KR20170133656A - Iron-zinc complex metal oxide coated activated carbon adsorbent for acidic gas removal and manufacturing method the same - Google Patents

Abstract

The present invention relates to an activated carbon adsorbent for removing acidic gas, composed of iron-zinc composite metal oxide, activated carbon powder, and silicate. In addition, the present invention relates to a method for producing the activated carbon adsorbent for removing acidic gas, comprising the following steps: (a) heating and mixing a solution consisting of a ferric salt, a zinc salt, a first basic metal compound, and water so as to produce the iron-zinc composite metal oxide; (b) producing an activated carbon powder mixture containing the activated carbon powder and the silicate; and (c) mixing the iron-zinc composite metal oxide and the activated carbon powder mixture together so as to produce the activated carbon adsorbent for removing acidic gas.

Description

FIELD OF THE INVENTION [0001] The present invention relates to an activated carbon adsorbent for removing acidic gases containing iron-zinc composite metal oxides,

The present invention relates to an activated carbon adsorbent for removing acidic gases containing an iron-zinc composite metal oxide and a method for producing the same. More particularly, the present invention relates to a method for producing an adsorbent for removing an acid gas using a powdery activated carbon, a composite metal oxide of iron and zinc. The present invention facilitates the production process and does not generate wastewater such as an impregnation aqueous solution and significantly improves the initial adsorption removal efficiency of the acid gas. The present invention also relates to an adsorbent comprising an activated carbon for removing an acidic gas and an iron-zinc composite metal oxide having an adsorption life remarkably longer than that of general activated carbon, and a method for producing the same.

In order to remove the various acid gases generated in the industrial field, technologies for understanding the characteristics of acid gases and extending the adsorption lifetime by adding functionalities to general activated carbon have been developed.

Acidic gases such as fluoride (HF), hydrogen chloride (HCl), chlorine (Cl ₂ ), sulfur dioxide (SO ₂ ) and hydrogen sulfide (H ₂ S) are decomposed and removed by combustion or catalytic oxidation unlike volatile organic compounds And the life span of the activated charcoal activated carbon is very short using general activated carbon, resulting in poor economical efficiency.

In order to overcome the above disadvantages, impregnated activated carbon has been developed in which a catalytic function is imparted to a general activated carbon to remove harmful gas by supporting a metal, a metal salt, or glassy materials on the activated carbon to increase the chemical activity. These impregnated activated carbons are accompanied by neutralization reaction, chemical reaction, catalytic reaction, etc., and thus are capable of removing gases which are difficult to be removed by ordinary activated carbon.

Such impregnated activated carbon is generally prepared by using activated carbon as a raw material and impregnating activated carbon with potassium iodide or potassium permanganate aqueous solution. However, in order to maximize the economical efficiency of treatment, an adsorbent having a longer lifetime is required to be.

Korean Patent No. 10-1123042 discloses a method in which basic oxides such as CaCO ₃ , CaO, ZnO, and MgO are used as an absorbent in an absorption reactor installed in a CBC protection system to remove acid gas, However, the present invention is not limited to the use of a material having a specific preparation method.

Korean Patent No. 10-0426926 discloses a method for producing a hydrogen sulfide gas produced by attaching activated carbon to a diethanolamine solution in order to remove hydrogen sulfide. In Korean Patent Laid-Open No. 10-1998-0073620, hydrogen sulfide A process for producing impregnated activated carbon for adsorbing and removing hydrogen sulfide by impregnating a raw activated carbon in a specific size range with an aqueous potassium iodide solution and drying it.

However, in the case of the impregnated activated carbon prepared using the alkaline organic compound produced by such a production method, hydrocarbons may be generated as a byproduct while reacting with the acid gas, and there are limitations in simultaneously treating various acid gases.

In addition, for the purposes of oxidation catalytic and antibacterial purposes, for the purpose of removing sulfide gas, and for the purpose of air purification, activated carbon in which metal phthalocyanine compounds, basic alkali metal salts, iron or copper oxides or chlorides and zinc oxides, alkali metal hydroxides and ferric sulfate are impregnated However, there is no research using active carbon impregnated with iron-zinc composite metal oxide for air purification.

Therefore, it is possible to solve the problem that the adsorption performance is deteriorated when the acid gas is removed by the conventional coalescing method, thereby increasing the lifetime of the adsorbent, simplifying the production method, and requiring the adsorbent .

