KR20200056343A - Adsorbent for offensive order removal and method to manufacture thereof - Google Patents

Abstract

An adsorbent for malodor removal according to an embodiment of the present invention includes: layered double hydroxides (LDHs) containing non-precious metal ions; and an interlayer interposed between the LDHs. A malodorous substance containing hydrogen sulfide can be removed by reacting with a non-metallic ion contained in the LDHs.

Description

Adsorption agent for odor treatment and its manufacturing method {ADSORBENT FOR OFFENSIVE ORDER REMOVAL AND METHOD TO MANUFACTURE THEREOF}

The present invention relates to an adsorbent for odor treatment and a method for manufacturing the same, and more specifically, it is capable of efficiently removing odor substances having high concentrations and high flows, and continuously sterilizing odor treatment efficiency even in harsh environmental conditions with high relative humidity. The present invention relates to a sorbent and a method for producing the same.

Recently, as social demand for creating a comfortable living environment has increased, the number of odor complaints has reached about 10,000 in the early 2010s, and on average, it has increased by about 20% each year.

In addition to the facilities specified by the Odor Prevention Act, odor substances are also generated in odor emission facilities and non-regulated odor facilities that are smaller than the scale. Ammonia (NH ₃ ) and sewage septic tanks have been confirmed to emit odorous substances based on hydrogen sulfide (H ₂ S).

Accordingly, the present invention introduces an adsorption method through the development of a deodorization technology that has a small facility capacity, low facility installation cost and low operation cost, and has high processing efficiency, and the treatment process using activated carbon (hereinafter referred to as AC) as an adsorbent is frequently used. .

However, the technology using activated carbon has limitations because it is difficult to remove acid gas. In addition, the scrubber technology using a chemical liquid has a disadvantage in that the chemical liquid smell and moisture may be leaked.

On the other hand, the adsorbent is affected by odor characteristics (acid gas) and environmental conditions (humidity, temperature, etc.). At this time, the malodor gas has a low throughput for activated carbon, which is a physically based adsorbent. The reason is that activated carbon having a non-polar surface cannot be treated because the main odor-causing substance is a substance having polar properties. In addition, the presence of moisture in the gas hinders the physical adsorption of activated carbon.

Therefore, there is a need to continuously operate a malodor prevention facility while maintaining a high efficiency malodor removal performance, and there is a need to develop an adsorbent applicable thereto.

As related prior art, Korean Patent Registration No. 10-1970499 (Invention name: Adsorption deodorant for removing odors, manufacturing method thereof, and odor removal device using prepared adsorption deodorant, registration date April 15, 2019), etc. have.

An embodiment of the present invention provides an adsorbent for odor treatment and a method for manufacturing the odor treatment efficiency, which is capable of efficiently removing odor substances at high concentrations and high flows, and continuously maintaining stable odor treatment efficiency even in harsh environmental conditions with high relative humidity.

The problem to be solved by the present invention is not limited to the problem (s) mentioned above, and another problem (s) not mentioned will be clearly understood by those skilled in the art from the following description.

The adsorbent for malodor treatment according to an embodiment of the present invention includes a double layered hydroxide layer (LDH) containing non-precious metal ions and an intervening layer interposed between the double layered hydroxide layers. Included, the malodorous substance containing hydrogen sulfide can be removed by reacting with the non-metallic ions contained in the hydroxide layer.

In addition, the intervening layer according to an embodiment of the present invention is provided with carbonate ions or water vapor, and the malodorous substance containing the hydrogen sulfide may be removed by reacting with the carbonate ions or water vapor.

In addition, the hydroxide layer according to an embodiment of the present invention is a CoFe-LDH containing a cobalt ion (Co ^{2 +)} or iron ions (Fe ^3+), hydrogen sulfide is to be removed by the general formula (1).

[Formula 1]

_{CoFe-LDH + H 2 O +} CO 3 2- + H 2 S + → CoFe-HS + H 2 O + CHO 3 - + HS - → CoFeS 2 + H 2 O + CO 2

In addition, it is manufactured in a powder type according to an embodiment of the present invention and may be used after being coated on a polyurethane foam.

In addition, it is made of a powder type according to an embodiment of the present invention and can be used fixed to an organic support or an inorganic support.

In addition, the organic support according to an embodiment of the present invention is activated carbon, and the inorganic support may be zeolite or silica gel.

