062 states - 10

5 2 Membrane separation and selective separation method. In that patent, the separation membrane can separate carbon dioxide from a mixture of carbon dioxide and methane using a thick membrane or asymmetric membrane which has the following as a major component:

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Polyimide resin contains fluorine and has a high ability to separate carbon dioxide and a large permittivity.

To date, several carbon dioxide separation and collection methods have been proposed that incorporate previous conventional techniques. However, it is difficult to prepare a 5-separation membrane with a large size of 10 square centimeters or larger. In addition, when partial pressure is applied on both sides, a huge amount of energy is consumed, and a separation membrane cannot be formed that can withstand such a large pressure difference.

Description of the invention

Aspects of this invention provide an apparatus for selectively separating and collecting carbon dioxide from an exhaust gas (methane, carbon dioxide and other gases which will collectively be referred to as “byproduct gas”) using a separator or plate on which It is made of porous silicone membrane.

As part of this invention, a method is also developed to efficiently separate carbon dioxide by simplifying the process of manufacturing a separation membrane in order to increase the size of the separation device and reduce the energy required to separate carbon dioxide.

According to an aspect of this invention, an apparatus for separating carbon dioxide is prepared, the apparatus comprising: A tank for storing byproduct gas, which stores the byproduct gas generated by the basic environmental treatment facility. This gas contains a large amount of methane and carbon dioxide. And an inlet for the byproduct gas, through which the byproduct gas is fed from the byproduct gas storage tank, and an outlet for the byproduct gas, through which the byproduct gas containing the byproduct is emptied. methane by separating carbon dioxide from the byproduct gas being fed; A separation container, which includes a separator made of a porous silicone membrane that separates carbon dioxide.

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carbon dioxide from the byproduct gas being fed; a discharge tube which is located in a separation container to discharge the carbon dioxide separated from the porous silicon membrane; a carbon dioxide storage tank that receives and stores the separated carbon dioxide; And a tank to store the remaining part

5 of the byproduct gas, which stores the byproduct gas containing methane, which is obtained by separating carbon dioxide from the byproduct gas that is fed.

According to another aspect of this invention, a carbon dioxide separation membrane is prepared comprising: a separation membrane which is made of porous silicon; A coating layer is obtained

<p dir="rtl">0 1 Non-ceramic powder coating on porous silicone separation membrane.</p>

According to another aspect of this invention, a method is prepared for separating carbon dioxide from a byproduct gas using a carbon dioxide separation device which includes a carbondioxide separation membrane.

According to this invention, a separator or plate is used which is made of a porous ceramic-coated membrane.

51 Therefore, carbon dioxide can be selectively separated from a by-product gas using a very small pressure difference and a simple method.

There is a traditional carbon dioxide separation device that uses a pressure difference. Whereas the traditional carbon dioxide separation apparatus separates carbon dioxide by feeding a mixed gas at a pressure ranging from 3 to 0.4 kgf/cm

<p dir="rtl">02 square or higher. Therefore, there is a large energy consumption. In addition, since there is a limit to the increase in the size of the apparatus, there is a limit to production. However, this invention sets up a device for separating carbon dioxide at room temperature by maintaining a pressure difference between the inner and outer parts of the separation membrane at less than 4 kgf/cm2. Therefore, the energy consumption rate is low.</p>

25 Also, since the device is simple, the cost of producing the device can be saved.

Also, ease of loading is emphasized because the apparatus can be carried even in

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Unclean water that generates byproduct gas or underwater.

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Brief explanation of the drawings

Figure 1 is a schematic diagram of a device for separating carbon dioxide from byproduct gas;

5 Figure 2 shows a device for separating and collecting carbon dioxide from the byproduct gas fed to a separator;

Figure 3 shows a device for separating carbon dioxide, through a separator, from a by-product gas fed to a separation container;

Figure 4 shows a separation container with a set of separation units as 0 1 separation container tubes and lid;

Figure 5 shows a box-type separation unit with separation membranes, which are in the form of plates, positioned facing each other;

Figure 6 shows a mesh and backing located between separation membranes of a box-type separation unit extending along the length of that unit;

5 1 Figure 7 shows nanoceramics coated on the surface of a separation membrane;

Figure 8a is a detailed perspective view of carbon dioxide separation membranes made in sheet form;

Figure 8b shows a combined carbon dioxide separation device, in which carbon dioxide separation membranes are manufactured in sheet form;