Korean Patent No. 10-1123042 (Feb. 27, 2012) Korean Patent No. 10-0426962 (March 31, 2004) Korean Patent Publication No. 10-1988-0073620 (November, 1998)

In order to solve the above-mentioned problems, the present invention provides an adsorbent which has a longer adsorption life than an adsorbent prepared by a conventional coalescing method in order to maximize the acidic gas adsorption amount, maximizes the chemical adsorption power and physical adsorption power, An object of the present invention is to provide an activated carbon adsorbent for acidic gas removal comprising an iron-zinc composite metal oxide which can improve an adsorption ability of an acid gas even in an environment of high temperature or high space velocity and is easy to mass-produce, and a method for producing the same. do.

In order to accomplish the above object, the present invention relates to an activated carbon adsorbent for removing acidic gases containing iron-zinc composite metal oxide, powdered activated carbon and silicate.

According to an embodiment of the present invention, the activated carbon adsorbent for removing acidic gas may be any one or two selected from sodium carbonate (Na ₂ CO ₃ ), calcium carbonate (CaCO ₃ ), sodium hydroxide (NaOH) and potassium hydroxide But it is not limited thereto.

According to another embodiment of the present invention, there is provided a process for producing iron-zinc composite metal oxide, comprising the steps of: a) heating and mixing a solution containing an iron salt, a zinc salt, a first basic metal compound and water to prepare an iron- And c) mixing the iron-zinc composite metal oxide and the powdered activated carbon mixture to produce an activated carbon adsorbent for acidic gas removal. The method for producing an activated carbon adsorbent for acidic gas removal according to claim 1, .

According to an embodiment of the present invention, in step a), the iron salt may be at least one selected from the group consisting of iron sulfate, iron ammonium sulfate, iron oxide, iron hydroxide, iron nitrate and iron chloride, hydrates thereof, But the present invention is not limited thereto. The zinc salt may be one or more kinds selected from zinc sulfate, zinc sulfate, ammonium sulfate, zinc oxide, zinc hydroxide, zinc nitrate and zinc chloride, hydrates thereof, But is not limited thereto.

According to an embodiment of the present invention, in the step a), the first basic metal compound may include any one or a mixture of two or more selected from sodium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide, Do not.

According to an embodiment of the present invention, in the step a), the iron salt and the zinc salt may include a weight ratio of the iron salt: zinc salt of 1: 9 to 9: 1, and the first basic metal compound may include iron salt and / But is not limited to, 10 to 100 parts by weight based on 100 parts by weight of the sum of zinc salts.

According to an embodiment of the present invention, in the step b), the silicate may include 1 to 50 parts by weight based on 100 parts by weight of powdered activated carbon, but is not limited thereto.

According to an embodiment of the present invention, in the step b), the powdered activated carbon mixture may be any one selected from sodium carbonate (Na ₂ CO ₃ ), calcium carbonate (CaCO ₃ ), sodium hydroxide (NaOH) and potassium hydroxide And may further comprise a second basic metal compound comprising one or a mixture of two or more.

According to an embodiment of the present invention, in the step c), 20 to 200 parts by weight of the powdered activated carbon mixture may be included per 100 parts by weight of the iron-zinc composite metal oxide, but the present invention is not limited thereto.

According to an embodiment of the present invention, in the step a), the iron-zinc composite metal oxide may further be heated and mixed, and then cooled with water.

As acid gas removal activated carbon adsorbent according to the present invention, general industrial chloride fluoride (HF) in the exhaust gas discharged from the hydrogen chloride (HCl), chlorine (Cl _2), sulfur dioxide (SO ₂₎ and hydrogen sulfide (H ₂ S) It is possible to efficiently adsorb and remove acidic gases harmful to the human body by physicochemical methods, and to control the emission concentration of each gas and to be chemically adsorbed at various temperatures, so that it can be usefully applied in an industrial field.

In addition, the activated carbon adsorbent for removing acidic gas by impregnating the iron-zinc composite metal oxide according to the present invention is economical because the manufacturing cost is lower than that of the imported product, and the adsorption removal process is relatively simple, Since it has a longer lifetime than conventional products, it minimizes the cost incurred by exchanging the adsorbent and minimizes the disconnection of the production line. Therefore, it is possible to reduce costs such as facility cost and maintenance cost, And the like.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a manufacturing process diagram of a method for producing an activated carbon adsorbent for removing an acidic gas according to an embodiment of the present invention,
FIG. 2 is a photograph of a surface of an activated carbon adsorbent for removing acidic gas prepared according to an embodiment of the present invention, taken by scanning electron microscope (SEM)
3 is a photograph of a surface of an impregnated activated carbon for commercial use of RBAA3 commercially available from Norit, which was used in a comparative example of the present invention, by scanning electron microscope (SEM)
4 is a schematic view showing a reaction system for measuring acidic gas adsorption performance of an activated carbon adsorbent for acidic gas production according to an embodiment of the present invention,
FIG. 5 is a photograph of a final product of an activated carbon adsorbent for removing an acidic gas according to an embodiment of the present invention.

