KR20040091344A - Active carbon absorbent containing copper, silver and chrome and method for preparing same - Google Patents

Abstract

PURPOSE: An active carbon adsorbent containing copper, silver and chromium is provided which is capable of efficiently removing toxic gas such as HCl by introducing copper, silver and chromium into active carbon through a transition metal electroplating method, and a method for preparing the active carbon adsorbent is provided. CONSTITUTION: The method comprises the step of impressing current to a space between the two electrodes by using copper, silver and chromium plates as the anode and using active carbon fixed between conductive metal meshes as the cathode in an electroplating pot, wherein the active carbon is active carbon particle or active carbon fiber, wherein a weight ratio of copper, silver and chromium is 2:0.5:1 to 1:0.1:1, and wherein particle size of copper, silver and chromium introduced into active carbon is 5 to 300 nm.

Description

Cu / Ag / Cr / Activated Carbon Adsorbent and Manufacturing Method Thereof {ACTIVE CARBON ABSORBENT CONTAINING COPPER, SILVER AND CHROME AND METHOD FOR PREPARING SAME}

The present invention relates to Cu / Ag / Cr / active carbon adsorbent for removing toxic gases in which Cu / Ag / Cr is simultaneously introduced into activated carbon through an electrolytic transition metal plating method and a method of manufacturing the same.

With the rapid development of modern industry, attention has been focused on environmental pollution. Activated carbons (ACs) have a large specific surface area, so the adsorption capacity is large and the developed micropores are exposed to the pore surface. Because of its fast advantage, it is not only highly effective in removing contaminants, but also advantageous in terms of economic and environmental friendliness. In particular, activated carbon has good stability and reproducibility and is easy to process, so it is made in the form of powder, granular or fibrous form. Widely used in devices and the like.

On the other hand, the recent terrorist incidents around the world have heightened the sense of crisis on chemical weapons. Activated carbon has been reported in many journals to show high efficiency in removing various industrial and toxic gases.

As a method for removing various toxic gases using activated carbon, a method of packing activated carbon, a method of making impregnated activated carbon using various transition metal solutions ( Applied Chemistry 5 (2): 292-295, 2001), and precursors Carbonation and activation after the introduction of the transition metal in the state ( HWAHAK KONGHAK 39 (1): 54-58, 2001) and the like has been used. However, this method has a limitation in removing toxic gases, and in particular, the impregnation method does not maintain a high specific surface area of activated carbon. In addition, when mixing in the precursor state does not use the previously produced activated carbon, there is a problem that must greatly change the production system. Above all, in this case, the transition metal that becomes the active point is present in the fiber, so that the loss of the transition metal is large.

Accordingly, the present inventors have diligently researched to solve the above problems, and by using the electrolytic transition metal plating method, a simple introduction of Cu / Ag / Cr into activated carbon can effectively remove toxic gases such as HCl. The present invention has been completed by developing Cu / Ag / Cr / active carbon adsorbent.

An object of the present invention is to provide a Cu / Ag / Cr / activated carbon adsorbent capable of efficiently removing toxic gases such as HCl by introducing Cu / Ag / Cr into the activated carbon through the electrolytic transition metal plating method.

1 shows a conceptual diagram of the electrolytic transition metal plating according to the present invention,

Figure 2 shows the HCl removal test results of the Cu / Ag / Cr / activated carbon adsorbent prepared in Examples 1 and 5 of the present invention,

Figure 3 shows the HCl removal test results of the Cu / Ag / Cr / activated carbon adsorbent prepared in Examples 2 and 6 of the present invention,

Figure 4 shows the HCl removal test results of the Cu / Ag / Cr / activated carbon adsorbent prepared in Examples 3 and 7 of the present invention,

Figure 5 shows the HCl removal test results of the Cu / Ag / Cr / activated carbon adsorbent prepared in Examples 4 and 8 of the present invention.

In accordance with the above object, the present invention is to remove the toxic gas by applying a current between the two electrodes using a copper, Ag and Cr plate as an anode in the electroplating tank and the activated carbon or activated carbon fiber fixed between the conductive metal mesh as a cathode Provided are methods for preparing Cu / Ag / Cr / Activated Carbon Adsorbents.

In the present invention, it is preferable to use activated carbon having fine pores well developed and a large specific surface area in order to realize exposed activation sites, and in the present invention, activated carbon is not only existing activated carbon fibers present in fibrous or nonwoven fabrics. It includes all the conventional activated carbon etc. which exist in granular form or powder form. In addition, the activated carbon of the present invention may be prepared and used in the form of a filter.