0 2 Figure 9a is a detailed perspective view of a carbon dioxide separation membrane manufactured in the form of a tube;

Figure 9b shows a combined carbon dioxide separation device containing a membrane

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To separate carbon dioxide, a plant in the form of a tube

Figure 1 is a flow chart showing a method for constructing a carbon dioxide separation membrane

Dioxide

The steel row:

5 This invention prepares a device for separating carbon dioxide. The device includes: A tank for storing byproduct gas, which stores the byproduct gas generated by the basic environmental treatment facility. This gas contains a large amount of methane and carbon dioxide. And an inlet for the byproduct gas, through which the byproduct gas 0 1 is fed from the byproduct gas storage tank, and an outlet for the byproduct gas, through which a byproduct gas containing methane by separating carbon dioxide from the byproduct gas being fed; A separation container, which includes a separator made of a porous silicone membrane that separates carbon dioxide.

5 1 carbon dioxide from the byproduct gas being fed; a discharge tube which is located in a separation container to discharge the carbon dioxide separated from the porous silicon membrane; a carbon dioxide storage tank that receives and stores the separated carbon dioxide; And a tank to store the remaining part of the byproduct gas, which stores the byproduct gas containing 20 methane, which is obtained by separating carbon dioxide. carbon dioxide from the byproduct gas being fed.

Below, exemplary embodiments of this invention will be detailed in detail by reference to the accompanying drawings. The gas separation membrane method is used to separate a specific component from a mixed gas or organic vapor by using the permeation of the gas through the membrane. When a gaseous mixture comes into contact with the membrane surface, the gaseous components diffuse through the membrane by being dissolved or adsorbed to the membrane. Here, the stability and permissibility

The tolerance to each gaseous component can vary depending on the membrane material used for separation. For example, when

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Carbon dioxide, water vapor, helium, and hydrogen sulfide can easily pass through a membrane and be easily absorbed or dissolved in the membrane. Nitrogen, methane, ethane, and other hydrocarbons are the gaseous components. Which passes through the membrane at a very low speed. 5 This is a major reason for using a membrane to separate oxygen from nitrogen and carbon dioxide from methane in the air.

Figure 1 is a schematic diagram of an apparatus for separating carbon dioxide from byproduct gas according to an embodiment of this invention. The apparatus that separates and collects carbon dioxide includes a byproduct gas storage tank 10 byproduct 0 6 which stores a byproduct gas containing a large amount of methane and carbon dioxide, and an inlet for the byproduct gas 0 3 through which it is The byproduct gas feed from the byproduct gas storage tank* 6, and the byproduct gas outlet 0 5 through which the byproduct gas containing methane is discharged methane, which is obtained by separating carbon dioxide from the byproduct gas being fed, a separation container 10 which includes a separator 20 for separating carbon dioxide from the byproduct gas being fed, and a vacuum tube 0 4 during which the separated carbon dioxide is discharged from the separation vessel, a carbon dioxide storage tank 0 7 which receives and stores the separated carbon dioxide 0 2 dioxide, and a tank 80 which It receives and stores the byproduct gas contained

Methane is extracted by separating carbon dioxide from the byproduct gas being fed.

Generally, when the gas separation membrane method is used to separate a certain gas, there is a need to increase the pressure at the feed side and reduce the pressure at the outlet side, so that the gas 25 can pass through the separation membrane effectively. In this invention, however, the difference in negative pressure applied to the inside and outside of a separation membrane, which is carried in a separation container, is used for a particular gas component. In this case, the separation vessel can be kept at

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Temperature ranges from 0 to 6.0 degrees Celsius, and the best is in the lower range of temperature, which ranges from 2.0 to 4.0 degrees Celsius. In addition, the separation vessel can be a carbon dioxide separation device that does not change phase by maintaining a pressure of 0 to 4 kgf/cm2 and with low energy consumption. Here, 5, carbon dioxide can be separated more efficiently by the phenomenon of osmotic pressure, which results from a difference between the concentration of carbon dioxide contained in the byproduct gas and the concentration of carbon dioxide separated from the byproduct gas, even when the concentration Carbon dioxide is the same inside and outside the separation tube, so the separation of carbon dioxide can continue 0 1 difference in negative pressure.