Hereinafter, the activated carbon adsorbent for removing acidic gases including the iron-zinc composite metal oxide according to the present invention and a method for producing the same will be described in detail. The present invention can be better understood by the following examples, which are for the purpose of illustrating the present invention and are not intended to limit the scope of protection defined by the appended claims.

Since the activated carbon adsorbent for removing acid gases of the present invention contains an iron-zinc composite metal oxide, powdered activated carbon and silicate, compared with the conventional activated carbon produced by a simple alkali treatment or the like, hydrogen chloride (HCl) The adsorption efficiency is good for an acidic gas such as hydrogen sulfide (H ₂ S) and sulfur dioxide (SO ₂ ), and the adsorbent has an excellent adsorption life.

Furthermore, the activated carbon adsorbent for removing acid gases of the present invention contains an iron-zinc composite oxide and is characterized in that it has higher acid gas adsorption efficiency than impregnated activated carbon for removing acid gases in the past.

In addition, the activated carbon adsorbent for acidic gas removal of the present invention has a long adsorption lifetime due to desorption even at a relatively high temperature range of 40 to 80 DEG C, so that it can be applied to an industrial field discharged at a high temperature, There are features you can use.

In the present invention, in order to increase the adsorption amount of acid gas, an iron-zinc composite metal oxide and powder activated carbon mixture are separately prepared and mixed to prepare an activated carbon adsorbent for acid gas removal, And can reduce the cost of the process.

Hereinafter, one embodiment of the present invention will be described in more detail.

The present invention relates to an activated carbon adsorbent for removing acidic gases containing iron-zinc composite metal oxides, powdered activated carbon and silicates.

20 to 100 parts by weight, preferably 30 to 70 parts by weight, more preferably 40 to 60 parts by weight, of a powdered activated carbon mixture comprising powdered activated carbon and silicate may be contained per 100 parts by weight of the iron-zinc composite metal oxide, But is not limited thereto. It is possible to improve the adsorption performance and the adsorption amount of the acid gas while maintaining the fine pores of the activated carbon within the above range.

The silicate may contain 1 to 50 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of powdered activated carbon. The specific surface area of the activated carbon is not reduced within the above range, the adsorption amount of the acidic gas is not reduced, and the strength of the pellet can be maintained at the time of molding.

The activated carbon adsorbent for removing an acid gas may further include any one or a mixture of two or more selected from sodium carbonate (Na ₂ CO ₃ ), calcium carbonate (CaCO ₃ ), sodium hydroxide (NaOH) and potassium hydroxide (KOH) , But is not limited thereto.

A method for producing an activated carbon adsorbent for acidic gas removal according to an embodiment of the present invention comprises the steps of: a) heating and mixing a solution containing an iron salt, a zinc salt, a first basic metal compound and water to prepare an iron-zinc composite metal oxide B) preparing a powdered activated carbon mixture comprising powdered activated carbon and silicate, c) mixing the iron-zinc composite metal oxide and powdered activated carbon mixture to produce an activated carbon adsorbent for acidic gas removal, can do.

According to an embodiment of the present invention, the step a) is a step of heating and mixing a solution containing an iron salt, a zinc salt, a first basic metal compound and water to prepare an iron-zinc composite metal oxide. The mixing method may be used without limitation as long as it is a mixing method well known in the art.

Specifically, the iron salt is iron sulfate (FeSO _4), ferrous sulfate ammonium _{((NH 4) 2 SO 4} · FeSO 4), iron oxide (Fe ₂ O _3), iron hydroxide (Fe (OH) _3), iron nitrate (Fe (NO ₃ ) ₃ ), iron chloride (FeCl ₂ ), hydrates thereof, and mixtures thereof, and preferably one or two or more selected from the group consisting of iron sulfate (FeSO ₄ .4H ₂ O, FeSO ₄ 7H ₂ O) may be preferred, but is not limited thereto.

Specifically, the zinc salt is zinc sulfate (ZnSO _4), zinc sulfate ammonium _{(ZnSO 4 · (NH 4)} 2 SO 4), zinc oxide (ZnO), zinc hydroxide (Zn (OH) _2), zinc nitrate (Zn (NO ₃ ) ₂ ), zinc chloride (ZnCl ₂ ), hydrates thereof, and mixtures thereof, and preferably zinc sulfate hydrate (ZnSO ₄ .7H ₂ O) But is not limited thereto.

