KR102005016B1 - Method manufacturing activated carbon for removal of aldehydes gas - Google Patents

Abstract

The present invention relates to a process for producing an activated carbon for removing an aldehyde gas having an excellent adsorption rate to aldehydes.
The activated carbon according to the present invention comprises the steps of: forming a carbonized activated organic support; Dissolving piperazine and phosphoric acid in distilled water to prepare an impregnated material aqueous solution; Impregnating the impregnated material aqueous solution with the organic material support; Separating the impregnated organic support from the impregnated material aqueous solution; And drying the organic material support separated from the aqueous solution. In the impregnation step, vibration is generated in the aqueous solution to increase the impregnation rate of the impregnation material to the organic material support, and in the separation step, The organic support is separated from the aqueous solution by centrifugation to remove phosphate remaining on the surface of the support.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing an activated carbon for removing an aldehyde gas,

The present invention relates to a process for producing an activated carbon for removing an aldehyde gas, and more particularly, to a process for producing an activated carbon for removing an aldehyde gas having an excellent adsorption rate to aldehydes.

There are three main causes of indoor air pollution. First of all, in order to conserve energy, the building is gradually becoming more airtight. In order to improve the insulation performance, interior and exterior parts are installed more airtightly and the natural ventilation is reduced. . In addition, building materials used in interior and exterior materials emit more pollutants using more chemicals than before, resulting in an increase in indoor pollutants. In addition, external vehicles and dust from the construction site accumulate in the room.

Because of this, indoor air pollution inside the building is serious. Today, indoor air pollution is a social problem because the modern outdoor activities are reduced and the time spent living in the indoor area is increased compared to the past. This is caused by sick house syndrome and chemical hypersensitivity.

With this indoor air pollutants and carbon dioxide (CO _2), carbon monoxide (CO), nitrogen oxides (NOx), radon (Rn), volatile organic compounds (TVOC), formaldehyde (HCHO) and acetaldehyde (CH ₃ CHO) .

Among them, formaldehyde, which is mainly studied in the present invention, is a major cause of indoor air pollution. Urea resin foam insulation used for general houses and public buildings, fiber cloth, paint for indoor furniture, combustion process of heating fuel, smoking , Household goods, medicines, adhesives, and the like.

Therefore, the concentration of formaldehyde in the room is high in new buildings, and it is also emitted in cooking, fireplaces and other stoves.

Short-term exposure to formaldehyde gives rise to severe irritation to eyes, nose, and bronchus, causing headache, dizziness, and tears. In case of prolonged exposure, skin may develop allergic contact dermatitis and eczema, respiratory tract cough, Asthma, and chronic bronchitis. The effect on the reproductive system causes spontaneous abortion, low birth weight and pregnancy addiction.

In order to remove such formaldehyde, active carbon produced by treating wood with palm kernel, coal, pitch, cellulose fiber and chemical fiber as raw materials and using inert gas was used. These activated carbons are well suited for adsorbing various harmful gases because of their relatively wide specific surface area and fine pores. However, since the formaldehyde gas is simply removed through physical adsorption, the adsorption and desorption are repeated.

Acetaldehyde is a colorless, fruity volatile substance that is a harmful substance defined by the World Health Organization as a substance capable of carcinogenic to humans.

To date, there have been developed activated carbons which have relatively good adsorption performance on aldehydes of formaldehyde and aldehydes of acetaldehyde. However, in comparison with the activated carbons developed to date, No activated carbon has been developed to exhibit excellent adsorption performance.

KR 10-1648551 B

SUMMARY OF THE INVENTION The present invention has been conceived to solve the problems as described above, and it is an object of the present invention to provide a method and a system for the production of an aldehyde having excellent adsorption amount on acetaldehyde, which is another harmful substance of aldehyde as well as formaldehyde, And a method for producing an activated carbon for degassing.

Another object of the present invention is to provide a method for producing an activated carbon for removing aldehyde gas, which makes it possible to use phosphoric acid which has become a use-hindrance due to whitening due to residual surface and pore-closing phenomenon.