On the other hand, the manufacturing method of the odor treatment adsorbent according to an embodiment of the present invention, between the hydroxide layer arrangement step of disposing the hydroxide layer containing a non-precious metal-based ion in a double layered structure and the hydroxide layer disposed in a double layered structure It includes a step of placing an intervening layer to arrange the intervening layer, the malodorous material containing hydrogen sulfide is removed by reacting with the non-metallic ions contained in the hydroxide layer or by reacting with carbonate ions or water vapor present in the intervening layer. You can.

In addition, the hydroxide layer disposed in the hydroxide layer arrangement step according to an embodiment of the present invention is CoFe-LDH including cobalt ion (Co ^{2 +} ) or iron ion (Fe ^{3 +} ), and hydrogen sulfide is removed by the following Chemical Formula 1 Can be.

[Formula 1]

_{CoFe-LDH + H 2 O +} CO 3 2- + H 2 S + → CoFe-HS + H 2 O + CHO 3 - + HS - → CoFeS 2 + H 2 O + CO 2

In addition, the adsorbent for the malodor treatment according to the embodiment of the present invention is made of a powder type, it can be used is coated with a polyurethane foam.

In addition, the odor treatment agent according to an embodiment of the present invention is made of a powder type, it can be used is fixed to an organic support or an inorganic support.

According to an embodiment of the present invention, using a non-precious metal-based double-layered hydroxide-based odor-treating adsorbent having a treatment performance for odor-causing substances hydrogen sulfide, high-concentration, high-flow odor substances are efficiently removed, and relative humidity It can have stable and stable odor treatment efficiency even under high environmental conditions.

In addition, in order to prevent pressure loss of the adsorbent, it is possible to maintain strength and maintain an appropriate filling rate, and to adsorb and remove high concentrations of odors with high efficiency. Accordingly, the adsorbent can be made lighter and smaller, and gaseous odor treatment is possible.

1 is a view showing the optimization conditions for the production of a non-precious metal-based double layer structure hydroxide according to an embodiment of the present invention.
2 is a view showing the XRD results for the powder constituting the hydroxide layer of a double-layer structure according to an embodiment of the present invention.
Figure 3 is a view showing the XRD results for the powder constituting the hydroxide layer of a double-layer structure coated on a polyurethane foam according to an embodiment of the present invention.
FIG. 4 is an actual photograph of a double layer structure hydroxide prepared according to the optimization conditions of FIG. 1 coated on a polyurethane foam.
5 is a view showing the results of observing the surface of the fine particles of the double-layered hydroxide according to an embodiment of the present invention using an electron scanning microscope (SEM).

Advantages and / or features of the present invention and methods for achieving them will become apparent by referring to embodiments described below in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various different forms, and only the present embodiments allow the disclosure of the present invention to be complete, and common knowledge in the art to which the present invention pertains. It is provided to completely inform the person having the scope of the invention, and the present invention is only defined by the scope of the claims. The same reference numerals refer to the same components throughout the specification.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a view showing the optimization conditions for the production of a non-precious metal-based double layer structure hydroxide according to an embodiment of the present invention.

As shown in this, the adsorbent for odor treatment of a double layer structure according to an embodiment of the present invention, a non-precious metal-based double layer structure hydroxide (LDH, layered double hydroxide) for removing acid gas containing hydrogen sulfide As including, more specifically, it may include a double-layered hydroxide layer containing a non-precious metal-based ion, and an intervening layer interposed therebetween.

With this configuration, an acidic gas containing hydrogen sulfide, that is, a malodorous substance, can be removed by non-metal-based ions contained in the hydroxide layer, and can also be removed by carbonate ions or water vapor present in the intervening layer.

Through this, odor-causing substances contained in contaminated air can be effectively removed through a metal oxide-based adsorbent. In addition, the adsorbent of this embodiment can be used continuously and efficiently.

Specifically, the adsorbent for the malodor treatment of the double layer structure of this embodiment is easy to treat an acid gas containing hydrogen sulfide and can maintain the removal efficiency under high humidity conditions.

Referring to FIG. 1, hydroxide layers containing non-precious metal ions may be provided in a double layer structure. When each hydroxide layer (CoFe-LDH) is structurally described, cobalt ions (Co ^{2 +} ) or iron ions (Fe ^{3 +} ) are disposed in the center, and a total of four oxygens are connected, and hydrogen is connected to each oxygen. . Referring to FIG. 1, five such hydroxide layers are arranged in series, and five hydroxide layers arranged in series form a double layer structure.

