KR20200093898A - Preparation method of phase material composite using porous carrier - Google Patents

Abstract

A method for manufacturing a phase change material composite using a porous body of the present invention provides excellent stability by sufficiently securing a phase change space and prevents easy destruction due to shear force. In addition, the method for manufacturing a phase change material composite using a porous body of the present invention can contain a large amount of a phase change material in the porous body, and has excellent energy storage efficiency, thereby being used in various industrial fields.

Description

Manufacturing method of phase transition material complex using porous body {PREPARATION METHOD OF PHASE MATERIAL COMPOSITE USING POROUS CARRIER}

The present invention relates to a method of manufacturing a phase change material composite using a porous body, and more particularly, to a method for producing a phase change material composite using a porous body having sufficient stability and not being easily destroyed by shear force, and having excellent energy storage efficiency.

PCM (Phase Change Material), an abbreviation for phase change material, causes its own temperature change (about 10°C) through phase change according to the change of external temperature, which means that endotherm and heat are repeated. If you look at it again, the phase change material has a melting point and a freezing point, so it releases the stored heat at the moment of entering the freezing point and absorbs the surrounding heat at the moment of entering the melting point. The phase change material dissipates heat at a low temperature and absorbs heat at a high temperature to protect any object or living body to which the phase change material is bound from severe temperature changes.

In general, latent heat is heat that is absorbed and released at an isotherm when the phase of a material changes, and 80cal/g of fusion heat absorbed when ice melts or 540cal/g of heat absorbed when water evaporates are typical examples. The method of storing thermal energy using latent heat is called latent heat storage, which can store a larger amount of heat per unit volume or per unit weight than a method of storing thermal energy using sensible heat. In general, the latent heat storage material can store thermal energy using a phase change material whose phase changes at a predetermined temperature. In order to use PCM as a latent heat storage material, the transition temperature should be the desired temperature range, the heat capacity and latent heat should be large, the supercooling phenomenon should be small, non-toxic, environmentally stable, chemically stable, repeatable, and reproducible. In addition, a space is required for the phase change material to phase change, and if it is confined without space, phase change may be difficult.

Accordingly, there is a high interest in technology for encapsulating phase change materials, and the production and manufacturing are performed in a batch process rather than a continuous process. Specifically, the Republic of Korea Patent Publication No. 2003-0018155 provides a technology for microencapsulation by preparing a phase change material into spherical fine particles and then applying a polymer material to the particle surface in one layer or two layers to microencapsulate. Strength and stability were improved.

However, there is still a limitation in that it is insufficient to secure a space for phase change, the safety is low to actively utilize the phase change material, and it is easily destroyed by shear force. There is a need for a technique for a structure or a three-dimensional structure that can replace encapsulation of a phase change material that has sufficient stability and is not easily destroyed by shear forces and can easily withstand.

Republic of Korea Patent Publication No. 2003-0018155

The first problem to be solved by the present invention is to provide a method for manufacturing a phase change material composite using a porous body that has sufficient space for phase change and has improved stability and is not easily destroyed by shear force.

The second problem to be solved by the present invention is to provide a method for manufacturing a phase change material complex using a porous body that is excellent in the content of the phase change material and has excellent energy storage efficiency and can be utilized in various industrial fields.

In order to solve the above problems, the present invention (1) by adding a phase change material to 150 to 300 parts by weight based on 100 parts by weight of the porous body to form a mixture; (2) forming a pre-phase transition material complex by depressurizing the mixture so that a phase change material is impregnated into the pores of the porous body; (3) separating the pre-phase transition material complex by removing the phase transition material not impregnated in the pores of the porous body from the mixture; And (4) obtaining a phase change material complex by coating the surface of the pre-phase change material complex.

According to a preferred embodiment of the present invention, the porous body in step (1) may be any one or more selected from the group consisting of silica, zeolite, bentonite, activated carbon, alumina, silicon carbide, zirconia, and fly ash.

According to a preferred embodiment of the present invention, the pressure reduction in step (2) may be performed under a pressure of 100 ~ 700mmHg.

According to a preferred embodiment of the present invention, step (3) is performed through a centrifugal separation method, the rotation speed may be 70 ~ 140 rpm.

According to a preferred embodiment of the present invention, the coating of the phase change material in step (4) may be performed by any one selected from the group consisting of surface coating and spray coating by mixing.

According to one preferred embodiment of the present invention, in the step (1), the porous body may have a moisture content of 1.5% by weight or less.

Furthermore, the present invention provides a phase change material composite prepared from any one of the above manufacturing methods.