It is another object of the present invention to provide a method for producing an activated carbon for removing an aldehyde gas, which can improve the impregnation rate of the impregnated material to the micropores of the organic support through the generation of vibration to the aqueous solution.

It is still another object of the present invention to provide a method for producing an activated carbon for removing an aldehyde gas, which is capable of producing activated carbon by carrying out the impregnation, separation and drying steps collectively in one manufacturing apparatus.

According to an aspect of the present invention, there is provided a method of manufacturing an activated carbon for removing an aldehyde gas, comprising: forming a carbonized activated organic support; Dissolving piperazine and phosphoric acid in distilled water to prepare an impregnated material aqueous solution; Impregnating the impregnated material aqueous solution with the organic material support; Separating the impregnated organic support from the impregnated material aqueous solution; And drying the organic material support separated from the aqueous solution. In the impregnation step, vibration is generated in the aqueous solution to increase the impregnation rate of the impregnation material to the organic material support, and in the separation step, The organic support is separated from the aqueous solution by centrifugation to remove phosphate remaining on the surface of the support.

In the preparation of the aqueous solution, 3 to 6 parts by weight of piperazine and 2 to 6 parts by weight of phosphoric acid are mixed with distilled water, 100 parts by weight of the distilled water to prepare an impregnated material aqueous solution. When the piperazine and phosphoric acid are mixed, It is preferable that the mixture of piperazine and phosphoric acid is mixed at a weight ratio of 1: 0.3 to 1.

The impregnating step, the separating step, and the drying step may include: holding the organic material support and the aqueous solution in a container to generate vibration in the container; discharging the aqueous solution to the outside by rotating the container; And an impregnated activated carbon manufacturing apparatus for discharging the air inside the container to the outside.

At this time, in the impregnating step, the vibration by the ultrasonic vibrator installed in the container in the state that the organic material support and the aqueous solution are accommodated in the hermetically sealable container, or the vibration of the rotary shaft through the center of the container, A minute flow of the aqueous solution is impregnated in the aqueous solution caused by the supplied air for 1 to 2 hours.

Further, in the separating step, in the vessel containing the organic material support and the aqueous solution, the outer cylinder closely attached to the outer periphery of the inner cylinder having a plurality of water holes formed on the side thereof is slid while the rotation shaft is rotated to rotate the inner cylinder of the vessel And the aqueous solution is discharged to the water hole by centrifugal separation.

The rotary shaft is rotatably connected to the lower end of the rotary shaft to rotate the rotary shaft vertically and horizontally. In the drying step, the container arranged in a vertical state in the separation step is rotated by the rotary unit Wherein the container is rotated by rotation of the rotary shaft and air at a high temperature of 70 to 90 DEG C is supplied from the air supplier connected to the lower space of the rotary shaft to the inside of the container from the air hole, And the air in the container is discharged to the outside through the water hole so that the water content of the organic material support is 10% or less.

According to the process for producing an activated carbon for removing an aldehyde gas according to the present invention, an appropriate amount of piperazine and phosphoric acid are mixed to form a single activated carbon as well as formaldehyde as well as acetaldehyde, which is another harmful substance of aldehyde, There is an advantage that the damage to the aldehyde can be prevented.

According to the present invention, it is possible to use phosphoric acid, which has been hindered by the whitening and pore-closing phenomenon due to the residual surface, thereby maximizing the adsorption performance to aldehydes without deteriorating the performance and appearance of the activated carbon.

Further, according to the present invention, the impregnation rate of the impregnated material to the micropores of the organic support can be improved through the generation of vibration to the aqueous solution, thereby increasing the adsorption performance of the aldehyde by the impregnated material, There is an advantage that can be made.

In addition, according to the present invention, the impregnation, separation and drying steps can be collectively carried out in one production apparatus, and high-efficiency activated carbon can be produced, thereby increasing the efficiency for producing activated carbon.