In the present invention, as the transition metal capable of electroplating introduced into activated carbon, it is preferable to use Cu, Ag, and Cr in a weight ratio of 2: 0.5: 1 to 1: 0.1: 1. At this time, the particle size of Cu, Ag and Cr introduced into the activated carbon is preferably 5 to 300 nm.

The electrolytic transition metal plating may be performed under the conditions of the current density range of 60 to 70 A / m 2, plating time 5 seconds to 10 minutes using a plate of metal to be plated with an anode and using activated carbon as a cathode.

In electroplating, the activated carbon is preferably used after pressing and fixing with a conductive metal mesh to increase the conductivity. If the conductive metal mesh is not used, sufficient carbon coating film can be obtained as desired in a short time.

In the transition metal plating according to the present invention, the plating bath includes metal salts of Cu, Ag and Cr, and metal plates for Cu, Ag and Cr plating as a source of initial metal ions, and may include a stabilizer or the like as an additive. The introduction amount of the metal can adjust the plating time, the thickness of the plating can be from several nm to several mm, but can be treated by adjusting as necessary according to the application.

The Cu / Ag / Cr / Activated Carbon Adsorbent prepared according to the present invention maintains the shape of the transition metal protruding outward by minimizing the transition metal present in the pores or fibers while maintaining the high adsorption characteristics of the activated carbon. Since it has excellent properties for the removal of the same toxic gas, it can be usefully used for the selective adsorption / reduction treatment of toxic gas such as HCl. In addition, the Cu / Ag / Cr / activated carbon adsorbent prepared according to the present invention can be applied to products such as gas masks or protective materials for the selective adsorption / reduction treatment of toxic gases.

Hereinafter, the present invention will be described in detail by way of examples.

However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited to the following examples.

<Example 1>

The activated carbon used in this experiment was AW2001 (Taiwan KOTHmax Co.) having a specific surface area of 2121 m 2 / g. Cu, Ag and Cr plating of activated carbon was performed sequentially using the electrolytic transition metal plating method (SJ Park et al , Journal of the Korean Industrial and Engineering Chemistry 13 (8): 777-781, 2002). Activated carbon fibers were crimped and clamped between a plate of metal to be plated and a wire mesh (mesh size 5 × 5 mm), respectively. At this time, by varying the plating time by controlling the amount of Cu, Ag and Cr introduced into the activated carbon electrolytic plating so that Cu: Ag: Cr is 1: 1: 1, the current density is 60 A / ㎡ conditions Treated. Each electroplated sample was sufficiently washed with secondary distilled water and then completely dried in a drier.

The HCl removal rate of the Cu / Ag / Cr / Active Carbon adsorbent prepared as described above was measured using gas chromatography (GC; Donam Instruments). At this time, the reaction tube is P.I.D. The temperature was kept constant at 25 ° C using a temperature controller, and the flow rate of HCl gas was M.F.C. (Mass Flow Controller) was used to maintain 10 ml / min. The sample was purged with ultra high purity helium (He) in the reactor for 1 hour prior to analysis to remove moisture, and a standard curve was calculated using 100, 300, 600 and 1000 ppm HCl standard gas from which the HCl removal rate was obtained. Was measured.

In addition, the BET specific surface area (m ² .g ^-1 ) of Cu / Ag / Cr / active carbon adsorbent was measured by taking about 0.1 g of a sample under a 77 K liquid nitrogen atmosphere and measuring the adsorption amount using nitrogen gas as an adsorbate. Investigate. Pretreatment of the sample was degassed for about 9-12 hours at 573 K until the residual pressure in the sample was below 10 ^-3 torr. After the N ₂ isothermal adsorption test, in the range of about 0.05 to 0.3, P / P _o (P is the partial pressure and P _o is the saturated vapor pressure) showed a linear slope with respect to the adsorption amount, from which the BET specific surface area was obtained. .

The size of the transition metal introduced into the Cu / Ag / Cr / Activated Carbon adsorbent was measured by atomic force microscope (Atomic Forced Microscope, AFM) and scanning electron microscope (Scanning Electron Microscope, SEM).

HCl removal efficiency measurement results of Cu / Ag / Cr / activated carbon adsorbent prepared according to the present invention is shown in Figure 2 , the specific surface area measurement results are shown in Table 1 , the size of the introduced metals are shown in Table 2 , respectively.

<Example 2>

A Cu / Ag / Cr / Activated Carbon Adsorbent was prepared in the same manner as in Example 1 except that the introduction amount of Cu: Ag: Cr was adjusted to 0.5: 1: 1, and the result of measuring HCl removal efficiency thereof is shown in FIG . The specific surface area measurement results are shown in Table 1 and the sizes of the introduced metals are shown in Table 2 , respectively.