According to a preferred embodiment of the present invention, the phase change material composite may satisfy both of the following conditions (a) and (b).

(a) It should contain 38 to 55% by weight of phase change material.

(b) The phase transition energy amount should be 80 ~ 100J/g

The method of manufacturing a phase change material composite using the porous body of the present invention has an effect that it is possible to sufficiently secure a space for phase change and thus has excellent stability and is not easily destroyed by shear force.

In addition, the method for manufacturing a phase change material complex using the porous body of the present invention may contain a large amount of phase change material in the porous body, and has excellent energy storage efficiency, and thus can be utilized in various industrial fields.

1 is a system diagram of a method for manufacturing a phase change material composite using a porous body according to an embodiment of the present invention.
Figure 2 is a schematic diagram of a phase change material complex using a porous body according to an embodiment of the present invention.
Figure 3 is a graph showing the amount of energy of the phase change material complex according to an embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily practice according to an embodiment of the present invention.

First, terms used in the present invention will be described.

The term'pre-phase transition material complex' refers to materials that can be obtained from the steps prior to obtaining the phase transition material complex of the present invention, by performing additional processes on the materials, the phase transition material complex of the present invention Means that can be obtained.

As described above, in the related art, in order to utilize the phase change material in the industrial field, it was intended to secure stability through encapsulation. However, even in this case, there is still a lack of space for phase change, the safety is low to actively utilize the phase change material industrially, and there are limitations that are easily destroyed by shear force.

Accordingly, the present invention comprises the steps of (1) forming a mixture by adding 150 to 300 parts by weight of a phase change material relative to 100 parts by weight of the porous body; (2) forming a pre-phase transition material complex by depressurizing the mixture so that a phase change material is impregnated into the pores of the porous body; (3) separating the pre-phase transition material complex by removing the phase transition material not impregnated in the pores of the porous body from the mixture; And (4) coating the surface of the pre-phase change material complex to obtain a phase change material complex; to provide a method for preparing a phase change material complex, the solution of the above-described limitation was sought.

Accordingly, the present invention has an effect that it is possible to sufficiently secure a space to be phase shifted, which is excellent in stability, and is not easily destroyed by shear force. In addition, it is possible to contain a large amount of phase change material in the porous body, it has an effect that can be utilized in various industrial fields because of excellent energy storage efficiency.

In this regard, FIG. 1 is a system diagram of a method for manufacturing a phase transition material complex using a porous body according to a preferred embodiment of the present invention. Referring to Figure 1, the method of manufacturing a phase change material composite using a porous body of the present invention is a step of forming a mixture by adding 150 to 300 parts by weight of phase change material with respect to 100 parts by weight of the porous body (S1), the mixture is decompressed free (pre )- forming a phase change material complex (S2), separating the pre-phase change material complex from the mixture (S3) and coating the surface of the pre-phase change material complex to form a phase change material complex. Step (S4) is obtained.

First, (1) step (S1) of forming a mixture by adding a phase change material to 150 to 300 parts by weight with respect to 100 parts by weight of the porous body will be described.

Through the step (1), it is possible to ensure that the phase change material is sufficiently impregnated in the porous carrier, that is, the porous body in which a plurality of pores are formed. Specifically, when the mixture is formed through mixing after the phase change material is added, the phase change material may penetrate into the pores of the porous body. Thereafter, an additional process is performed as described below, so that the phase change material is impregnated into the pores of the porous body to form a complex.

A porous body means a carrier having a plurality of pores, preferably a carrier having one or more pores having a size of 1 to 1000 nm therein, and microporous (pores <2 nm), meso according to the size of the pores It can be divided into a porous (mesoporous, 2 nm <pore <50 nm), a macroporous (macroporous, pore> 50 nm) material.

The porous body can form a phase change material complex by impregnating a phase change material inside the pore, and can be used without any size limitation if it is commonly used in the art, and preferably silica, alumina, niobium, tantalum, and zirconium. , Carbon, magnesium, titanium, and any one or more selected from the group consisting of polymers, MPS (mesoporous silica), MCM (mobil composition of matter), SBA (Santa Barbara materials), CNS (MPS with cyanofuntional groups), OMC It can be used in the form of (ordered mesoporous carbon), MCF-C (mesocellular carbon foam) or SCMS (supplementary cementitious materials), and more preferably MCF (mesocellular foam).

In addition, the porous body may be dried to remove moisture before performing step (1). In addition, the drying may be performed for 2 to 4 hours at a temperature of 100 ~ 130 ℃.