More specifically, the iron salt and the zinc salt may comprise a weight ratio of iron salt: zinc salt of 1: 9 to 9: 1, preferably 2: 8 to 8: 2, more preferably 7: 3, But is not particularly limited as long as the object is achieved.

The oxidation lattice in which the surface of the crystal lattice is oxidized can be formed by mutual exothermic reaction between the iron salt and the zinc salt in the above range, and the produced iron-zinc composite metal oxide can increase the acidic gas adsorption amount due to a large number of protruding functional groups Lt; / RTI >

Specifically, the first basic metal compound may include any one or a mixture of two or more selected from sodium carbonate (Na ₂ CO ₃ ), calcium carbonate (CaCO ₃ ), sodium hydroxide (NaOH) and potassium hydroxide (KOH) , So long as the object of the invention is achieved.

More specifically, the first basic metal compound may be used in an amount of 10 to 50 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the sum of the iron salt and the zinc salt, but is not limited thereto. It may be preferable to form the iron-zinc composite metal oxide slurry within the above range effectively. In addition, it may be preferable to form the iron-zinc composite metal oxide slurry by forming the hydrogen ion concentration (pH) of 7 to 9 by the first basic metal compound to effect the initial adsorption reaction with the acid gas and the adsorption force.

Specifically, in the step a), a solution containing an iron salt, a zinc salt, a first basic metal compound and water is heated and mixed to prepare a mixed solution of an iron-zinc composite metal oxide in which a slurry is formed.

More specifically, a solution containing both the iron salt, the zinc salt, the first basic metal compound and water is prepared, or a solution containing the iron salt, the first basic metal compound and water, and the zinc salt and the water, It can be heated and mixed, but it can be used without any particular limitations as long as it is a method capable of producing an iron-zinc composite metal oxide.

More specifically, the heating temperature may preferably be in the range of 60 to 100 占 폚, 70 to 90 占 폚. The heating and stirring time may preferably be within a range of 5 minutes to 5 hours, preferably 20 minutes to 2 hours, but is not limited thereto. The gel can be formed well within the above range, the water is not evaporated quickly, the stability of the reaction system is maintained, the reaction rate is not excessively increased, and particles of uniform size can be formed.

In the present invention, the method may further include a step of adding water to the mixed solution of the iron-zinc composite metal oxide having the slurry and cooling the mixed solution.

Specifically, in order to rapidly cool the temperature of the iron-zinc composite metal oxide mixed solution in which the slurry is formed to the range of 25 to 40 ° C, it may be preferable to use water having a temperature in the range of 10 to 30 ° C, The amount of water may be preferably 2 to 15 times, preferably 3 to 10 times, the volume of the iron-zinc composite metal oxide mixed solution, but is not limited thereto.

It is possible to increase the specific surface area of the iron-zinc composite metal oxide and to maintain the generated functional group while rapidly cooling the mixed solution of the iron-zinc composite metal oxide in which the slurry is formed within the above range.

In the present invention, the step of cooling may further include washing and removing the unreacted salt to prepare an iron-zinc composite metal oxide.

Specifically, the washing can be performed by a conventional method using a filter device, and unreacted salts and impurities such as carbon can be removed by a washing process. The cleaning solution may be preferable, but is not limited to, using an excess amount of water may facilitate cleaning only without side reaction.

Specifically, the amount of excess water may be preferably 3 to 50 times, preferably 5 to 40 times, more preferably 10 to 30 times, the volume of the iron-zinc composite metal oxide mixed solution volume, Not limited.

The iron-zinc composite metal oxide thus prepared may preferably be used while maintaining the moisture content at 10 to 50% by weight, preferably 20 to 40% by weight, in order to facilitate molding.

According to an embodiment of the present invention, the step b) is a step of preparing a powdered activated carbon mixture comprising powdered activated carbon and silicate. Specifically, the powdered activated carbon mixture can be prepared by mixing the powdered activated carbon and the silicate, and the mixing can be used without limitation as long as it is a mixing method well known in the art.

Specifically, as the raw material of the activated carbon used in the present invention, any one or more selected from coal, wood, coconut fruit, and the like can be used, and any activated carbon known in the art can be used without limitation. Powdered charcoal, granular charcoal and fibrous activated carbon may be used in the form of activated charcoal. Powder charcoal is preferably used for smooth mixing, but the present invention is not limited thereto. More specifically, the activated carbon preferably has a micro pore of 50% or more, an average pore radius of 1 to 2.5 nm, and a specific surface area of 800 m 2 / g or more, but is not limited thereto.

