KR20120015782A - Method of preparing spherical active carbon for adsorptive removal of iodide and hydrogen sulfide and superior active carbon prepared therefrom - Google Patents

Abstract

PURPOSE: A method for manufacturing spherical activated carbon and the spherical activated carbon are provided to improve the absorptive effect of iodide and hydrogen sulfide by mixing activated carbon, titanium oxide, copper, or the mixture of the same, a binder, and an organic solvent, shaping the mixture into a spherical shape, and carbonating and activating the shaped mixture. CONSTITUTION: Activated carbon, titanium oxide, copper, or the mixture of the same, a binder, and an organic solvent are mixed(1). The mixture is shaped into pellets(2). Vibrations are applied to the pellets at a temperature between 80 and 90 degrees Celsius using a shaker such that the pellets are formed into spherical shapes(3). The spherical shaped materials are carbonated at a temperature between 600 and 800 degrees Celsius under inert gas atmosphere(4). The carbonated materials are activated at a temperature between 750 and 950 degrees Celsius under carbon dioxide gas atmosphere(5).

Description

Method of preparing spherical activated carbon excellent in adsorption and removal of iodine and hydrogen sulfide {Method of preparing spherical active carbon for adsorptive removal of Iodide and Hydrogen sulfide and superior active carbon prepared therefrom}

The present invention relates to a method for producing spherical activated carbon excellent in adsorption and removal of iodine and hydrogen sulfide and spherical activated carbon prepared therefrom, and more particularly, activated carbon; Titanium oxide, copper, or mixtures thereof; Binder; And mixing and kneading an organic solvent, forming a spherical shape, and carbonizing and activating the same, thereby improving spherical fire resistance and producing spherical activated carbon having excellent iodine and hydrogen sulfide adsorption and removal effect.

As the production of high precision products and the standard of cultural life have increased, the demand for highly functional adsorbents with low flammability even at relatively high temperatures such as for air cleaners, semiconductor processes, precision automobile processes, various air conditioners, and exhaust gas removal has increased rapidly. .

Therefore, researches for the removal of noxious gases using commercial adsorbents such as activated carbon, zeolite and alumina have been actively conducted.

In particular, activated carbon is an adsorbent that causes physical adsorption of fine mesh plane structure, and due to its advantages such as meat porosity, heat resistance, chemical resistance, etc., organic ash recovery, deodorization, harmful gas removal, gas separation, water treatment, decolorization, medical, It is used in a wide range of fields such as electrode materials and catalyst tints.

Effective and continuous removal of solvent recovery process, odors, harmful gases and pathogens is difficult to realize with general purpose activated carbon alone. Therefore, doping of metal compounds effective for the removal of harmful gases and pathogens based on high-performance activated carbon with highly developed surface area and pores Adsorption, decomposition and removal are required to an acceptable level through the selection and complexation of photocatalysts.

By the way, the activated carbon containing the active substance lowers the ignition temperature by about 50 to 100 ° C. due to the catalytic action of the supported active substance, thereby causing a safety problem that ignition occurs easily in the adsorption process.

In addition, in the method described in Japanese Patent Application Laid-Open No. 49-115110, an activated carbon molded article is produced by adding a phenolaldehyde-based resin to carbon materials such as charcoal and extruding it and then reactivating it after carbonization or carbonization. In 42039, a carbon material is mixed with a powdered activated carbon and a phenol resin-based binder, and then carbonized and reactivated. However, in the manufacturing process, since the activated carbon moldings need an activating process after molding, the mechanical strength of the molded body is lowered, and it is expensive and difficult to use industrially.

In addition, Japanese Patent Laid-Open Publication No. 55-167118 and Japanese Patent Laid-Open Publication No. Hei 7-207119 disclose a method for producing an activated carbon molded article by molding, drying and curing the activated carbon using a liquid phenolaldehyde-based resin as a binder at room temperature. This is described. In the case of this method, activation is not performed, but there is a problem that the binder component occludes the pores of the activated carbon and the adsorption capacity of the activated carbon is significantly lowered.

Therefore, in this study, the inorganic-activated carbon fused material was developed to increase the ignition temperature and adsorption capacity of the metal fused activated carbon, thereby developing advanced metal fused activated carbon with improved fire resistance and satisfying the needs of domestic and foreign markets through the molding process.

In order to overcome the problems of the prior art, the present inventors activated carbon; Titanium oxide, copper, or mixtures thereof; Binder; And kneading and kneading an organic solvent, forming a spherical shape, and carbonizing and activating it to improve spontaneous fire resistance and to provide a method for producing spherical activated carbon excellent in adsorption and removal effect of iodine and hydrogen sulfide and spherical activated carbon prepared therefrom. will be.

In order to achieve the above object, the present invention relates to a method for producing spherical activated carbon excellent in adsorption removal of iodine and hydrogen sulfide and spherical activated carbon prepared therefrom.