According to a preferred embodiment of the present invention, in the step (1), the porous body may have a water content of 0.1 to 2% by weight. In this case, since the porous body is in a state where impurities and moisture are removed, it can be usefully used for the production of a phase change material complex.

Phase change material (PCM) is a substance that causes phase change at various temperatures, and can be classified into organic and inorganic materials, and vegetable that can be obtained from nature. Examples of organic materials include materials such as tetradecane, octadecane, and nonadecan, which are hydrocarbon-based hydrocarbons, and examples of inorganic materials include hydrate-type calcium chloride.

The phase change material of the present invention can be used without limitation as long as it can be impregnated into the porous body to form a phase change material complex. Preferably, it may include a hydrated inorganic salt, polyhydric alcohol, PET-PEG copolymer, PEG, PTMG or a linear chain hydrocarbon.

In addition, the step (1) is 150 to 350 parts by weight of the phase change material relative to 100 parts by weight of the porous body to form a mixture. As described above, by adding the phase change material in an excess amount compared to the porous body content, and mixing to form a mixture, it is possible to improve the efficiency of the phase change material penetration into the porous body.

More preferably, a phase change material may be added in an amount of 180 to 320 parts by weight with respect to 100 parts by weight of the porous body, and more preferably, a phase change material may be added in an amount of 200 to 300 parts by weight with respect to 100 parts by weight of the porous body.

If the phase change material is added in excess of the above range, if the phase change material is added below the above range, the phase change material does not sufficiently penetrate the porous body, resulting in a problem that the content of the phase change material in the phase change material complex is lowered. Can.

Next, (2) the step (S2) of forming the pre-phase transition material complex by depressurizing the mixture so that the phase transition material is impregnated into the pores of the porous body will be described.

Through the step (2), the phase change material can be effectively impregnated into the pores of the porous body to form a pre-phase change material complex. Through the depressurization, the content of the phase change material impregnated in the pores of the porous body may be enhanced.

Further, the porous body has a plurality of pores formed therein, and can function as a carrier. When a phase change material is impregnated in a plurality of pores of a porous body, a certain amount of phase change materials may be dispersed and impregnated into a plurality of pores. Through this, it is possible to efficiently secure the phase change space of the phase change material, thereby improving stability.

Specifically, the impregnation method of infiltrating/impregnating a phase change material into a porous body having a structure such as a porous inorganic material, when the phase change material is impregnated into the porous body, the phase change material stays in the space between the pores, surfaces, and particles of the porous body.

In the related art, when a heat storage material impregnated with a phase change material in the porous body is used as an additive for the polymer material, the phase change material that does not stay in the pores of the porous body is dispersed between the polymer materials, resulting in insufficient space for phase change and insufficient space for phase change. There was a limit to the loss of phase transition energy.

Accordingly, the present invention can make the phase change material impregnate the pores of the porous body as much as possible by impregnating the phase change material more effectively.

In this regard, Figure 2 is a schematic diagram of a phase change material complex using a porous body according to an embodiment of the present invention. Referring to FIG. 2, the porous body 10 used in the phase change material composite 1 of the present invention has a plurality of pores. The phase change material 20 is impregnated in the pores of the porous body 10, and thereafter, it is possible to obtain the phase change material composite 1 of the present invention through predetermined treatment processes.

According to a preferred embodiment of the present invention, the pressure reduction in step (2) may be performed at a pressure of 700 mmHg or less. More preferably, the reduced pressure may be performed at a pressure of 600 mmHg or less, and more preferably, may be performed under a pressure of 50 to 500 mmHg.

When the pressure reduction is performed in the above range, phase change materials can be easily penetrated and impregnated into the pores of the porous body. Accordingly, it is possible to manufacture a phase change material complex containing a high content of a phase change material, and the step of performing the impregnation can be performed by a simple process, thereby increasing process efficiency.

If the depressurization in step (2) is performed in excess of the above range, a problem that impregnation of the phase change material may not be efficiently performed. In addition, if the pressure reduction in step (2) is performed below the above range, the phase change material is excessively added to the pores of the porous body, making it difficult to secure the phase change space of the phase change material, and the stability of the phase change material complex is deteriorated. Problems may arise.

On the other hand, the phase change material'impregnated' inside the pores of the porous body may be impregnated in a state where the phase change material is filled inside the carrier and without physical bonding.

When the phase change material is impregnated in the pores of the porous body, a pre-phase change material complex capable of forming the phase change material complex may be formed through a predetermined treatment process.