Specifically, the silicate is at least one selected from calcium silicate (Ca ₂ SiO ₄ ), sodium silicate (Na ₂ SiO ₃ ), magnesium silicate (H ₂ Mg ₃ (SiO ₃ ) ₄ ), hydrates thereof, And preferably calcium silicate (Ca ₂ SiO ₄ ) is preferable because it has a good chlorine gas removal efficiency by calcium, but is not limited thereto.

More specifically, the silicate may be used in an amount of 1 to 50 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of powdered activated carbon. When extruded and molded within the above-mentioned range, the strength of the pellet is not lowered, the specific surface area of the activated carbon is not reduced, and the adsorption amount of the acid gas to be removed may not be reduced.

The b) may further include a second basic metal compound. Specifically, the second basic metal compound is sodium carbonate (Na ₂ CO ₃ ), calcium carbonate (CaCO ₃ ), sodium hydroxide (NaOH), and potassium hydroxide (KOH) And the like. However, the present invention is not limited thereto.

 More specifically, the amount of the second basic metal compound is preferably 1 to 50 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the powdery activated carbon, but is not particularly limited as far as the object of the invention is attained. It is preferable that the pH of the adsorbent is 7 to 9 within the above range so that the adsorption force of the acid gas can be improved.

The step b) may further comprise water. Specifically, it may include, but is not limited to, 1 to 30 parts by weight, preferably 5 to 15 parts by weight, of water relative to 100 parts by weight of activated carbon powder. The powdered activated carbon and the silicate can be effectively mixed within the above-mentioned range.

According to an embodiment of the present invention, the step c) is a step of mixing an iron-zinc composite metal oxide and a powdered activated carbon mixture to prepare an activated carbon adsorbent for removing an acid gas. Mixing can be applied without limitation as long as it is a method well known in the art.

Specifically, it may include, but is not limited to, 20 to 200 parts by weight, preferably 30 to 170 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the iron-zinc composite metal oxide . It is possible to improve the adsorption performance and the adsorption amount of the acid gas while maintaining the fine pores of the activated carbon within the above range.

In the present invention, after the step (c), the method may further comprise molding an activated carbon adsorbent for removing an acid gas.

The adsorbent may be extruded into a pellet, a granule, a monolith, or the like. However, the adsorbent may be extruded by a known method, But is not limited thereto.

And may further include an organic lubricant or an organic binder to facilitate the molding. The organic-inorganic lubricant and the organic binder are not limited as long as they are well known in the art. Specifically, it may include any one or a mixture of two or more selected from Boehmite, bentonite, limestone and dolomite, and is not particularly limited as far as the object of the invention is attained.

In the present invention, after the step c), d) may further include a step of drying and aging the activated carbon adsorbent for removing an acid gas.

Concretely, the drying may be carried out at 60 to 120 ° C for 1 to 24 hours, preferably at 80 to 110 ° C for 3 to 10 hours. It is possible to have an appropriate moisture content of 1 to 10% by weight within the above range, and to produce an adsorbent effective for acid gas removal.

If the drying temperature is lower than 60 ° C, the strength of the adsorbent may be weak due to moisture. If the drying temperature is higher than 150 ° C, the moisture content in the adsorbent may be very low, which may result in a low adsorption amount of the acidic gas adsorbent. And it is effective to dry and aged in water.

In addition, through the above drying, the microvoids of the oxidation lattice of the iron-zinc composite metal oxide impregnated in the activated carbon powder mixture are maximized, and the adsorption performance of the adsorbent can be improved.

In the present invention, the acid gas may include any one or a mixture of two or more selected from fluorine (HF), hydrogen chloride (HCl), chlorine (Cl ₂ ), sulfur dioxide (SO ₂ ) and hydrogen sulfide (H ₂ S) (HCl), hydrogen sulfide (H ₂ S), and sulfur dioxide (SO ₂ ), but the present invention is not limited thereto and may be usefully applied to various acid gas generating sites.

Hereinafter, an activated carbon adsorbent for removing acidic gases containing an iron-zinc composite metal oxide according to the present invention and a method for producing the same will be described in more detail. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In addition, the following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms, and the drawings presented below may be exaggerated in order to clarify the spirit of the present invention.

Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

The physical properties of the activated carbon adsorbent for acidic gas removal prepared by the following examples and comparative examples were measured as follows.

