KR20210045587A - Adsorbent Using Alginate Gel and Manufacturing Method thereof - Google Patents

Abstract

The present invention provides an adsorbent and manufacturing method thereof, wherein the adsorbent comprises: a support; and an alginate gel formed on the surface of the support. The alginate gel is manufactured by a reaction of a polyvalent cation solution and 0.5 to 2 wt% of an aqueous alginate solution. Thus, the adsorbent is excellent in removing harmful substances such as fine dust, volatile organic compounds (VOCs), cigarette smoke, food odors and bad smell in an eco-friendly and economical way.

Description

Adsorbent Using Alginate Gel and Manufacturing Method thereof TECHNICAL FIELD

The present invention relates to an adsorbent using an alginate gel and a method for manufacturing the same, and specifically, to remove by adsorbing fine dust, volatile organic compounds (VOCs), cigarette smoke, food odor and odor contained in the air. It relates to an adsorbent using an alginate gel and a method for preparing the same.

Alginate is a natural material derived from polysaccharides that can be extracted from seaweed or kelp, and usually exists in the form of granules such as sodium alginate or potassium alginate. The molecular formula is (C ₆ H ₆ O ₆ ) _n , which is an acid in the form of a chain, but it exists as a weak acid due to its low ionization degree, and has excellent biocompatibility, low toxicity, and low cost. The main constituents of alginate are D-mannuronic acid (M) and L-gluronic acid (G) (Nelson & Cretcher, 1929; Fischer & Dorfel, 1955). M blocks, G blocks, and MG blocks are formed. The composition ratio of M and G can vary depending on the seaweed from which the alginate is derived, so alginate containing a lot of G is stable and strong against heat, but forms a brittle gel, and alginate containing a lot of M is weak against fire and has excellent elasticity. Forms a gel. In addition, depending on the type of divalent cation to be bonded, the ionic crosslinking structure changes and the physical properties change (Lee & Mooney, 2012).

Alginate has excellent biocompatibility and low toxicity, and has been widely used in various fields such as tissue engineering as well as cooking as a medical material. For example, alginate gel is used as a tooth pattern or as an artificial tissue support (Jae-Won Lee & Geun-Yong Lee, 2011), and recently, a drug delivery mechanism using alginate beads or a method of application as a stem cell culture have been actively studied. In addition, alginate is known to adsorb and solidify heavy metals such as cadmium, barium, copper, and manganese, as well as radioactive materials such as strontium 90, and has been in the spotlight as a way to environmentally remove heavy metal contamination from water resources.

In the present invention, by using the adsorption properties of the alginate gel to remove harmful substances such as VOC and fine dust, it is intended to present a technical method that can utilize alginate gel as an eco-friendly air purification means.

<prior art literature>

Nelson, W. L., & Cretcher, L. H. (1929). THE ALGINIC ACID FROM MACROCYSTIS PYRIFERA1,2. Journal of the American Chemical Society, 51(6), 1914-1922. doi:10.1021/ja01381a045

Progress in Polymer Science, 37(1), 106-126. doi:10.1016 / j.progpolymsci. 2011.06.003

Lee, G., & Lee, J. (2011). Alginic acid hydrogel for tissue regeneration. Polymer Science and Technology, 22(1), 34-70.

An object of the present invention is to solve the technical problems that have been requested from the past as described above.

Specifically, an object of the present invention is to provide an adsorbent using alginate gel that can remove harmful substances such as fine dust, volatile organic compounds (VOCs), cigarette smoke, food odor and odor contained in the air using alginate gel. To provide.

An object of the present invention is to provide a method for producing an adsorbent using alginate gel that can remove harmful substances in an economical and environmentally friendly manner.

The present invention,

Support; And

Including; alginate gel formed on the surface of the support,

The alginate gel provides an adsorbent using an alginate gel prepared by a reaction of a polyvalent cation solution and an alginate aqueous solution of 0.5 to 2% by weight.

The support may be at least one selected from the group consisting of pure paper, paper towel, filter paper, dishcloth, and felt.

The polyvalent cation may be one or more selected from the group consisting ^{of Ca 2+} , Sr ^2+, and Co ^2+.