1 is a schematic flow chart of a method for producing activated carbon according to the present invention,
2 is a perspective view showing a configuration of an apparatus for producing activated carbon according to the present invention,
3 is an exploded perspective view showing the structure of a container according to the present invention,
4 is a conceptual diagram illustrating the impregnation step according to the present invention,
5 is a conceptual diagram illustrating a separation step according to the present invention,
6 is a conceptual diagram illustrating a drying step according to the present invention,
7 is a graph comparing adsorption amounts of acetaldehyde in Examples and Comparative Examples,
8 is a graph comparing adsorption amounts of formaldehyde in Examples and Comparative Examples.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method of manufacturing an activated carbon for aldehyde gas removal according to the present invention will be described in detail with reference to the accompanying drawings.

1 is a schematic flowchart of a method for producing activated carbon according to the present invention. FIG. 3 is an exploded perspective view showing the structure of a container according to the present invention, and FIG. 4 is a conceptual view explaining the impregnation step according to the present invention. FIG. FIG. 5 is a conceptual view for explaining a separation step according to the present invention, and FIG. 6 is a conceptual view for explaining a drying step according to the present invention.

As shown in the drawings, the method for producing activated carbon according to the present invention includes the steps of: forming a carbonized activated organic support; Dissolving piperazine and phosphoric acid in distilled water to prepare an impregnated material aqueous solution; Impregnating the impregnated material aqueous solution with the organic material support; Separating the impregnated organic support from the impregnated material aqueous solution; And drying the organic support separated from the aqueous solution. Through this step, active carbon impregnated with the impregnated material composed of piperazine and phosphoric acid on the pores and on the surface can be produced.

More specifically, in the organic material support forming step, the coal-based, palm-based, and charcoal-based materials are heat-treated under an inert gas and carbonized to form an organic material support. Here, the activation step of heat-treating the carbonized organic material support under a carbon dioxide and steam mixture may be further included.

And the organic support is not made solely of the materials described above, and various materials based materials available as precursors are all usable. By using such an inexpensive material-based material as a precursor, it is possible to manufacture low-cost activated carbon.

As the precursor, a polymer resin material may be used. That is, the present invention provides a method for producing a poly (vinylidene fluoride), a poly (vinylidene fluoride-co-hexafluoropropylene), a poly (vinylidene fluoride) Poly (vinylidene chloride-co-acrylonitrile), poly (vinylidene chloride-co-acrylonitrile-co-methyl poly (vinylidene chloride-co-vinyl chloride)] and poly (vinylidene chloride-co-methyl [poly (vinylidene chloride-co-methyl acrylate) acrylate] may be used as a precursor.

In the organic material support forming step, the step of crushing the carbonated organic material support, the washing step and the sorting step may be added. The pulverization step is a step of uniformly pulverizing the organic material support, the washing step is washing with an acid to remove impurities, and the step of selecting is selected according to the particle size, and the uniform particle size is selected and used .

It may further comprise a pelletizing step. The pelletizing step couples the organic support to the binder and transforms it into pellets or granules.

The activated carbon precursor is then carbonized by heat treatment under an inert gas. As the inert gas, an inert gas generally known can be used without limitation. Specifically, it may include nitrogen (N ₂ ) or argon (Ar), but is not limited thereto.

The heat treatment temperature in the carbonization step may be 700 to 1000 ° C. If the temperature is too low, carbonization may not be completely achieved. It is not necessary to carry out a heat treatment at a higher temperature because carbonization is sufficiently carried out at a temperature of 700 to 1000 ° C. If the temperature is too high, an unnecessary expense may occur and a problem may arise that the rate of carbonization is reduced.

Thereafter, the carbide is introduced into a mixed gas containing carbon dioxide and steam and is activated by heat treatment. At this time, by activating the activated carbon precursor (carbon dioxide-steam activation) using a mixed gas containing carbon dioxide and steam, the activity of the steam molecule is increased to selectively enhance the expression of ultrafine pores having a diameter of 1 nm or less on the surface of the carbon . Accordingly, the specific surface area and the uniformity of the pores of the activated carbon can be increased.