Property measurement

1. Measurement of specific surface area (BET)

In order to measure the specific surface area of the activated carbon used as the carrier and the adsorbent prepared in Example 1, the adsorbent pretreated at 200 ° C under vacuum using a specific surface area meter (Micromeritics, ASAP 2420, USA) was subjected to nitrogen adsorption and desorption The adsorption desorption curve was obtained and the specific surface area was calculated by the BET (Brunaure-Emmett-Teller) method.

2. Adsorption amount measurement

The activated carbon adsorbent for acidic gas removal prepared according to the embodiment of the present invention was charged into a cylindrical cylindrical reactor having an inner diameter of 9.5 mm and a height of 45 mm to a reactor at a charging height of 30 mm and a charged amount of 1.5 g, ₂ S), sulfur dioxide (SO ₂ ) and hydrogen chloride (HCl). The adsorption performance was measured using a Toxic Gas Tansmitter (Analytical Technology, INC., Series F12, USA) at the outlet of the reactor. FIG. 4 shows a schematic diagram of a reaction system for measuring acid gas adsorption performance. The adsorption performance (L / L) was expressed in terms of the amount of gas adsorbed per liter of the adsorbent, and the adsorption performance was evaluated by determining the time point when the concentration of the acid gas collected at the outlet was 5.0 ppm .

[ Example  One]

Sulfate withdrawal cargo _{(FeSO 4 · 7H 2 O)} 764 g and the sodium carbonate in 1 basic metal compound (Na ₂ CO ₃₎ 250 g was dissolved in distilled water to _{2ℓ, (7H 2 O ZnSO 4} ·) of zinc sulfate monohydrate, zinc salt 255 g was dissolved in 1 liter of distilled water to prepare each solution. Each of the prepared solutions was mixed and stirred at 80 DEG C for 30 minutes to form a slurry.

10 L of distilled water at 20 캜 was added to the slurry-formed solution, and the solution was rapidly cooled to 25 캜. Thereafter, a large amount of distilled water was added to the slurry until the amount of unnecessary impurities such as unreacted salt and carbon became 100 ppm or less , And then filtered using a filter to obtain 200 g of an iron-zinc composite metal oxide having a water content of 30% by weight.

200 g of powdered activated carbon (BSC-001, manufactured by Baek Seok Chemical Co., Ltd.), 25 g of calcium silicate and 30 g of calcium carbonate as a second basic metal compound were mixed in separate reactors, 20 g of distilled water was added, To prepare a powdered activated carbon mixture.

In the separate reactor, the iron-zinc composite metal oxide and the powdered activated carbon mixture were uniformly mixed at 25 DEG C for 30 minutes and molded into pellets having a diameter of 3.0 mm. The molded pellets were dried at 100 DEG C for 3 hours to prepare an activated carbon adsorbent for removing acidic gases having a water content of 5 wt%.

Using the prepared activated carbon adsorbent for acid gas removal, hydrogen sulfide (H ₂ S, a standard gas prepared from 5,000 μmol / mol / N ₂ balance), sulfur dioxide (SO ₂ , standard prepared with 5,000 μmol / Gas) and hydrogen chloride (standard gas prepared with HCl, 1,000 μmol / mol / N ₂ balance) at a reaction temperature of 25 ° C. and a gas hourly space velocity (GHSV) of 1,512 hr ^-1 And an acid gas supply flow rate of 50 cc / min.

[ Example  2]

Space velocity (GHSV) 3025 hr ^{- 1} person And the acid gas was supplied at a flow rate of 100 cc / min. The results are shown in Table 3 below.

[ Example  3]

The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 60 ° C, and the results are shown in Table 3 below.

[Example 4]

Reaction temperature 60 ℃, a space velocity (GHSV) 3025 hr ^{- 1} of And the acid gas was supplied at a flow rate of 100 cc / min. The results are shown in Table 3 below.

[Comparative Example 1]

The results are shown in Table 3, except that the adsorbent prepared in Example 1 was not used and commercial impregnated activated carbon for removing acid gases (Norit Corp., RBAA3, Netherlands) was used.

[Comparative Example 2]

The same procedure as in Example 2 was carried out except that the adsorbent prepared in Example 1 was not used and commercial impregnated activated carbon for removing acid gases (Norit Corp., RBAA3, Netherlands) was used, and the results are shown in Table 3 below.

[Comparative Example 3]

Example 3 was repeated except that the adsorbent prepared in Example 1 was not used and commercial impregnated activated carbon for removing acid gases (Norit, RBAA3, Netherlands) was used. The results are shown in Table 3 below.

[Comparative Example 4]

The same procedure as in Example 4 was carried out except that the adsorbent prepared in Example 1 was not used but commercial impregnated activated carbon for removing acid gases (Norit Corp., RBAA3, Netherlands) was used, and the results are shown in Table 3 below.