The polyvalent cation solution may be 0.5 to 2% by weight.

When the amount of the polyvalent cation solution is less than 0.5% by weight, the alginate gel cannot be sufficiently obtained, and the intended effect of the present invention cannot be obtained, and when it exceeds 2% by weight, side reactions may occur, which is not preferable. Specifically, it may be 1 to 2% by weight.

The alginate aqueous solution may be an aqueous sodium alginate solution.

The adsorbent may include 2 or 3 layers of alginate gel formed on the surface of the support.

The adsorbent may adsorb and remove one or more harmful substances selected from the group consisting of fine dust, volatile organic compounds (VOCs), cigarette smoke, food odor, and odor contained in the air.

In addition, the present invention

The process of preparing the support;

Immersing the support in 0.5 to 2% by weight of alginate aqueous solution for 10 to 60 seconds;

Taking out the support immersed in the alginate aqueous solution and immersing it in the polyvalent cation solution for 0.5 to 2 minutes; And

It provides a method for preparing an adsorbent using an alginate gel comprising a step of drying for 20 to 40 minutes after removing the support immersed in the polyvalent cation solution.

As the adsorbent according to the present invention uses alginate, a non-toxic natural polymer, it can remove harmful substances such as fine dust, volatile organic compounds (VOCs), cigarette smoke, food odor and odor contained in the air in a very eco-friendly and efficient way. I can.

As the adsorbent according to the present invention uses alginate gel formed on the surface of the support, it is possible to efficiently remove harmful substances without causing secondary pollutants, and at the same time, the deterioration of the adsorption performance is low when repeatedly used, so it is excellent in economy.

1 is a photograph showing whether alginate gel was formed according to metal cations in Experimental Example 1-1;
2 is a result of measuring the strength of the alginate gel according to the metal cation in Experimental Example 1-1;
3 is a result of measuring the water absorption rate of the support in Experimental Example 1-2.
4(a) to (d) are results showing the adsorption trend and final adsorption rate of PM2.5 and PM10 by production concentration in Experimental Example 2;
5(a) to (c) are results showing the IPA adsorption trend and final adsorption rate by production concentration in Experimental Example 3-1;
6(a) to (c) are results showing the IPA adsorption trend and final adsorption rate for each thickness in Experimental Example 3-2;
7 (a) and (b) are results showing the adsorption rate of VOCs in Experimental Example 4;
8 is a result showing the adsorption rate of fine dust of the adsorbent completely dried in Experimental Example 5;
9 is a photograph confirming the regeneration of the adsorbent in Experimental Example 6-1;
10 is a graph showing the adsorption trend and adsorption rate according to the reuse of the adsorbent in Experimental Example 6-2; And
11 is a result of a PM10 fine dust adsorption experiment and a VOC (ISA) adsorption experiment in Experimental Example 7.

The present invention,

Support; And

Including; alginate gel formed on the surface of the support,

The alginate gel provides an adsorbent using an alginate gel prepared by a reaction of a polyvalent cation solution and an alginate aqueous solution of 0.5 to 2% by weight.

As the adsorbent according to the present invention uses alginate, a non-toxic natural polymer, it can remove harmful substances such as fine dust, volatile organic compounds (VOCs), cigarette smoke, food odor and odor contained in the air in a very eco-friendly and efficient way. I can. In addition, since the adsorbent uses alginate gel formed on the surface of the support, it can efficiently remove harmful substances without causing secondary contaminants, and at the same time, the deterioration of the adsorption performance is low when repeatedly used, which is excellent in economy.

When the content of the alginate aqueous solution is 0.5% by weight or less, the pores of the net structure formed by the alginate are too large to obtain the intended effect of the present invention, and when it exceeds 2% by weight, the alginate polymerization reaction occurs excessively, causing the surface of the support to be damaged. It is not preferable because it can be covered smoothly and the area available for adsorption can be reduced. Specifically, the alginate aqueous solution content may be 1 to 2% by weight.

The support may be at least one selected from the group consisting of pure paper, paper towel, filter paper, dishcloth, and felt, and in detail, it may be a paper towel.