As described above, the pre-phase transition material complex refers to materials that can be obtained from the steps prior to obtaining the phase transition material complex of the present invention, and additional processes are performed on the materials to perform the phase transition material of the present invention. It may mean materials capable of obtaining a complex.

In this case, the pre-phase transition material complex formed through the step (2) may exist together with phase transition materials that are not impregnated into the porous body in the mixture, and the phase transition material is separated from the mixture to perform coating. It can be a complex.

According to a preferred embodiment of the present invention, after performing the depressurization in step (2), an ultrasonic treatment process is further performed so as to ultrasonicate the phase change material present on the surface of the porous body to penetrate into the pores of the porous body. can do. The ultrasonic treatment may improve the impregnation efficiency by allowing the phase change material attached to the surface of the porous body to move and finely disperse using an ultrasonic generator.

In addition, it is preferable that the ultrasonic treatment is performed at a temperature of 0 to 20° C. or higher, and a frequency range of 10 to 100 kHz, for 15 to 60 minutes, than the maximum value of the phase transition temperature range of the phase change material.

Next, the step (S3) of separating the pre-phase transition material complex by removing the phase transition material not impregnated into the pores of the porous body from the mixture (3) will be described.

Through the step (3), a pre-phase transition material complex can be separated from a mixture of a pre-phase transition material complex and an unimpregnated phase transition material. At this time, the term'unimpregnated phase transition material' means that the pores of the porous body are not impregnated because they are added in excess of the porous body in step (1).

According to a preferred embodiment of the present invention, step (3) is performed through a centrifugation method, and the rotation speed may be 70 to 140 rpm.

Using the centrifugal separation method, the mixture may be separated into a phase change material and a pre-phase change material complex that are not impregnated into the pores of the porous body according to centrifugal force. Accordingly, the pre-phase transition material complex can be easily separated, thereby improving the efficiency of the process.

More preferably, the rotation speed when performing the centrifugation method may be 80 ~ 120 rpm. If the rotational speed exceeds the above range, the rotational speed may be too high, so that the phase transition material carried on the pre-phase transition material complex is separated, thereby causing a problem that the impregnation rate of the phase transition material for the porous body is lowered. . In addition, if the rotational speed is less than the above range, there may be a problem that separation of the pre-phase transition material complex and the unimpregnated phase transition material is not efficiently performed.

On the other hand, at this time, the temperature of the phase change material, the centrifuge inside and the porous body is preferably about 5 ~ 20 ℃ higher than the maximum value of the phase change temperature range of the phase change material. If the temperature is lower than the above range, a problem may be caused that the impregnation rate of the phase change material to the porous body is lowered due to the volume expansion of the phase change material.

In addition, the centrifugal separation method may be performed for a time suitable for separating the mixture into a phase change material and a pre-phase change material complex that are not impregnated into the pores of the porous body, and preferably may be performed for 15 to 60 minutes. have.

Next, (4) step (S4) of obtaining a phase change material composite by coating the surface of the pre-phase change material composite will be described.

Through the step (4), the surface of the pre-phase change material composite may be coated, and accordingly, the impregnation rate of the phase change material to the porous body may be improved.

The coating proceeds with a polymer dispersion such as PU emulsion, EVA emulsion, rubber latex, and acrylic emulsion, and can be performed through a spray dryer or oven and natural drying, which is a method of removing moisture after a simple mixing process using a blender.

According to a preferred embodiment of the present invention, the coating of the phase change material in step (4) may be carried out by any one selected from the group consisting of mixed coating, surface coating and spray coating through simple stirring. More preferably, it may be performed by spray coating.

Furthermore, the present invention provides a phase change material composite prepared from any one of the above manufacturing methods.

Accordingly, the present invention can provide a phase change material complex having an improved impregnation rate of the phase change material, and the phase change material complex can sufficiently secure a phase change space in a polymer matrix, thereby reducing phase change energy to exhibit improved phase change energy performance. Can. In addition, it is possible to sufficiently secure a space to be phase shifted, and thus has excellent stability and has an effect of not being easily destroyed even by shearing force.

According to a preferred embodiment of the present invention, the phase change material composite may satisfy both of the following conditions (a) and (b).

(a) It should contain 38 to 55% by weight of phase change material.

(b) The phase transition energy amount should be 80 ~ 100J/g

The present invention, by containing the phase change material in 38 to 55% by weight, it is possible to contain a large amount of phase change material can provide a phase change material composite excellent in the impregnation rate of the phase change material. In addition, the present invention can store the phase change energy in the above range, it is possible to provide a phase change material composite using a porous body having excellent energy storage efficiency.