[Comparative Example 5]

The same procedure as in Example 1 was carried out except that the adsorbent prepared in Example 1 was not used and commercial impregnated activated carbon for removing acid gases (Tong Yang Activated Carbon Co., Ltd., IPGA , Korea) was used. Respectively.

[Comparative Example 6]

The same procedure as in Example 2 was carried out except that the adsorbent prepared in Example 1 was not used and commercial impregnated activated carbon for removing acid gases (TYOYAN ACTIVE CARBON CO., LTD., IPGA, Korea) was used. Respectively.

[Comparative Example 7]

The procedure of Example 3 was repeated except that the adsorbent prepared in Example 1 was not used and commercial impregnated activated carbon for removing acid gases (Tong Yang Activated Carbon Co., IPGA, Korea) was used, Respectively.

[Comparative Example 8]

Without using the adsorbent prepared in Example 1, commercially available impregnated activated carbon for removing acid gases (manufactured by TYOYAN ACTIVE CARBON, IPGA, Korea) was used, and the results are shown in Table 3 below.

[Comparative Example 9]

The procedure of Example 1 was repeated except that no iron salt was used in Example 2, and the results are shown in Table 3 below.

[Comparative Example 10]

The procedure of Example 1 was repeated except that no zinc salt was used in Example 2, and the results are shown in Table 3 below.

[Comparative Example 11]

The procedure of Example 1 was repeated except that no activated carbon was used in Example 2. The results are shown in Table 3 below.

[Comparative Example 12]

The procedure of Example 1 was repeated except that silicate was not used in Example 2, and the results are shown in Table 3 below.

Description Powder activated carbon
(Baek Seok Chemical) Iron-zinc composite metal oxide
(Example 1) Activated carbon adsorbent for acid gas removal
(Example 1) BET (m < 2 > / g) 1,117 280 387

Table 1 shows changes in physicochemical properties of activated carbon before and after impregnation of iron-zinc composite metal oxide. As shown in Table 1, the specific surface area of the activated carbon adsorbent for removing acidic gas was increased by 38.3% as compared with the iron-zinc composite metal oxide.

Iron salt Zinc salt The first basic metal compound Powder activated carbon Silicate The second basic metal compound Moisture content Weight (g) Example 1 764 255 250 200 25 30 5 wt% Example 2 764 255 250 200 25 30 5 wt% Example 3 764 255 250 200 25 30 5 wt% Example 4 764 255 250 200 25 30 5 wt% Comparative Example 1 RBAA3 (Norit)
Impregnated activated carbon Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Dongyang Activated Carbon Co., Ltd.
Impregnated activated carbon Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 - 255 250 200 25 30 5 wt% Comparative Example 10 764 - 250 200 25 30 5 wt% Comparative Example 11 764 255 250 - 25 30 5 wt% Comparative Example 12 764 255 250 200 - 30 5 wt%

Table 2 shows the composition of the activated carbon adsorbent for removing acidic gases of Examples 1 to 4 and Comparative Examples 1 to 12. As shown in Table 2, Comparative Examples 1 to 8 used commercial impregnated activated carbon at home and abroad.

H ₂ S adsorption amount SO ₂ adsorption amount HCl Adsorption amount sample reaction
Temperature Space velocity Breakup
time
(min) (L / L) Breakup
time
(min) (L / L) Breakup
time
(min) (L / L) Example 1 The composition of Example 1 25 ℃ 1,512h ^-1 210 26.58 104 13.10 - - Example 2 25 ℃ 3,025h ^-1 26 6.58 36 9.07 450 22.57 Example 3 60 ° C 1,512h ^-1 145 18.35 60 7.56 - - Example 4 60 ° C 3,025h ^-1 35 8.86 16 4.03 280 14.04 Comparative Example 1 RBAA3 (Norit)
Impregnated activated carbon 25 ℃ 1,512h ^-1 35 4.43 75 9.45 - - Comparative Example 2 25 ℃ 3,025h ^-1 10 2.53 10 2.52 270 13.54 Comparative Example 3 60 ° C 1,512h ^-1 25 3.16 59 7.43 - - Comparative Example 4 60 ° C 3,025h ^-1 5 1.26 15 3.78 160 8.03 Comparative Example 5 Dongyang Activated Carbon Co., Ltd.
Impregnated activated carbon 25 ℃ 1,512h ^-1 2 0.25 9 1.13 - - Comparative Example 6 25 ℃ 3,025h ^-1 One 0.25 One 0.25 25 1.25 Comparative Example 7 60 ° C 1,512h ^-1 2 0.25 4 0.50 - - Comparative Example 8 60 ° C 3,025h ^-1 One 0.25 One 0.25 17 0.85 Comparative Example 9 The composition without the iron salt of Example 1 25 ℃ 3,025h ^-1 16 4.03 15 3.78 180 9.03 Comparative Example 10 The composition without the zinc salt of Example 1 25 ℃ 3,025h ^-1 15 3.78 20 5.04 250 12.54 Comparative Example 11 The composition without the activated carbon of Example 1 25 ℃ 3,025h ^-1 20 5.04 23 5.79 400 20.06 Comparative Example 12 The composition without calcium silicate of Example 1 25 ℃ 3,025h ^-1 12 3.02 13 3.27 140 7.02