The manufacturing method of the spherical activated carbon of this invention,

a) activated carbon; Titanium oxide, copper, or mixtures thereof; Mixing the binder and kneading by adding an organic solvent;

b) a primary molding step of molding the kneaded mixture into pellets;

c) a secondary molding step of forming the pellets into a sphere by applying vibration to the pellets at 80 to 90 ℃ using a shaker;

d) carbonizing the spherical shaped body by heat treatment at 600 to 800 ° C. in an inert gas atmosphere; And

e) carbonizing the spherical shaped body and activating it by heat treatment at 750 to 950 ° C. in a carbon dioxide gas atmosphere;

Characterized in that it comprises a.

Hereinafter, the steps of the present invention will be described in detail.

Activated carbon, which is a material used to prepare the spherical activated carbon, is a kind of carbonaceous powder, and has an average particle size of 100 to 400 mesh.

The carbonaceous powder may use a kind of charcoal such as wood charcoal, keratin shell charcoal, chaff charcoal or charcoal charcoal, and the like according to the present invention. Kinds of organics may be used.

Step a) is activated carbon; Titanium oxide, copper, or mixtures thereof; And preferably a binder, but more preferably a mixture of activated carbon, titanium oxide, copper and a binder.

The titanium oxide is not particularly limited, but among them, titanium dioxide (TiO ₂ ) is preferably used.

The spherical activated carbon according to the present invention includes a metal-supported activated carbon, which can reduce the cost of using expensive titanium oxide, as well as surprisingly synergistic two of the adsorption effect and decomposition effect. This is because iodine adsorption and removal efficiency for hydrogen sulfide can be greatly increased.

Copper (Cu) is preferable as the metal supported on the activated carbon, and the effect of the activated carbon is increased, hydrogen sulfide removal, iodine adsorption, antibacterial activity, and ignition point are increased.

The titanium oxide is preferably used 4 to 15 parts by weight based on 100 parts by weight of activated carbon, and the copper is preferably used 3 to 10 parts by weight based on 100 parts by weight of activated carbon. If the titanium oxide is less than 4 parts by weight, the iodine adsorption capacity and the hydrogen sulfide removal effect is low and not suitable, and if more than 15 parts by weight, the efficiency of the adsorption power is reduced and it is not economical due to expensive titanium dioxide. If the copper is less than 3 parts by weight, the efficiency of iodine and hydrogen sulfide adsorption removal is not good, and if it is 10 parts by weight or more, it is not economical.

The binder of step a) of the present invention is a phenol resin, characterized in that using 35 to 55 parts by weight based on 100 parts by weight of activated carbon. The phenolic resin is used in the form of a powder, if the phenolic resin is less than 35 parts by weight spherical form is not made, there may be a problem that the crack easily occurs in the sphere during the stirring process, if more than 55 parts by weight the sphere in the stirring process It is easily distorted, resulting in poor spheroidization, as well as reduced pore remodeling and specific surface area.

The phenol resin was used in the form of a powder of a noblock-type solid phenol resin.

The organic solvent of step a) of the present invention uses a lower alcohol having 1 to 4 carbon atoms, which is activated carbon; Titanium oxide, copper, or mixtures thereof; And kneaded and added to impart moldability and flowability of the binder mixture.

The organic solvent is preferably used 25 to 55 parts by weight based on 100 parts by weight of activated carbon. If the alcohol, the organic solvent, is less than 25 parts by weight, the flowability of the kneaded mixture is too low, so that molding may not be performed well. If the content is 55 parts by weight or more, the moldability is not good. .

The primary molding step b) is a step of molding and pelletizing the kneaded mixture of step a) into pellets in a plurality of short cylindrical molds, the spherical activated carbon of the present invention This is a preceding molding step in order to facilitate the molding into a sphere in production.

The secondary molding of step c) is performed using a sieve having a scale of the size of 30 to 50 mesh, and a hot air of 80 to 90 ° C. is applied for 10 minutes to 20 minutes. A spherical shaped body is produced by applying vibration during the process.

If the scale of the sieve is less than 30 mesh or more than 50 mesh, the pellets formed by the vibrations formed on the sieve are not well formed and the spherical shape is not well formed.

In addition, the hot air is to penetrate the sieve (sieve), the heating effect is lowered if the temperature of the hot air is 80 ℃ or less, the curing phenomenon of the phenol resin occurs if it is 90 ℃ or more is not spherical to form.

The shaker of the step c) refers to a form in which a vibrating portion causing vibration is connected to a sieve, and the vibration has a structure repeatedly moving in the x and y axes.

Step d) of the present invention is a step of carbonizing, it is preferable to carbonize the spherical shaped body by circulating 100 to 150 minutes at a circulation rate of 100 to 200 ml / min at a temperature of 600 to 800 ℃.