More preferably, the phase change material complex may include 40 to 60% by weight of the phase change material. When the phase change material is included in the above range, the impregnation rate is excellent, but the phase change space of the phase change material can be secured efficiently. Accordingly, there is an effect of providing a phase change material composite having excellent stability and excellent energy storage efficiency.

Hereinafter, the present invention will be described in more detail through specific examples.

Example One

The porous carrier silica was dried such that the water content was 2% by weight or less. Then, 200 parts by weight of a phase change material (rubitherm (Germany) RT 24) was added to 100 parts by weight of the silica, followed by stirring to prepare a mixture. After putting the mixture in a vacuum oven, the pressure was reduced to 600 mmHg, and then left for 45 minutes, so that the phase change material was impregnated into the silica. A pre-phase transition material complex was formed. The pre-phase transition material complex was introduced into a centrifuge, and centrifugation was performed at 100 rpm to separate excess phase transfer material not supported on silica from the mixture. At this time, the centrifugation was performed until 66% by weight of the total amount of phase change material added with an excess of phase change material not supported on silica.

Example 2

It was carried out in the same manner as in Example 1, except that it was carried out according to the experimental conditions shown in Table 1.

Example 3

It was carried out in the same manner as in Example 1, except that it was carried out according to the experimental conditions shown in Table 1.

Example 4

After carrying out according to the experimental conditions shown in Table 1, the surface of the pre-phase transition material complex was mixed with an acrylic emulsion solid content (about 40%) and dried to obtain a phase transition material complex coated with a coating on the surface. It carried out similarly to Example 1.

Comparative example One

It was carried out in the same manner as in Example 1, except that it was carried out according to the experimental conditions shown in Table 1.

Comparative example 2

It was carried out in the same manner as in Example 1, except that it was carried out according to the experimental conditions shown in Table 1.

Table 1

Experimental Example One

The content of the phase change material impregnated in the phase change material composite prepared through Examples and Comparative Examples was measured and is shown in Table 2.

Experimental Example 2

Table 2 shows the amount of phase change energy of the phase change material composites prepared through Examples and Comparative Examples.

Experimental Example 3

Table 2 shows the appearance of the phase change material composites prepared through Examples and Comparative Examples.

Table 2

Referring to Table 2, it can be seen that in Examples 1 to 4, the phase transition energy amount is higher than Comparative Example 1 and Comparative Example 2. In addition, it can be seen that the content of the impregnated phase change material also has a higher value in the case of Example 1 to Example 4 than Comparative Example 1 and Comparative Example 2.

Figure 3 is a graph showing the amount of energy of the phase change material complex according to an embodiment of the present invention. Referring to FIG. 3, it can be confirmed that in the case of Examples 1 to 4, the phase transition energy amount has a significantly higher value than Comparative Example 1 and Comparative Example 2.

Claims (8)

(1) forming a mixture by adding 150 to 300 parts by weight of a phase change material relative to 100 parts by weight of the porous body;
(2) forming a pre-phase transition material complex by depressurizing the mixture so that a phase change material is impregnated into the pores of the porous body;
(3) separating the pre-phase transition material complex by removing the phase transition material not impregnated in the pores of the porous body from the mixture; and
(4) obtaining a phase change material complex by coating the surface of the pre-phase change material complex.
According to claim 1,
In the step (1), the porous body is a phase transition material composite manufacturing method characterized in that at least one selected from the group consisting of silica, zeolite, bentonite, activated carbon, alumina, silicon carbide, zirconia and fly ash.
According to claim 1,
Decompression of the step (2) is a phase change agent complex, characterized in that is performed under a pressure of 700mmHg.
According to claim 1,
The step (3) is performed through a centrifugal separation method, the rotational speed is 70 ~ 140 rpm method for producing a phase change material complex.
According to claim 1,
In the step (4), the method of manufacturing a phase change material composite is characterized in that the coating of the phase change material is performed by any one selected from the group consisting of surface coating and spray coating by mixing.
According to claim 1,
In the step (1), the porous body is a phase change material composite manufacturing method characterized in that the moisture content is 1.5% by weight or less.
Claims 1 to 6 of the phase change material composite prepared from the manufacturing method.
The method of claim 7,
Phase transition material complex characterized in that it satisfies both of the following conditions (a) and (b).
(a) The phase change material should contain 38 to 55% by weight.
(b) The phase transition energy amount should be 80~100J/g or more.

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