The polyvalent cation ^{may be one or more selected from the group consisting of Ca 2+} , Sr ²⁺ and Co ²⁺ , and in detail, it may be ^{Ca 2+} which is commonly found in organisms and is relatively free from environmental pollution problems.

The polyvalent cation solution may be 0.5 to 2% by weight.

The alginate aqueous solution may be an aqueous sodium alginate solution.

The adsorbent may include 2 or 3 layers of alginate gel formed on the surface of the support.

The two or three-ply alginate gel can be obtained by repeating the manufacturing process of the alginate gel prepared according to the present invention two or three times.

The adsorbent may adsorb and remove one or more harmful substances selected from the group consisting of fine dust, volatile organic compounds (VOCs), cigarette smoke, food odor, and odor contained in the air.

Representatively, the fine dust may be PM2.5 and PM10. The volatile organic compound is not limited as long as it is known in the art, but may be, for example, a polar volatile organic compound such as methanol, acetic acid, isopropanol, acetone, and formaldehyde, and a non-polar volatile organic compound such as hexane, and toluene. Since alginate exhibits polarity, the adsorption capacity of the polar volatile organic compound may be relatively higher.

In addition, the present invention is a method for producing an adsorbent using the alginate gel,

The process of preparing the support;

Immersing the support in 0.5 to 2% by weight of alginate aqueous solution for 10 to 60 seconds;

Taking out the support immersed in the alginate aqueous solution and immersing it in the polyvalent cation solution for 0.5 to 2 minutes; And

It provides a step of drying for 20 to 40 minutes after taking out the support immersed in the polyvalent cation solution.

If the immersion time of the alginate aqueous solution is too short, the intended effect of the present invention cannot be obtained, and if the immersion time is too long, the support may be damaged, which is not preferable.

If the immersion time of the polyvalent cation solution is too short, the intended effect of the present invention cannot be obtained, and if the immersion time is too long, the support may be damaged, which is not preferable.

Hereinafter, an embodiment of the present invention will be described in detail. However, the following examples are only illustrative of the present invention, and the contents of the present invention are not limited to the following examples.

Manufacturing Example 1-1

For alginate gel formation, 1% by weight (% g/mL) CaCl ₂ A 1 wt% (% g/mL) alginate aqueous solution was added dropwise to the solution.

Preparation Examples 1-2 to 1-5

For alginate gel formation, each of 1% by weight (% g/mL) of Sr ²⁺ (Preparation Example 1-2), Co ²⁺ (Preparation Example 1-3), Cu ²⁺ (Preparation Example 1-4), And 1% by weight (% g/mL) alginate aqueous solution was added dropwise to the chloride of ^{Fe 2+ (Preparation Example 1-5).}

Experimental Example 1-1

In Preparation Examples 1-1 to 1-5, the Young's Modulus was calculated to determine whether alginate gel was formed, and to measure its strength. In order to calculate the Young's modulus, an alginate gel film was formed, and the thickness, length, and width of the film were measured using a ruler and a caliper. Apply a load to one end of the film, measure the force and elongated length using a force meter and a ruler, and calculate the Young's modulus by substituting it into the following equation. The higher the Young's modulus, the higher the strength of the gel is considered.

1 is a photograph of an alginate gel thus formed. According to this, it can be seen that the alginate gel was formed in Preparation Examples 1-1 to 1-4 excluding Preparation Example 1-5. This is because in the case of Preparation Example 1-5, formation of an ionic crosslinked structure is very slow and weak in the ^{Fe 2+ state, and it is difficult to form an alginate gel.}

2 is a graph measuring the strength of the alginate gel thus formed. According to this, as a result of measuring the Young's modulus, Preparation Example 1-4 (Cu ²⁺ ), Preparation Example 1-1 (Ca ²⁺ ), Preparation Example 1-2 (Sr ²⁺ ), Preparation Example 1-3 (Co ²⁺⁾ ) Was measured high in the order of. Preparation Example 1-4 (Cu ²⁺ ) forms the strongest alginate gel, but Cu ²⁺ is Since it may cause contamination problems when exposed to the environment with heavy metal ions, ^{the alginate gel according to Preparation Example 1-1 (Ca 2+} ), which is commonly found in organisms and relatively free from environmental contamination problems, is considered to be the most suitable.