In particular, the separation vessel 01 of this invention can obtain the energy required to separate carbon dioxide from the difference in carbon dioxide concentration between the inside of the DI separation membrane, which is made of a porous silicone membrane, and the outside of the D2 separation unit. In this case, the byproduct gas flows into the DI 5 1 separator, and only carbon dioxide is separated from the byproduct gas that exits the D2 separator. When the initial pressure Ρ1 at which the byproduct gas is fed to the separator 02 is greater than or equal to the pressure Ρ2 inside the separator, carbon dioxide will permeate through the porous silicon membrane in all cases if the carbon dioxide concentration in DI is greater than the pressure in D2 · 20. In addition, the carbon dioxide45 has: 4 006 mm of separation and is periodically transferred to the carbon dioxide storage tank in order to prevent the carbon dioxide concentration in D2 from being larger than that of DI. In this way, carbon dioxide can be selectively separated by continuously permeating through the porous silicon membrane. As a result, carbon dioxide of high purity 25 can be obtained.

The permittivity towards carbon dioxide that is separated from the byproduct gas can be calculated by the following equation (1):

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(,cm;fi!per unit tune (m0 ya0f carbon diwiidepenne t ths Hint

partial pressure (Pa) at ths feed Sid; - partial pressure (Pa) at the pene te side

Permeability a

Permittivity = amount of carbon dioxide in force per unit time (mol/s.m2)/total pressure (Pa) at the supply side - partial pressure (Pa) at the outlet side]

5 In this invention, there may be a pump located at the outlet to facilitate the discharge of the byproduct containing methane without carbon dioxide through the outlet. In this case, the pump can be maintained at a pressure of 0 to 2 kgf/cm2 in order to maintain the pressure difference inside the separation vessel within the range of 0 to 4 kgf/cm2

<p dir="rtl">0 1 In addition, another pump can be placed at the carbon dioxide collection line in order to efficiently collect the separated carbon dioxide. In this case, the pump can be maintained at a pressure of about 0 to 1 kgf/cm2</p>

The separation membrane can be made of a polymeric material such as cellulose acetate or polysulfone, a new polymeric material, a ceramic material or a carbon molecular sieve material. Preferably, the separation membrane can be made of porous silica-based ceramic, porous silica-based glass, porous alumina-based ceramic, porous stainless steel, porous titanium, or porous silver. Better yet, the separation membrane can be made from porous silicone.

<p dir="rtl">0 2 In this invention, the separation unit 0 2 which is made of a porous silicone membrane can be in the form of a vertical plate, a horizontal plate, or a tube. Better yet, the 02 separation unit can be in tube form.</p>

Figures 2 and 3 show various embodiments in which the byproduct gas is fed to either the separator 02 or the separation vessel 01 using the reversible characteristics of the separation unit. and on

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In particular, Figure 2 shows a case in which when byproduct gas is fed to separator 20 as shown by reference 30 and flows through separator 20, carbon dioxide is adsorbed and passes through the separator membrane to be collected in the separator vessel 10 as shown. Shown as reference number 40. Figure 3 shows a case in which when 5 byproduct gas is fed to a separation container 0 1 as shown by reference number 0 3 it is adsorbed and carried to the separator for discharge as shown by reference number 0 4.

Figure 4 shows a separation container with a set of separation units in the form of tubes and a lid for the separation container. In order to increase the rate of carbon dioxide collection, a group of separation units 20 can be placed in a separation container

10 As shown in Figure 4, separation containers can be placed 10

At a certain angle, for example, vertically or horizontally, a high-throughput carbon dioxide separation device can be made by connecting two or more separation vessels 01. In this case, support 0 9 can be placed in appropriate positions to support and protect the separation units.

In addition, the porous silicon membrane of this invention can be made into 15 sheets to produce a box-shaped separator with a higher separation area. Accordingly, the quantity

The carbon dioxide that separates and collects can increase. For example, Figure 5 shows a separator unit with a surface area that increases with loading of separating membranes, which are made in the form of plates, facing each other with space between them. The separation unit includes a 9 0 support shaped like a quadrilateral frame. The support 0 9 maintains a predetermined gap between the separation membranes

separation membranes 0 2

Figure 6(a) shows a box-type separator extending in a longitudinal direction and where there is a strut 90 and a mesh 100 between the separation membranes 20 to maintain a predetermined gap between the separation membranes 0 2 and protect the separation membranes 0 2 It allows the separation of carbon dioxide · 25 Figure 6(b) shows only 90 supports. The support 90 supports the mesh 100

To inhibit excessive expansion of separation membranes 0 2. Figure 6(c) shows the network

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mesh 0 0 1 only. The mesh 0 0 1 is a structure that inhibits excessive expansion of the separation membranes 0 2 due to the difference in pressure between the inside and outside of the separation unit in the process of separating carbon dioxide and maintaining a pre-determined gap between the membranes.