Argon gas (Argon gas), helium gas (Helium gas) or nitrogen gas (Nitrogen gas) may be used as the inert gas, and it is particularly preferable to use nitrogen gas.

If the carbonization temperature is less than 600 ℃ or the carbonization time is less than 100 minutes, the carbonization is not sufficiently achieved, the carbon content is low, and if the carbonization temperature is 800 ℃ or more or more than 150 minutes, the iodine adsorption power of the spherical activated carbon decreased.

Step e) of the present invention is an activation step, activated by circulating 100 to 150 minutes at a circulation rate of 100 to 200 ml / min at a temperature of 750 to 950 ℃. If the activation temperature is less than 750 ℃ or the activation time is less than 100 minutes, the sufficient activation is not achieved, the specific surface area is small, if the temperature is more than 950 ℃ or the activation time is more than 150 minutes, the economic loss is large, mass production This is because the process is difficult.

The spherical activated carbon prepared according to the present invention was confirmed that the remodeling and specific surface area of the pores were increased through the process of carbonization and pyrolysis of the binder and the activation step.

In addition, the spherical activated carbon produced by the production method of the present invention is characterized in that it is used for the adsorption removal of iodine and hydrogen sulfide.

As described in detail above, the present invention is activated carbon; Titanium oxide, copper, or mixtures thereof; Binder; And it is possible to manufacture spherical activated carbon excellent in the adsorption removal effect of iodine and hydrogen sulfide through the molding, carbonization and activation step using an organic solvent.

Therefore, the spherical activated carbon prepared by the manufacturing method as described above removes hydrogen sulfide gas generated from malignant wastewater containing a large amount of organic matter such as sludge, dye wastewater, livestock wastewater, food wastewater, and wastewater generated from leather goods processing plants. It is effective to

1 is a flow chart showing a method for producing spherical activated carbon according to the present invention.
Figure 2 shows a molding frame photograph used in the first molding step of the present invention.
Figure 3 shows a photograph of the secondary molding step of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples, which are intended only for understanding the constitution and effects of the present invention, and are not intended to limit the scope of the present invention.

Example 1

Activated carbon powder having a mean particle size of 300 mesh (66 g of Coal based actibated carbon), 4 g of titanium dioxide (TiO ₂ ), and 30 g of phenol resin as a binder were mixed and ethanol (95%, Samchun Chmicals) was kneaded by adding 25 g. The kneaded mixture was put into a plurality of short cylindrical molds and pressed to form pellets (Fig. 2), and then placed on a 50 mesh sieve and placed in a shaker. A spherical molded body was prepared by vibrating with hot air at 85 ° C. (FIG. 3).

The spherical shaped body thus prepared was carbonized at 700 ° C. for 2 hours at a circulation rate of 150 ml / min. After carbonization, spherical activated carbon was prepared by activating at 950 ° C. for 2 hours using a carbon dioxide gas at a feed rate of 150 ml / min.

Example 2-3

Except for changing the content of titanium dioxide (TiO ₂ ) and phenol resin in Example 1 as shown in Table 1 was prepared in the same manner as in Example 1.

Example 4-5

Copper (Cu) was added instead of titanium dioxide (TiO ₂ ) in Example 1, and was prepared in the same manner as in Example 1 except that the content was changed as shown in Table 1.

Example 6-7

Copper (Cu) was further added in Example 1, and was prepared in the same manner as in Example 1 except that the content was changed as shown in Table 1.

Comparative Example 1-3

Charcoal was used instead of activated carbon in Example 1, and was prepared in the same manner as in Example 1 except that the contents were changed as shown in Table 1.

Comparative Example 4-5

Comparative Example 1 was prepared in the same manner as in Comparative Example 1 except that copper (Cu) instead of titanium dioxide and the content was changed as shown in Table 1.

Comparative Example 6-7

Copper (Cu) was further added in Comparative Example 1, and was prepared in the same manner as in Comparative Example 1 except that the content was changed as shown in Table 1.

Experimental Example 1 Measurement of Iodine Adsorption

Approximately 0.5 g of a 325 mesh dry sample is weighed accurately to 1 mg, 100 ml of a capped Erlenmeyer flask, 50 ml of N / 10 iodine solution is added correctly, shaken with a shaker for 15 minutes at room temperature, and then put into a 50 ml precipitate plate. The sample is precipitated using a separator. Take 10 ml of the supernatant, titrate with N / 10 sodium thiosulfate solution, and when the yellow color of iodine becomes light, add 1 ml of 1 weight / vol% starch solution with indicator and continue titration to stop the blue color of iodine starch. As the end point, the number of mg of iodine adsorbed per 1 g of the sample is obtained using Equation 1 below. The formula for calculating the iodine adsorption amount is as follows.