Manufacturing Example 2-1

37g of pureed paper was prepared as a support.

Preparation Examples 2-2 to 2-6

As a support, 80 g of pure paper (Production Example 2-2), paper towel (Production Example 2-3), filter paper (Production Example 2-4), dishcloth (Production Example 2-5), and felt paper (Production Example 2-6), respectively. ) Was prepared.

Experimental Example 1-2

The support according to Preparation Examples 2-1 to 2-6 was cut into a width of 1.5 cm and a height of 15 cm, and the lower 0.5 cm was immersed in water, and the water absorption rate according to the height of the water was measured and shown in FIG. 3 below.

According to FIG. 3, it can be seen that the water absorption heights of Preparation Example 2-1 (37g pure paper) and Preparation Example 2-3 (paper towel) each exhibit the highest water absorption rate of about 12 cm or more. Preparation Example 2-1 (80 g of pure paper) absorbed about 11 cm of water, and Preparation Example 2-4 (filter paper), Preparation Example 2-5 (cloth cloth), and Preparation Example 2-6 (felt paper) were 8 cm Showed a low water absorption rate of less than. Preparation Example 2-1 (37g pure paper) and Preparation Example 2-3 (paper towel) show the best water absorption, but pure paper has some advantages in maintaining the shape of the support due to its dense and stiff structure, but economical compared to paper towels It is disadvantageous in terms of accessibility and accessibility. Therefore, it is judged that Preparation Example 2-3 (paper towel), which can be obtained easily and inexpensively while showing a compliant water absorption rate, is suitable as a support.

Example 1

Paper towels were immersed in 1% by weight (% g/mL) alginate aqueous solution for 30 seconds, then removed and CaCl ₂ It was immersed in 1% by weight (% g/mL) aqueous solution for 1 minute. This was taken out and dried for 30 minutes to prepare an adsorbent having alginate gel formed on the surface of the paper towel.

Example 2

The same adsorbent as in Example 1 was prepared, except that 0.5% by weight of alginate aqueous solution was used in Example 2.

Example 3

The same adsorbent as in Example 1 was prepared, except that a 2% by weight aqueous alginate solution was used in Example 2.

Example 4

After preparing an adsorbent in which one layer of alginate gel was formed on the surface of a paper towel according to Example 1, the same process was repeated two more times to prepare an adsorbent having three layers of alginate gel formed on the surface of the paper towel.

Example 5

After preparing an adsorbent in which one layer of alginate gel was formed on the surface of a paper towel according to Example 2, the same process was repeated two more times to prepare an adsorbent having three layers of alginate gel formed on the surface of the paper towel.

Example 6

After preparing an adsorbent in which one layer of alginate gel was formed on the surface of a paper towel according to Example 3, the same process was repeated twice to prepare an adsorbent having three layers of alginate gel formed on the surface of the paper towel.

Comparative Example 1

A dry paper towel was prepared.

Comparative Example 2

A water-soaked paper towel was prepared.

Experimental Example 2

Each of the adsorbents prepared in Examples 1 to 3 and the paper towels of Comparative Examples 1 and 2 were each prepared and attached to the wall of a 40 x 40 x 40 cube acrylic cylinder on a total of 4 sides to conduct an adsorption experiment. .

A fine dust environment of PM 2.5 or PM 10 is created by injecting tobacco smoke into the acrylic container for about 1 second and sealing it. The trend of adsorption of fine dust was observed every 10 minutes through a fine dust measuring device arranged in the center, and is shown in FIGS. 4(a) to (d) below.

4(a) to (d), it can be seen that the adsorbents according to Examples 1 to 3 exhibit a high adsorption rate of fine dust compared to the control (empty acrylic box) and the paper towels according to Comparative Examples 1 and 2. .

The adsorbent according to Example 1 (1 wt% alginate aqueous solution) showed the best adsorption rate in both PM2.5 and PM10, and particularly, in the case of PM10, it showed an adsorption rate of about 70% or more. In the case of the adsorbent according to Example 2 (0.5% by weight alginate aqueous solution), the amount of alginate is too small, so that the pores of the net structure formed on the surface of the support become too large, which may be disadvantageous for trapping fine dust, and Example 3 (2% by weight alginate) In the case of the adsorbent according to the aqueous solution), the amount of alginate is too high and the gel polymerization reaction occurs too much to smoothly cover the surface of the rough paper towel. It is judged to be.