·Separation membranes separation

5 To increase the carbon dioxide separation area, a set of canister-shaped separation units 0 2 is loaded into a separation container 0 1. In this case, by-product gas is injected from outside the 200 separation units, carbon dioxide is discharged and each of the 200 separation units is collected through a 400 discharge tube. In addition, there can be a hole in each of the separation units 20 for direct connection between

<p dir="rtl">0 1 Separation units 0 2 by pressure. In this case, carbon dioxide can be collected through those openings, or there can be a carbon dioxide collection tube between the separation units. Since the separator is reversible, byproduct gas can be injected into the separator, and the separated carbon dioxide can be collected outside the separator.</p>

5 1 Figure 7 shows nanoceramic coated on the surface of the separation membrane. In this invention, the nano-sized ceramic powder can be coated inside and outside the porous silicone separation membrane. The ceramic can be any one or more of a Fe-based oxide, a Fe-based oxide, or a Fe-based oxide. Palladium Pd-based oxide, Ti-base oxide,

<p dir="rtl">02 and aluminum-based oxide, which has an affinity for carbon dioxide. It is preferable that the ceramic can be one or more of a mixture of</p>

·Zeolite; and zeoliteFeO. TOPdO, AlO.MgO, NiO, Υ2Ο3. so. zo.

In general, ceramic is better than an organic polymer membrane in terms of heat resistance, chemical stability, and mechanical/physical properties. And so,

5 2 It can be used in an atmosphere at high temperature and high pressure, and in corrosive conditions. In addition, when porous ceramic is used on

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In the separation membrane, gas molecules can be passed through micropores by Knudsen-type diffusion, surface diffusion, or activated diffusion in the molecular sieve area depending on the size or surface characteristics of the micropores. Also, to improve the separation performance, diffusion through the surface can be activated by controlling the size and composition of the micropores and reshaping the surface of the micropores. Accordingly, it is possible to preferably use the layer

The ceramic coating of this invention serves as a separation membrane for the adsorption and diffusion of carbon dioxide because of the great affinity of that layer for carbon dioxide.

Depending on the ceramic coating method, the separation membrane can be dipped in a suspension obtained by diluting ceramic powder in water and then taken from the suspension.

0 1 and dried 0 The thickness of the ceramic coated membrane can be adjusted according to the size of the ceramic powder and the number of times the separation membrane is dipped in the suspension. Alternatively, the ceramic coating can be used by spraying the suspension or by the ceramic deposition method.

In addition, the surface of the separation membrane can be reshaped to be alkaline by coating the separation membrane with an alkali metal or with an alkaline earth metal such as

<p dir="rtl">5 1 Sodium, potassium, magnesium or barium In this case, carbon dioxide, which is an acid gas, can be separated with high efficiency.</p>

In addition, the support 0 9 or mesh » 1 can be made of metal to apply an electric field· and the electric field applied to the support or mesh

<p dir="rtl">» 2 It can facilitate the movement of carbon dioxide molecules. When the mesh is made from an organic material, an electrode is made from a metallic conductive wire to supply a potential difference. When the mesh or support is metal, there is no need to add an electrode</p>

Electrode

In particular, an electric field is applied to the mesh, and the electrode support H2 can supply either a direct current or an alternating current.

In particular, direct current ranging from 0.01 to 0.5 kilovolts or alternating current

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alternating current ranges from 0.01 to 50 kV in the case of 1 Hz to 1 MHz. This facilitates the movement of carbon dioxide molecules, thus increasing the speed of passage of carbon dioxide molecules through the carbon dioxide separation membrane. Accordingly, carbon dioxide can be separated more easily5. In this case, care must be taken to prevent damage to the separator unit due to overcurrent.