The activation step may be performed at a temperature of 700-1000 < 0 > C. The activation effect is not good at too low a temperature, and a rapid yield drop may occur at a too high temperature.

The activation step may be performed for a time of 1 hour to 5 hours or less. If the activation time is too long, the problem of the yield and the problem of collapsing the pore structure of the entire material may occur. On the other hand, if it is too short, a problem of insufficient activation effect may occur (step S10).

Next, an impregnated material aqueous solution for impregnating and impregnating the organic support is prepared. The impregnated aqueous solution is composed of distilled water, 3 to 6 parts by weight of piperazine and 2 to 6 parts by weight of phosphoric acid (H ₃ PO ₄ ) per 100 parts by weight of the distilled water.

In this case, when the impregnated material was mixed with distilled water in an amount of 3 to 6 parts by weight of piperazine, the adsorption amount of acetaldehyde increased 2.6 to 3.5 times and the adsorption amount of formaldehyde was 2.4 to 2.6 And the increase in the number of test specimens.

However, when piperazine and phosphoric acid are mixed and the piperazine and phosphoric acid are mixed at a weight ratio of 1: 0.3 to 1, the amount of acetaldehyde adsorption is increased by 4.25 to 7.3 times as compared with the case of using general activated carbon, The adsorption amount of aldehyde increased 2.65 ~ 3.65 times.

Therefore, when a mixture of piperazine and phosphoric acid is used, the amount of formaldehyde adsorption is somewhat smaller than that of using piperazine alone. However, when 3 to 6 parts by weight of piperazine and 2 to 6 parts by weight of phosphoric acid are mixed, Since the overall adsorption performance to aldehyde and formaldehyde is improved, in the present invention, in order to develop an adsorbent having improved adsorption performance to aldehydes, piperazine and phosphoric acid are mixed in the above weight ratio to prepare an impregnated material aqueous solution, And phosphoric acid were mixed at a weight ratio of 1: 0.3 to 1 (Step S20).

Next, in the impregnation step, the organic material support is impregnated in the impregnated material solution as described above for 1 to 2 hours. At this time, if vibration is generated in the impregnated material aqueous solution, the impregnated material can be remarkably increased by about 2 to 3 times even if the impregnated material solution flows into the micropores of the organic material more smoothly and the impregnation time is shortened.

In order to generate such vibration, an ultrasonic vibrator or an air feeder is used in the present invention. More specifically, in the impregnation step, vibration caused by the ultrasonic vibrator installed in the container 10 in a state in which the organic material support O and the aqueous solution L are accommodated in the sealable container 10, (L) by the air supplied through the air hole (21) of the rotating shaft (20) penetrating the center of the rotating shaft (20) coupled to the container (10).

The container 10 is a hermetically closable container for containing the organic support O and the aqueous solution L. The container 10 has a rotary shaft 20 at the bottom and a plurality of water holes 11a at the side, A cover 12 inserted into a through hole 12a formed at the center of the rotary shaft 20 and seated on the inner cylinder 11 and a cover 12 fitted to the outer periphery of the inner cylinder 11, And an outer tube 13 having one end inserted into the cover 12 and the other end fixed to a lower bottom portion of the inner tube 11. As shown in FIG. A plurality of through holes may be formed in the cover 12 to allow air and moisture to be discharged.

The rotary shaft 20 is formed in a cylindrical shape and is engaged with the container 10 while passing through the center of the container 10 and rotated in a vertical and horizontal state by the rotary part 30, 10).

Therefore, when the ultrasonic vibrator is used to generate vibration in a state where the rotary shaft 20 is vertically arranged by the rotary unit 30, the ultrasonic vibrator is mounted on the bottom of the inner cylinder 11 of the container 10 An air generator 40 is connected to the rotary shaft 20 so that a bubble is formed inside the container 10 through a vent hole 21 formed in the rotary shaft 20, (Step S30).