<Example 3>

A Cu / Ag / Cr / Activated Carbon Adsorbent was prepared in the same manner as in Example 1 except that the introduction amount of Cu: Ag: Cr was adjusted to 1: 0.5: 1, and the result of measuring HCl removal efficiency thereof is shown in FIG . The specific surface area measurement results are shown in Table 1 and the sizes of the introduced metals are shown in Table 2 , respectively.

<Example 4>

Cu: Ag: Cr introduced amount of 1: 1: the exception that was adjusted to 0.5 Example 1, and were prepared the Cu / Ag / Cr / activated carbon adsorbent in the same way, its HCl removal efficiency measurements are 2 The specific surface area measurement results are shown in Table 1 and the sizes of the introduced metals are shown in Table 2 , respectively.

Example 5

A Cu / Ag / Cr / Activated Carbon Adsorbent was prepared in the same manner as in Example 1 except that the introduction amount of Cu: Ag: Cr was adjusted to 1: 0.5: 0.5, and the results of measuring HCl removal efficiency thereof are shown in FIG . The specific surface area measurement results are shown in Table 1 and the sizes of the introduced metals are shown in Table 2 , respectively.

<Example 6>

A Cu / Ag / Cr / Activated Carbon Adsorbent was prepared in the same manner as in Example 1 except that the introduction amount of Cu: Ag: Cr was adjusted to 0.5: 1: 0.5, and the result of measuring HCl removal efficiency thereof is shown in FIG . The specific surface area measurement results are shown in Table 1 and the sizes of the introduced metals are shown in Table 2 , respectively.

<Example 7>

Cu: Ag: Cr introduced amount to 0.5: in the first one in Example 1 and Cu / Ag / Cr / activity were prepared carbon adsorbent, its HCl removal efficiency measured for 2 also in the same manner except that adjusted to 0.5 The specific surface area measurement results are shown in Table 1 and the sizes of the introduced metals are shown in Table 2 , respectively.

<Example 8>

A Cu / Ag / Cr / Activated Carbon Adsorbent was prepared in the same manner as in Example 1 except that the introduction amount of Cu: Ag: Cr was adjusted to 1: 0.1: 1, and the result of measuring HCl removal efficiency thereof is shown in FIG. 2 . The specific surface area measurement results are shown in Table 1 and the sizes of the introduced metals are shown in Table 2 , respectively.

Example BET specific surface area (㎡.g ^-1 ) Untreated 2121 Example 1 1500 Example 2 1752 Example 3 1710 Example 4 1692 Example 5 1821 Example 6 1884 Example 7 1798 Example 8 1921 Each measurement is an average value obtained by repeating the experiment ten times.

Example Particle Size (nm) Example 1 40-300 Example 2 10-80 Example 3 15-75 Example 4 10-80 Example 5 20-65 Example 6 15-70 Example 7 20-60 Example 8 5-70 Each measurement is an average value obtained by repeating the experiment ten times.

From the results of Table 1 and Table 2 and Figures 2 to 5 , according to the present invention, the activated carbon in which Cu / Ag / Cr is introduced has a relatively specific surface area while minimizing metal ions present in the pores or fibers. It can be seen that the removal rate of toxic gases such as HCl is very good.

As described above, the method of the present invention maintains the shape of the transition metal protruding to the outside by minimizing the transition metal present in the pores or fibers while maintaining the high adsorption characteristics of the activated carbon to remove toxic gases such as HCl Cu / Ag / Cr / activated carbon adsorbent having excellent properties can be prepared.

Claims (8)

In the electroplating bath, the Cu / Ag / Cr / Activated Carbon Adsorbent comprising applying a current between the two electrodes using the Cu, Ag and Cr plates as the anodes respectively and the activated carbon fixed between the conductive metal meshes as the cathodes. Manufacturing method. The method of claim 1, Activated carbon production method characterized in that the activated carbon particles or activated carbon fibers. The method of claim 1, Cu, Ag and Cr ratio of 2: 0.5: 1 to 1: 0.1: 1 weight ratio. The method of claim 1, Cu, Ag and Cr introduced particle size of 5 to 300 nm characterized in that the manufacturing method. Cu / Ag / Cr / activated carbon adsorbent prepared by the process according to any one of claims 1 to 4. A method of selectively adsorbing / reducing toxic gas using the Cu / Ag / Cr / Active Carbon adsorbent according to claim 5. A selective adsorption / reduction treatment product of a toxic gas comprising a Cu / Ag / Cr / active carbon adsorbent according to claim 5. The method of claim 7, wherein Product characterized in that it is a gas mask filter or protective material.