In this invention, a sound wave generator can also be placed on the byproduct gas movement path inside the separation unit that is made of the porous silicone membrane. The sound wave generator can cause vibration of the porous silicone membrane. Thus, the separation of carbon dioxide is made efficient

higher. The sound wave generator can cause the porous silicone membrane to vibrate by generating a sound wave ranging from 1 Hz to 1.0 kHz. Accordingly, carbon dioxide can easily pass through the porous silicone membrane and be separated more easily. In this case, when the sound wave generated by the sound wave generator is very high, care must be taken to prevent damage to the separator by the resonance phenomenon.

Figure 8(a) is a detailed perspective view of carbon dioxide separation membranes made in sheet form. Figure 8b shows an assembled carbon dioxide separation device. To assemble the carbon dioxide separation device, an inlet and outlet 400, a mesh 0 0 E and an electrode 0 55 are placed between the upper separation membranes 20 and the lower 100 in the form of plates, and then The upper and lower separator membranes 100 are bonded together

Using an adhesive on the edges of the upper and lower separation membranes 100.

Mesh 0 0 e is a flexible mesh-shaped material that acts as a support in a hose pipe. The mesh 0 0 e is made of nylon, resin, or a metal material such as a spring. When the pressure between the upper and lower plates becomes negative, the mesh 0 0 H prevents the upper and lower plates H2 from contacting each other and thus they lose the separation function. It can be manufactured

The mesh is in the form of a tube or plate.

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A separation container for the device to separate carbon dioxide can use a stacked plate, which is in the form of a flat plate, or a tube. A byproduct gas is passed through the separation vessel, which contains a stack of separation membranes in flat plates, and only carbon dioxide is separated and extracted through the inlet or outlet 4,000. The opposite is possible. Since the heavy product gas can be passed through the inlet or outlet 400, carbon dioxide can only be separated and extracted into the separation vessel. Therefore, the inlet or outlet 4 0 0 can be formed only on one side or on both sides. Separation membranes in flat panels.

0 1 Figure 9(a) is a detailed perspective view of a carbon dioxide separation membrane manufactured in the form of a tube. Figure 9b shows an assembled carbon dioxide separation device. The carbon dioxide separation device is assembled by inserting a 400 inlet or outlet, a 0.0 mesh, and a 0.55 electrode into a carbon dioxide separation membrane tube and tightly closing the separation membrane tube. Carbon with an adhesive used on both ends of the carbon separation membrane tube

Figure 1 shows a method for constructing a carbon dioxide separation membrane according to another embodiment of this invention. The porous silicone membrane can be formed by mixing silicone rubber raw material, ceramic powder, and a curing agent, extruding the mixture, and curing the extruded mixture at a temperature of 0.8 to 0.3°C.

20 In particular, the method of forming a membrane for carbon dioxide separation may include a) preparing a mixture by mixing a raw material of silicone rubber, ceramic and a curing agent, b) stirring the mixture, c) extruding the stirred mixture as a silicon composite membrane containing Ceramics by injecting the stirred mixture into an extrusion unit at a temperature ranging from 0°C to 100°C, and d) curing the composite film at a temperature ranging from 100°C to 300°C.

E2 In general, silicone rubber maintains its properties even at high temperatures. Therefore, silicone rubber has a tensile strength and elongation rate

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rate, and its resistance in water is better than general organic rubber. Unlike other organic rubbers, silicone rubber has a molecular structure without a double bond, which causes cracks by reacting with oxygen, ozone, and ultraviolet rays in the atmosphere. Therefore, silicone rubber has excellent resistance, which makes it difficult to suffer from changes in physical properties even if used for a long period of time. In addition, silicone rubber has heat resistance, low-temperature flexibility, excellent strength, and Retard the fire. Often, since the permittivity of silicone rubber to oxygen and organic vapor is high, silicone rubber is used to concentrate oxygen in the air and collect organic vapor.

0 1 The ceramic powder may be any one or more of Fe-based oxide, Pd-based oxide, Ti-base oxide and ΑΙ-based oxide which has a level Attraction towards dioxide

FeOg, preferably ceramic powder, which is any one of or a mixture of carbon dioxide, carbon dioxide, zeolite, TOPdO, Al₂O3,MgO, NiO, Υ2Ο3. so. Ζ1Ό2

E1 An amount of ceramic powder can be used from 0.001 to 10 carbon dioxide in the separating membrane.