However, even in the control group without any treatment on the acrylic barrel, it appears that the concentration of fine dust naturally decreases by about 40% after about 70 minutes, which is believed to be due to fine dust adsorbed on the walls and floors due to static electricity of acrylic material. .

Experimental Example 3-1

Using the adsorbents prepared in Examples 1 to 3 and the paper towels of Comparative Examples 1 and 2, respectively, an adsorption experiment of Isopropyle Alcohol (IPA), which is one type of VOC, was conducted. After applying IPA lightly to the tip of a toothpick, the tube was sealed for about 1 second, and the adsorption behavior was measured every 10 minutes through a VOC meter, and are shown in FIGS. 5(a) to (c) below.

According to this, it was confirmed that the adsorbents according to Examples 1 to 3 showed a high IPA adsorption rate compared to the control (empty acrylic box) and the paper towels according to Comparative Examples 1 and 2. In particular, in the case of the adsorbent according to Example 2 (0.5 wt% alginate aqueous solution), IPA was initially rapidly adsorbed, but the adsorption efficiency rapidly decreased over time, and the final adsorption rate was Example 1 (1 wt% alginate aqueous solution) and It showed a lowering phenomenon compared to Example 3 (2% by weight alginate aqueous solution). The adsorption rate was reversed around 40 minutes, which is thought to occur because the net structure of the alginate gel surface of Example 2 (0.5 wt% alginate aqueous solution) was rapidly saturated. Examples 1 and 3 showed no significant difference in the adsorption rate weight or the final adsorption rate. This is interpreted as because the effect of the net density on the gel surface on the IPA adsorption mechanism decreases after a certain concentration. Unlike fine dust, the IPA concentration in the control group (empty acrylic box) did not decrease naturally. This means that the electrostatic properties of the acrylic barrel are independent of VOC adsorption.

Experimental Example 3-2

Using the adsorbents prepared in Examples 4 to 6, respectively, an adsorption experiment of Isopropyle Alcohol (IPA), which is one type of VOC, was conducted. IPA was slightly buried at the tip of the toothpick, and then the tube was sealed for about 1 second, and the adsorption behavior was measured every 10 minutes through a VOC meter, and are shown in Figs. 6(a) to (c).

6(a) to (c) show the IPA adsorption trend and final adsorption rate by thickness of the adsorbent.

In the case of the adsorbent according to Example 2 (0.5 wt% alginate aqueous solution), it was confirmed that the thicker the thickness, the more finally adsorbed, but the adsorbent according to Example 1 (1 wt% alginate aqueous solution) and Example 3 (2 wt% alginate aqueous solution) % Alginate aqueous solution), there was no significant difference in the final adsorption rate. In the case of all three-ply thicknesses, IPA was rapidly adsorbed at the beginning, but the efficiency rapidly decreased as time passed, showing an overall exponential adsorption trend. In the case of one ply, it showed a linear adsorption trend at a constant rate. Accordingly, it is judged that the adsorption mechanism mainly occurs on the surface of the gel.

Experimental Example 4

Using the adsorbent prepared in Example 1, the adsorption trends of methanol, acetic acid, isopropanol, acetone, formaldehyde, hexane, and toluene were confirmed as VOCs.

The material was slightly buried at the tip of a toothpick, and then put in for about 1 second, the container was sealed, and the adsorption behavior was measured every 10 minutes through a VOC measuring device, and are shown in FIGS. 7(a) and (b) below.

7(a) and (b), it can be seen that the adsorbent according to Example 1 shows a difference in the adsorption capacity of non-polar and polar VOCs. Non-polar VOCs, hexane and toluene, decreased by about 60% over a period of 60 minutes, but polar VOCs, ethanol, acetic acid, isopropanol, acetone, and formaldehyde, all showed a reduction of more than 80%. This seems to be because alginate is a material showing polarity and causes dipole-dipole interaction with polar VOCs.