[Wherein A is the mass number of iodine,

B is the normal concentration of sodium thiosulfate,

S is the weight of the sample,

12.69 is the amount of iodine (mg) corresponding to 1 ml of N / 10 sodium thiosulfate solution.]

Experimental Example 2 Hydrogen Sulfide Removal Efficiency

H ₂ S standard gas was used as H ₂ S 10% / N ₂ 90%. The flow rate was 80 mL for 20 minutes and the column diameter was filled with 5 g of activated carbon at 15 mm to measure the initial supply and later emissions. As measured by the amount adsorbed.

Table 2 shows the results of iodine adsorption capacity and hydrogen sulfide removal efficiency of the spherical activated carbon containing titanium dioxide in the above Examples and Comparative Examples.

TABLE 2

In Table 2, it was confirmed that the examples using activated carbon had better iodine adsorption and hydrogen sulfide removal efficiency than the comparative examples using charcoal.

The results of iodine adsorption capacity and hydrogen sulfide removal efficiency of the spherical activated carbon containing copper in the above Examples and Comparative Examples are shown in Table 3 below.

[Table 3]

Table 3 confirms that spherical activated carbon using activated carbon instead of charcoal has excellent iodine adsorption capacity and hydrogen sulfide removal efficiency.

In addition, it was confirmed that as the amount of copper added increased, the amount of iodine adsorption and the hydrogen sulfide removal efficiency also increased.

Table 4 shows the results of iodine adsorption capacity and hydrogen sulfide removal efficiency of the spherical activated carbon including titanium dioxide and copper in the examples and the comparative examples.

[Table 4]

Table 4 shows that spherical activated carbon using activated carbon instead of charcoal has excellent iodine adsorption capacity and hydrogen sulfide removal efficiency, and in Examples 6 to 7 and Comparative Examples 6 to 7 where both copper and titanium dioxide were added, iodine adsorption The amount and the hydrogen sulfide removal efficiency was confirmed to be significantly superior to other examples and comparative examples. As the amount added increased, the amount of iodine adsorption and the hydrogen sulfide removal efficiency also increased. In addition, when Example 6 and Example 7 were compared, the amount of iodine adsorption and hydrogen sulfide removal efficiency were excellent as the amount of copper added increased.

Accordingly, the iodine adsorption capacity of titanium activated carbon and copper-added spherical activated carbon was significantly improved rather than only titanium dioxide, and high iodine adsorption power was observed when phenol resin was used as the carbon raw material. Hydrogen sulfide removal efficiency also showed the same pattern as the iodine adsorption capacity.

Claims (12)

a) activated carbon; Titanium oxide, copper, or mixtures thereof; Mixing the binder and kneading by adding an organic solvent;
b) a primary molding step of molding the kneaded mixture into pellets;
c) a secondary molding step of forming the pellets into a sphere by applying vibration to the pellets at 80 to 90 ℃ using a shaker;
d) carbonizing the spherical shaped body by heat treatment at 600 to 800 ° C. in an inert gas atmosphere; And
e) carbonizing the spherical shaped body and activating it by heat treatment at 750 to 950 ° C. in a carbon dioxide gas atmosphere;
Spherical activated carbon manufacturing method comprising a. The method of claim 1,
Step a) is a method for producing spherical activated carbon, characterized in that the mixture of activated carbon, titanium oxide, copper and binder. The method of claim 2,
The titanium oxide is a method for producing spherical activated carbon, characterized in that 4 to 15 parts by weight based on 100 parts by weight of activated carbon. The method of claim 3,
The copper is a method for producing spherical activated carbon, characterized in that 3 to 10 parts by weight based on 100 parts by weight of activated carbon. The method of claim 1,
The binder is a phenol resin, and the manufacturing method of the spherical activated carbon, characterized in that 35 to 55 parts by weight based on 100 parts by weight of activated carbon. The method of claim 1,
The activated carbon is a method for producing spherical activated carbon, characterized in that it has an average particle size of 100 ~ 400 mesh. The method of claim 6,
The organic solvent is a method for producing spherical activated carbon, characterized in that the lower alcohol having 1 to 4 carbon atoms. The method of claim 7, wherein
The organic solvent is a method for producing spherical activated carbon, characterized in that 25 to 55 parts by weight based on 100 parts by weight of activated carbon. The method of claim 1,
The c) step is a method for producing spherical activated carbon, characterized in that carried out using a sieve (sieve) having a size of 30 to 50 mesh. The method of claim 9,
The c) step is a spherical activated carbon manufacturing method, characterized in that the production by applying hot air of 80 to 90 ℃. Spherical activated carbon produced by the manufacturing method according to any one of claims 1 to 10. 12. The method of claim 11,
The spherical activated carbon prepared is a spherical activated carbon, characterized in that for removing the adsorption of iodine and hydrogen sulfide.

Images