In addition, the curing agent may be organic peroxide, which can generate radicals by pyrolysis at temperatures ranging from

02 to 200°C. For example, a processing agent could be, but not limited to, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, ortho-methyl benzoyl peroxide. 0- methylbenzoyl peroxide, 2, 4-diquimmyl peroxide -2,4 25 •4L17100300hsa4,5,2-bis-dimethyl (2,5-butyl tert-peroxy) hexane -2,5

dimethyl-bis(2,5-t-butylperoxy) hexane, di-t-butyl peroxide

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peroxide, t-butyl perbenzoate, or 1,6-hexanediol-bis-

0l,6-hexanediol-bis-t-butyl peroxy carbonate butyl tert peroxycarbonate

In this invention, after mixing the ceramic and the curing agent, they can be mixed with a raw material of silicone rubber. The curing agent may be added in an amount ranging from 0.1 to 1.5 parts by weight, e.g., in particular, from 2.0 to 1 part by weight on a basis of 1 part by weight.

Total. When the curing agent is added in an amount of less than 0.1 parts by weight, the rubber raw material can become very soft or cheese-like in consistency after curing, and thus is unsuitable for use in the silicone separation membrane of this invention. When the curing agent is added in an amount greater than 5 1 fraction by weight, it can damage the mechanical/physical properties, and it may take longer than 10 to remove the remaining curing agent after the curing process.

In process b) of this invention, the ceramic mixture and curing agent may be mixed with a silicone rubber raw material and then stirred for a period of 10 minutes to five hours at room temperature for homogeneous mixing. Therefore, if the mixture of ceramic, curing agent and silicone rubber raw material is not mixed well, it can cause a difference in the density of 5 1 ceramic in the silicone rubber raw material, make the thickness of the formed separator not uniform, and cause peeling phenomenon. For this reason, the mixture of ceramic, curing agent and silicone rubber raw material must be stirred sufficiently.

In addition, in process c) of this invention, the stirred mixture from process b) is extruded. The stirred mixture is injected into an extrusion unit heated to a temperature ranging from 0.5 to 0.01.02°C and is extruded as a silicon composite membrane containing ceramic in the form of a tube. And then,

The silicon-ceramic composite membrane is cured down to the uncured portion at 100 to 300°C at atmospheric pressure to produce a tube-shaped silicon-ceramic composite membrane.

In this invention, the curing period can be reduced by increasing the content of the curing agent or by increasing the curing temperature in the mixture of the aforementioned raw materials. In addition, the use of far-wavelength infrared heating can also reduce the time required.

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For processing silicone rubber.

In this invention, the silicon composite film obtained by extruding the stirred mixture can be formed into a vertical sheet, horizontal sheet or tube.

In this invention, the composite membrane obtained by extruding the stirred mixture can also be a porous silicon composite membrane containing ceramic. And it could be

Ceramics have grain sizes ranging from 1 nanometer to 1.0 micrometers.

In this invention, the separation membrane made of porous silicon can be in the form of a tube with a diameter ranging from 1 to 100 millimeters, and preferably, from 2 to 50 millimeters. In addition, the separation membrane made of porous silicone can have a thickness ranging from 0.05 to 10.3 millimeters, and preferably from 0.1 to 2 millimeters. When the diameter and thickness of the separation membrane are outside the limits

predetermined, this can also affect the surface area and permittivity towards dioxide

·carbon dioxide carbon

In addition, the pores that form in the silicone membrane can have a diameter ranging from 0.3 to 0.37 nanometers, and preferably from 0.32 to 0.35 nanometers. When the silicon pores have a diameter greater than 0.38 nanometers, based on the kinetic molecular diameter, which is usually used

To compare gas diffusion, methane can be separated as well as carbon dioxide. When the silicon pores have a diameter of less than 0.33 nm, carbon dioxide may not be separated. Therefore, a porous silicon membrane must be used. siicone membrane with appropriate pore diameter.

<p dir="rtl">0 2 The nanoceramic powder used in this invention can have an average grain size from 1 to 100 nm, or preferably from 2 to 0 nm.</p>

In addition, the ceramic-coated membrane in this invention can have thicknesses ranging from 2 nanometers to 1000 micrometers. When the ceramic-coated film is too thick or too thin, it can develop cracks or peeling. Since carbon dioxide cannot penetrate through a very thick ceramic coating, the coating must be adjusted

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With ceramic.