Next, in the separation step, the impregnated organic support (O) is separated from the impregnated material aqueous solution (L). At this time, it is preferable that the organic support (O) is separated from the aqueous solution (L) by centrifugation in order to remove phosphate remaining on the surface of the organic support (O).

In this separation step, the outer cylinder 13 which is in close contact with the outer periphery of the inner cylinder 11 in which a plurality of water supply holes 11a are formed in the side is provided in the container 10 containing the organic material support O and the aqueous solution L The aqueous solution L is discharged to the water supply hole 11a by centrifugal separation by rotating the inner cylinder 11 of the vessel 10 by rotating the rotary shaft 20 while being slid and moved.

Through the separation of the aqueous solution L by the centrifugal separation method, the whitening phenomenon and the pore-closing phenomenon can be prevented as the salt component remains on the surface of the organic material support O (step S40).

Next, in the drying step, the step of drying the organic material support O separated from the aqueous solution L includes the steps of injecting hot air into the container 10 and discharging the air inside the container 10 to the outside A method of lowering the moisture content of the organic material support O is used.

In this drying step, the container 10 arranged in a vertical state in the separating step is horizontally arranged by the rotary part 30, the container 10 is rotated by the rotation of the rotary shaft 20, Air having a high temperature of 70 to 90 DEG C is supplied from the air feeder connected to the lower space of the rotary shaft 20 and the heater (not shown) to the inside of the container 10 from the vent hole 21, Is performed within a range of 10 to 24 hours so that the air in the vessel (10) is discharged to the outside through the water hole (11a) of the organic material support (11) so that the water content of the organic material support (O)

Since the inner cylinder 11 having the water supply hole 11a formed therein is rotated by the rotary shaft 20 in a horizontal state when the high temperature air is supplied thereto, the organic matter O flows smoothly and the moisture is easily discharged, The residual moisture in the inner tube 11 is discharged through the water hole 11a exposed at the upper portion of the inner tube 11 as the organic support O is driven to the lower portion of the vessel 10 at step S50.

≪ Examples and Comparative Examples &

Next, examples of activated carbon according to the present invention and comparative examples thereof will be described.

First, in order to confirm the amount of adsorption of aldehydes by the components of the impregnated material, Example 1 was prepared by adding 3 parts by weight of piperazine and 2 parts by weight of phosphoric acid, Example 2 was prepared by adding 3 parts by weight of piperazine and 3 parts by weight of phosphoric acid In Example 3, 6 parts by weight of piperazine and 2 parts by weight of phosphoric acid were added. In Example 4, 6 parts by weight of piperazine and 4 parts by weight of phosphoric acid were added. In Example 5, 6 parts by weight of piperazine and 6 parts by weight of phosphoric acid In Comparative Example 1, 3 parts by weight of piperazine, 3 parts by weight of piperazine and 3 parts by weight of piperazine were used. Comparative Example 1 was prepared by using activated carbon, Comparative Example 2 was prepared by adding 3 parts by weight of piperazine, Comparative Example 4 was prepared from an adsorbent containing 6 parts by weight of piperazine and Comparative Example 5 was prepared from an adsorbent containing 9 parts by weight of piperazine with the addition of phosphoric acid, And gun Steps were performed in the same manner.

The test method is as follows.

In other words, flow formaldehyde gas at 10 L / min, check the temperature and humidity (23 ℃ / 45% RH) before the test, and adjust the gas concentration. 10 ml of the adsorbent according to Examples 1 to 5 and Comparative Examples 1 to 5 is weighed, and then the test is carried out. When the adsorption efficiency decreases to 70% or less by measuring the concentration of the adsorbent, the test is terminated and the weight of the adsorbent is checked.

The test results for Examples 1 to 5 and Comparative Examples 1 to 5 are as shown in Figs. 7 and 8.