In addition, an intervening layer is provided between the double layered hydroxide layers, and the intervening layer contains carbonate ions (CO ₃ ^2- ) or water vapor (H ₂ O).

When an acidic gas such as hydrogen sulfide is brought into contact with the double layered adsorbent having such a structure, a reaction as shown in FIG. 1 may occur. This can be expressed by the following formula (1).

[Formula 1]

_{CoFe-LDH + H 2 O +} CO 3 2- + H 2 S + → CoFe-HS + H 2 O + CHO 3 - + HS - → CoFeS 2 + H 2 O + CO 2

When the reaction process is described, first, hydrogen sulfide (H ₂ S) reacts with the hydroxide layer (CoFe-LDH) to convert cobalt ions or iron ions to CoFe-HS, and also reacts with water vapor or carbonate ions in the intervening layer. It may generate ^a-hydrogen sulphide ions (HS). That is, the hydrogen sulfide contained in the acid gas is held in the hydroxide layer and the intervening layer, and thus, the odorous substance can be removed from the acid gas.

Subsequently, CoFe-HS, H ₂ O, and CHO ₃ ^- and HS ^- may react to form a solid material, CoFeS2, and water and carbon dioxide may be generated and discharged during this process. That is, when the acid gas including sulfide gas is treated by the adsorbent for malodor treatment of this embodiment, it can be treated as shown in the lower portion of FIG. 1.

Since the adsorbent for odor treatment including the double layered hydroxide layer has a hydroxide structure, less waste water is generated than the previously used washing method, and it has an advantage of being less affected by the environment, such as moisture, than the conventionally used adsorption method.

In addition, in the adsorbent of this embodiment, it is possible to optimize the blending ratio of the metal elements serving as the raw material for the double layered hydroxide layer. That is, the present invention is not limited to the above-described examples, and it is natural that other transition ions other than cobalt ions or iron ions may be used and reactions may be made in other chemical formulas.

Meanwhile, hereinafter, the results of XRD analysis using the adsorbent of this example will be described.

2 is a view showing the XRD results for the powder constituting the hydroxide layer of the double-layered structure according to an embodiment of the present invention, Figure 3 is a double-layered structure coated on the polyurethane foam according to an embodiment of the present invention It is the figure which shows the XRD result about the powder which comprises a hydroxide layer.

Referring to FIG. 2, it can be seen that a pattern in the form of a bilayer structure such as 11.5 degrees (003), 23.4 degrees (006), and 34,1 (009) appears at 2 theta (degree). Also, referring to FIG. 3, it can be understood that the powder of the double layered hydroxide layer coated on the polyurethane foam is the same as the powder form of FIG. 2.

Meanwhile, FIG. 4 is an actual photograph of a double layered hydroxide prepared according to the optimization conditions of FIG. 1 coated on a polyurethane foam, and FIG. 5 is a fine particle surface of a double layered hydroxide according to an embodiment of the present invention Is a diagram showing the results observed using an electron scanning microscope (SEM).

Since the adsorbent for malodor treatment of the present embodiment described above may be manufactured in a powder structure, it may be used, for example, coated with a polyurethane foam.

5, plate-shaped particles representing a double layered hydroxide layer can be found.

However, the adsorbent of the present embodiment is not only applicable to polyurethane foam, but may be, for example, manufactured in powder type and fixed to an organic support or an inorganic support. Here, the organic support may be activated carbon, and the inorganic support may be zeolite or silica gel. When the adsorbent is provided as a powder, pressure loss may occur, and thus it may be difficult to apply to the site. In this case, when the adsorbent is fixed to the support, it can facilitate on-site use.

On the other hand, hereinafter, a description will be given of a method of manufacturing an adsorbent for malodor treatment having a double layer structure according to an embodiment of the present invention.

The manufacturing method of the adsorbent of this embodiment includes a step of arranging a hydroxide layer in which hydroxide layers containing non-precious metal ions are arranged in a double-layered structure, and an intervening layer in which an intervening layer is arranged between hydroxide layers arranged in a double-layered structure. It may include steps.