The ceramic separation membrane can be coated with dip coating, flow coating, roll coating or spray coating, preferably with dip coating. In that case, the ceramic could dissipate

5 In water or in any alcohol-based organic solvents such as methanol, ethanol and propanol and then used to coat the separation membrane. It is most preferable for the ceramic to be dispersed in water. The ceramic can be dispersed for 30 minutes to 1 hour using an ultrasonic dispersion and then used to coat the separation membrane.

<p dir="rtl">0 1 In addition, this invention may provide a method for separating carbon dioxide from a by-product gas using a carbon dioxide separation device which includes a separator made of a porous silicon membrane.</p>

·sine membrane

In this invention, the difference in pressure between the inside and outside of the separation unit, which is made of a porous silicone membrane, is less than 4 kgf/square centimeter.

When the pressure difference between the inside and outside of the separation unit is 4 kgf/cm2 or greater, and the flow rate of the byproduct gas increases, it is thus difficult to absorb carbon dioxide and pass it through the porous silicone membrane.

In addition, expansion of the porous silicone film can be noticeable. And so, it is

20 It is preferable to separate carbon dioxide 45N00140 in pressure values close to atmospheric pressure.

Below, this invention will be described in greater detail through examples. The purpose of these examples is to illustrate this invention, and it will be clear to those with ordinary experience in this field that the scope of this invention is not limited to those examples.

25 (examples)

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In this invention, the collected carbon dioxide has been analyzed using gas chromatography, and the flow rate has been measured using a mass flow meter

·meter (MFC)

Example 1: An experiment carried out using a porous silicone tube as a separator.

5 A 2 mm thick porous silicon tube was used as the porous silicon membrane 20 in Figure 1, and a mixed gas containing 0% carbon dioxide and 0% nitrogen was used as a byproduct gas. The byproduct gas was injected into a reactor at a constant flow rate of 2.5 cm3/s using an MFC.

As the byproduct gas flows at a constant flow rate, carbon dioxide flows through the separation unit, which is made from a silicon tube. As a result, the collection rate of carbon dioxide separated from the byproduct gas was 94%.

Example 2: The experiment was carried out using a porous silicon tube coated with nanoceramics as a separation membrane.

After mixing 0.5 grams of nanoceramic with 1.0 grams of water, the mixture was sufficiently dispersed using an ultrasonic dispersion. After that, a 2 thickness silicone tube was immersed

mm in a dispersed mixture for 30 minutes. The silicone tube was taken from the dispersed mixture and dried for 3 to 4 hours at room temperature. This method was repeated three or more times so that the mixture could be coated homogeneously inside and outside the tube.

The 0005 pore silicon tube was loaded as a 20 porous silicon membrane for Figure 1, and 20 mixed gases containing 0% carbon dioxide 006M and 50% nitrogen were used as the by-product gas. The byproduct gas was injected into the reactor at a constant flow rate of 2.5 cc using an MFC.

As the byproduct gas flows at a constant flow rate, carbon dioxide flows through the separation unit, which is made of silicon tubing. As a result, the collection rate of carbon dioxide separated from the byproduct gas was 5.2

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97% byproduct

(comparative example)

Comparative example 1

Comparative example 1-1

The experiment was carried out in the same manner as in Example 1 of this invention except that a porous silicone tube with a thickness of 0.5 millimeters was used as a porous silicone membrane 20, starting from a porous silicone tube with a thickness of 2 millimeters in Example 1.

Comparative example 1-2

An experiment has been carried out in the same manner as Example 1 of this invention except that 1.0 mm thick porous silicon tube has been used as a porous silicone membrane.

20 Instead of the 2 mm thick porous silicone tube in Example 1.

Comparative example 2

Comparative example 2-1

An experiment has been carried out in the same manner as in Example 2 of this invention, except that instead of the 2 mm thick porous silicone tube in Example 2, 15 porous silicone tubes with a thickness of 5.0 mm have been coated with nanoceramic (nanoceramic) and used as a membrane.

0 02 porous silicone membrane porous silicone

Comparative example 2-2

An experiment was carried out in the same manner as in Example 2 of this invention, except that 20 porous silicone tubes with a thickness of 0.1 were coated instead of the porous silicone tube with a thickness of 2 millimeters in Example 2 with nanoceramic and were used as a porous silicone membrane. .