Experimental Example 5

The adsorption rate of fine dust through the experiment according to Experimental Example 2 by completely drying the adsorbent prepared in Example 1 is shown in FIG. 8 below.

According to FIG. 8, when the adsorbent prepared in Example 1 was completely dried, the adsorption rate of fine dust was decreased by about 25% compared to the adsorbent of Example 1 that did not go through the complete drying process. This is because the volume of the alginate gel increases when there is a lot of moisture in the gel, the surface area of the microporous structure increases, and the viscosity of the gel increases.When the gel is dried, the volume decreases and the surface area of the micropore structure decreases and the viscosity decreases, resulting in adsorption capacity. It seems to be diminishing. In other words, it can be seen that the adsorption rate decreases as the amount of fine dust trapped by the surface tension of moisture decreases, and it can be seen that the adsorption performance of alginate gel is guaranteed in an environment where moisture is sufficiently supplied.

Experimental Example 6-1

After completely drying the adsorbent according to Example 1, it was shown in FIG. 9 to confirm the regeneration by supplying moisture again.

According to this, when moisture is supplied to the dried adsorbent, the original volume and texture are regenerated as shown in FIG. 9 below.

Experimental Example 6-2

For the adsorbent according to Example 1, PM2.5 and PM10 fine dust adsorption experiments and VOC (ISA) adsorption experiments were performed (first use) with reference to Experimental Examples 2 and 3. After completely drying it, water was supplied again to perform the experiment again (first reuse). After completely drying it, water was supplied again to perform the experiment again (second reuse). The results are shown in Figures 10 (a) and (b) below.

According to FIGS. 10(a) and (b), the efficiency of adsorption of fine dust decreases by about 20% compared to the first use during the first reuse. It is believed that the efficiency decreases as all the fine dust adsorbed to the alginate gel net structure is not removed during the drying process. During the second reuse, the fine dust adsorption efficiency did not significantly decrease further. In the case of adsorption of VOCs, the adsorption efficiency did not significantly decrease compared to fine dust during reuse. This is presumed to be because most of the VOCs volatilize during the drying process.

Therefore, even if the adsorbent according to the present invention is reused several times, it is judged that there will be no big problem in terms of utility, and whether it can be reused when commercialized will serve as a great economic advantage.

Experimental Example 7

Prototype of the adsorbent according to Example 1 was prepared, and PM10 fine dust adsorption experiment and VOC (ISA) adsorption experiment were conducted in a room of 2.3 mx 2 mx 2 m with reference to Experimental Examples 2 and 3 ) And shown in Figs. 11 (a) and (b) below.

11(a) and (b), it can be seen that after 12 hours, the PM10 in the room decreased by 80%, and the VOC (ISA) decreased by 81%.

Claims (8)

Support; And
Including; alginate gel formed on the surface of the support,
The alginate gel is an adsorbent using an alginate gel, characterized in that prepared by a reaction of a polyvalent cation solution and 0.5 to 2% by weight of an alginate aqueous solution. The adsorbent according to claim 1, wherein the support is at least one selected from the group consisting of pure paper, paper towel, filter paper, dishcloth, and felt. The adsorbent according to claim 1, wherein the polyvalent cation is at least one selected from the group consisting ^{of Ca 2+} , Sr ²⁺ and Co ^2+. The adsorbent according to claim 1, wherein the polyvalent cation solution is 0.5 to 2% by weight. The adsorbent according to claim 1, wherein the alginate aqueous solution is an aqueous sodium alginate solution. The adsorbent according to claim 1, wherein the adsorbent comprises two or three layers of alginate gel formed on the surface of the support. The method of claim 1, wherein the adsorbent adsorbs and removes one or more harmful substances selected from the group consisting of fine dust, volatile organic compounds (VOCs), cigarette smoke, food odor, and odor contained in the air. Adsorbent using alginate gel. The process of preparing the support;
Immersing the support in 0.5 to 2% by weight of alginate aqueous solution for 10 to 60 seconds;
Taking out the support immersed in the alginate aqueous solution and immersing it in the polyvalent cation solution for 0.5 to 2 minutes; And
Drying for 20 to 40 minutes after taking out the support immersed in the polyvalent cation solution; method for producing an adsorbent using alginate gel comprising a.

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