As shown in the figure, the adsorbents of Examples 1 to 5 showed much higher adsorption rates to acetaldehyde and formaldehyde than those of Comparative Example 1, which is an adsorbent made of general activated carbon. Comparative Example 2, which is an adsorbent with 3 parts by weight of piperazine, Comparative Example 3, which is an adsorbent with 3 parts by weight of piperazine and 1 part by weight of phosphoric acid, Comparative Example 4, which is an adsorbent with 6 parts by weight of piperazine, and 9 parts by weight of piperazine, It can be seen that the adsorbents of Examples 1 to 5 also increase the adsorption rate to acetaldehyde and formaldehyde for Comparative Example 5 as the adsorbent added.

These results show that the addition of piperazine to the activated carbon alone can increase the adsorption rate of aldehydes. Moreover, 3 to 6 parts by weight of piperazine and 2 to 6 parts by weight of phosphoric acid are added to distilled water, And phosphoric acid in a weight ratio of 1: 0.3 to 1, it was confirmed that the adsorption rate of aldehydes can be maximized.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined by the appended claims. It is obvious that you can do it.

10: container 11: inner tube 12: cover
13: outer tube
20: rotating shaft 21:
30:
40: air generator
O: organic support
L: aqueous solution

Claims (6)

Forming a carbonized activated organic support (O);
Dissolving piperazine and phosphoric acid in distilled water to prepare an impregnated material aqueous solution (L);
Impregnating the impregnated material aqueous solution (L) with the organic material support (O);
Separating the impregnated organic support (O) from the impregnated material aqueous solution (L); And
Drying the organic support (O) separated from the aqueous solution (L)
In the impregnating step, a vibration is generated in the aqueous solution (L) in order to increase the impregnation rate of the impregnated material to the organic material support (O)
In the separation step, the organic support (O) is separated from the aqueous solution (L) by centrifugation in order to remove phosphate remaining on the surface of the organic support (O)
In the preparation of the aqueous solution (L), an impregnated material aqueous solution (L) is prepared by mixing distilled water, 100 parts by weight of distilled water, 3 to 6 parts by weight of piperazine and 2 to 6 parts by weight of phosphoric acid, When mixed, the piperazine and phosphoric acid are mixed in a weight ratio of 1: 0.3 to 1,
The impregnation step, the separation step, and the drying step are performed in such a manner that the organic material support O and the aqueous solution L are accommodated in the container 10 to generate vibration into the container 10, Is carried out by an impregnated activated carbon manufacturing apparatus which discharges the aqueous solution L to the outside and injects hot air into the vessel 10 and discharges the air inside the vessel 10 to the outside,
In the impregnating step, the vibration by the ultrasonic vibrator installed inside the container 10 in a state in which the organic material support O and the aqueous solution L are accommodated in the sealable container 10, (L) in which the fine flow of the aqueous solution (L) is caused by the air supplied through the air hole (21) of the rotary shaft (20) And,
In the separating step, an outer cylinder 13 which is in close contact with an outer circumference of an inner cylinder 11 having a plurality of water supply holes 11a formed on the side thereof in a container 10 containing the organic material support O and the aqueous solution L The aqueous solution L is discharged to the water supply hole 11a by centrifugal separation by rotating the inner cylinder 11 of the vessel 10 by rotating the rotary shaft 20 while the slide is being moved,
The rotary shaft 20 is rotatably connected to the lower end of the rotary shaft 20 to rotate the rotary shaft 20 vertically and horizontally.
In the drying step, the container 10 arranged in a vertical state in the separating step is horizontally arranged by the rotary part 30, the container 10 is rotated by the rotation of the rotary shaft 20, Air having a high temperature of 70 to 90 DEG C is supplied from the air feeder connected to the lower space of the rotary shaft 20 to the inside of the container 10 from the vent hole 21 and flows into the water hole 11a of the inner pipe 11 Wherein the drying is performed within a range of 10 to 24 hours so that the air in the vessel (10) is discharged to the outside so that the water content of the organic material support (O) is 10% or less. delete delete delete delete delete

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