[Table 1]

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<tr><td rowspan="2"><p dir="rtl">Carbon dioxide concentration</p><p>compound dioxide (%)</p></td><td rowspan="2"><p dir="rtl">Selectivity</p><p>(Ο/Ν</p></td><td colspan="2"><p dir="rtl">Flow rate (cubic centimeter/second)</p></td><td rowspan="2"><p dir="rtl">Thickness (mm) of membrane on the partition)</p></td><td rowspan="2"></td></tr><tr><td></td><td><p>CO.</p></td></tr><tr><td><p dir="rtl">Verse 9</p></td><td><p dir="rtl">١٣</p></td><td><p dir="rtl">٠،١٧</p></td><td><p dir="rtl">٢،٢</p></td><td><p dir="rtl">٢</p></td><td><p dir="rtl">Example 1</p></td></tr><tr><td><p dir="rtl">٩٧</p></td><td><p dir="rtl">١٥</p></td><td><p dir="rtl">٠،٢٢</p></td><td><p dir="rtl">A,3</p></td><td><p dir="rtl">٢</p></td><td><p dir="rtl">Example 2</p></td></tr><tr><td><p dir="rtl">Verse 9</p></td><td><p dir="rtl">١٣</p></td><td><p dir="rtl">٠،٢٥</p></td><td><p dir="rtl">٣،٣</p></td><td><p dir="rtl">٠٤٥</p></td><td><p dir="rtl">Comparative example 1-1</p></td></tr><tr><td><p dir="rtl">Verse 9</p></td><td><p dir="rtl">١٣</p></td><td><p dir="rtl">P6, 0</p></td><td><p dir="rtl">٨،٢</p></td><td><p dir="rtl">٠,١</p></td><td><p dir="rtl">Comparative example 1-2</p></td></tr><tr><td><p dir="rtl">٩٧</p></td><td><p dir="rtl">١٦</p></td><td><p dir="rtl">٠،٣٣</p></td><td><p dir="rtl">٥،٢</p></td><td><p dir="rtl">٠٤٥</p></td><td><p dir="rtl">Comparative example 2-1</p></td></tr><tr><td><p dir="rtl">٩٧</p></td><td><p dir="rtl">١٦</p></td><td><p dir="rtl">٠،٦٣</p></td><td><p dir="rtl">٩،٩</p></td><td><p dir="rtl">٠،١</p></td><td><p dir="rtl">Comparative example 2-2</p></td></tr>

A separation membrane made from pure porous silicon before coating with nanoceramics.

As shown in Table 1, the carbon dioxide collection rate is higher when using a porous silicone membrane with a nanoceramic material as a separator according to this invention compared to using a porous silicone membrane as a separator. Carbon dioxide can be separated more efficiently in this invention.

Example 3: An example of a method for manufacturing a carbon dioxide separation membrane by mixing silicone rubber raw material, ceramic powder, a curing agent, and an extrusion mixture.

10 First, 980 grams of silicone rubber raw material is prepared.

After that, 100 grams of nanoceramic powder with a grain size of 20 nanometers to 0.5 microns is mixed with 100 grams of benzoyl peroxide, which is the curing agent. The mixture is stirred for a period ranging from 10 to 200 minutes at room temperature. This is for homogeneous mixing of powder

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Nanoceramics and curing agent.

Then, 980 grams of silicone rubber raw material is added to the mixture and kneaded for several hours at room temperature.

After heating the extrusion unit to a temperature of about 100°C, the kneaded mixture of ceramic powder, curing agent and silicone rubber raw material is placed in the extruder hopper. Then, a tube is drawn through the extrusion die, which is shaped like a cross-section of the tube. The tube is cured for less than one hour in an oven heated to a temperature of about 200°C. A sheet separation film can be manufactured in the same way as a tube separation film but can be extruded using a flat sheet extrusion die.

<p dir="rtl">0 1 In this invention, a separator or plate is used, which is made of a porous silicone membrane coated with ceramic. Therefore, this invention can selectively separate carbon dioxide from byproduct gas using a very small pressure difference and a simple method. In this context, this invention can be used on a device to separate carbon dioxide from exhaust gas.</p>

5 1 In addition, since the apparatus operates at room temperature by maintaining the pressure difference between the inside and outside of the separator membrane at a rate of less than 4 kgf/cm2, energy consumption is low. Also, since the apparatus is simple, the cost of the apparatus can be saved. Also, the device can be installed even in dirty water that generates byproduct gas or underwater. This ease of loading makes the device industrially applicable.

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