The structure of FIG. 1 is provided by providing a space between hydroxide layers having a double layer structure and arranging an intervening layer in this space, as well as providing one hydroxide layer, then arranging an intervening layer, and then arranging another hydroxide layer. It is natural that such an adsorbent can be constructed.

Thus, according to the embodiment of the present invention, using a non-noble metal-based double-layered hydroxide-based odor treatment adsorbent having a treatment performance for the odor-causing substance hydrogen sulfide, the high-concentration, high-flow odor is efficiently removed, and the relative It can have stable and stable odor treatment efficiency even in harsh environment conditions with high humidity.

In addition, in order to prevent pressure loss of the adsorbent, it is possible to maintain strength and maintain an appropriate filling rate, and to adsorb and remove high concentrations of odors with high efficiency. Accordingly, the adsorbent can be made lighter and smaller, and gaseous odor treatment is possible.

So far, specific embodiments according to the present invention have been described, but various modifications are possible without departing from the scope of the present invention. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined not only by the scope of the claims described below, but also by the claims and equivalents.

As described above, although the present invention has been described by limited embodiments and drawings, the present invention is not limited to the above embodiments, and various modifications and modifications from these descriptions will be made by those skilled in the art to which the present invention pertains. Deformation is possible. Accordingly, the spirit of the present invention should be understood only by the claims set forth below, and all equivalents or equivalent modifications thereof will be said to belong to the scope of the spirit of the present invention.

Claims (10)

Layered double hydroxides (LDH) containing non-precious metal ions; And
An intervening layer interposed between the double layered hydroxide layers;
It includes,
The adsorbent for treating malodors having a double layer structure, characterized in that the malodorous substance containing hydrogen sulfide is removed by reacting with a non-metallic ion contained in the hydroxide layer.
According to claim 1,
The intervening layer is provided with carbonate ions or water vapor,
The odor substance containing hydrogen sulfide is an adsorbent for treating malodors having a double layer structure, characterized in that it is removed by reacting with the carbonate ions or water vapor.
According to claim 2,
The hydroxide layer is CoFe-LDH containing cobalt ion (Co ^{2 +} ) or iron ion (Fe ^{3 +} ),
Adsorbent for odor treatment, characterized in that to remove hydrogen sulfide by the formula (1).
[Formula 1]
_{CoFe-LDH + H 2 O +} CO 3 2- + H 2 S + → CoFe-HS + H 2 O + CHO 3 - + HS - → CoFeS 2 + H 2 O + CO 2
According to claim 3,
Adsorption agent for odor treatment of double layer structure, characterized in that it is used in powder form and coated on polyurethane foam.
According to claim 3,
Adsorption agent for the treatment of malodor having a double layer structure, characterized in that it is manufactured in powder type and fixed to an organic support or an inorganic support.
The method of claim 5,
The organic support is activated carbon,
The inorganic support is a zeolite or a silica gel adsorbent for the treatment of malodors having a double-layer structure.
A hydroxide layer arrangement step of arranging hydroxide layers containing non-precious metal ions in a double layer structure; And
An intervening layer arrangement step of arranging an intervening layer between the hydroxide layers arranged in a double layer structure;
It includes,
Preparation of the odor treatment adsorbent for a double layer structure, characterized in that the malodorous substance containing hydrogen sulfide is removed by reacting with non-metallic ions contained in the hydroxide layer or by reacting with carbonate ions or water vapor present in the intervening layer. Way.
The method of claim 7,
The hydroxide layer disposed in the step of arranging the hydroxide layer is CoFe-LDH including cobalt ion (Co ²⁺ ) or iron ion (Fe ^{3 +} ),
Method for producing an adsorbent for odor treatment, characterized in that to remove hydrogen sulfide by the following formula (1).
[Formula 1]
_{CoFe-LDH + H 2 O +} CO 3 2- + H 2 S + → CoFe-HS + H 2 O + CHO 3 - + HS - → CoFeS 2 + H 2 O + CO 2
The method of claim 8,
The odor treatment adsorbent is prepared in a powder type,
A method of manufacturing an adsorbent for treating malodors having a double layer structure, which is coated with a polyurethane foam and used.
The method of claim 8,
The malodor treatment agent is manufactured in a powder type, and is a method for manufacturing an adsorbent for malodor treatment having a double layer structure, which is fixed to an organic support or an inorganic support.

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