Table 3 is a table showing the adsorption amounts of acid gases in Examples 1 to 4 and Comparative Examples 1 to 12. As shown in Table 3, it can be seen that the adsorbents of Examples 1 to 4 are produced by attaching the iron-zinc composite metal compound to the activated carbon, whereby the adsorption amount of the acid gas and the adsorption performance are remarkably excellent regardless of the reaction temperature.

Comparative impregnated activated carbon was used in Comparative Examples 1 to 4 and Comparative Impregnated Activated Carbon in Comparative Examples 5 to 8, but it was confirmed that the impregnated amount of acid gas was significantly lower than in Examples 1 to 4. Therefore, it can be confirmed that the activated carbon impregnated with the iron-zinc composite metal compound produced in the present invention shows a very excellent adsorption amount and adsorption performance.

In Comparative Example 9, it was found that the adsorption amount of HCl gas was greatly reduced and the amount of adsorption of H ₂ S and SO ₂ gas was also reduced by preparing an activated carbon adsorbent for acid gas removal without using iron salts. Comparative Example 10 shows that the adsorption amount of H ₂ S, SO _2, and HCl gas is decreased by producing an activated carbon adsorbent for acid gas removal without using a zinc salt. Comparative Example 11 was produced without using activated carbon, but it was found that the adsorption amount of the acid gas was not greatly decreased. In Comparative Example 12, activated carbon was produced without using silicate, and it was found that the adsorption amounts of H ₂ S, SO _2, and HCl gases were all reduced.

Therefore, it can be seen that the activated carbon adsorbent for acid gas removal of Examples 1 to 4 produced in the present invention has a very excellent acid gas adsorption amount and adsorption performance.

2 and 3, FIG. 2 is a photograph of the surface and particle morphology of an activated carbon adsorbent for acid gas removal according to Example 1 of the present invention, taken by scanning electron microscope (SEM) And FIG. 3 is an SEM photograph of the surface of the RBAA3-impregnated activated carbon adsorbent of Norit used in Comparative Example 1. FIG. FIG. 5 is a photograph of a final product of an activated carbon adsorbent for acidic gas production according to an embodiment of the present invention.

As shown in FIG. 2, the shape of the salt particles impregnated on the surface of the activated carbon is rather large and irregularly distributed, but in the case of FIG. 3, it can be seen that the salt particles are evenly distributed throughout.

The specific surface area of the activated carbon adsorbent for removing acidic gas according to Example 1 of the present invention shown in FIG. 2 was measured to be 387.35 m 2 / g. The adsorbent of RBAA 3 impregnated activated carbon of Norit used in Comparative Example 1 of FIG. As the surface area was measured as 785.60 ㎡ / g, the adsorption amount of impregnated activated carbon increased depending on the type of impregnated metal or impregnation amount rather than specific surface area.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Accordingly, the above description should not be construed as limiting the scope of the present invention defined by the limits of the following claims.

Claims (10)

Activated carbon adsorbent for removing acidic gases containing iron-zinc composite metal oxide, powdered activated carbon and silicate. The method according to claim 1,
Wherein the activated carbon adsorbent for removing acidic gas further comprises any one or a mixture of two or more selected from sodium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide and the like. a) heating and mixing a solution containing an iron salt, a zinc salt, a first basic metal compound and water to prepare an iron-zinc composite metal oxide,
b) preparing a powdered activated carbon mixture comprising powdered activated carbon and silicate,
c) mixing the iron-zinc composite metal oxide and the powdered activated carbon mixture to produce an activated carbon adsorbent for acidic gas removal,
Wherein the activated carbon adsorbent is an activated carbon adsorbent. The method of claim 3,
In the step a), the iron salt may include one or more selected from the group consisting of iron sulfate, iron ammonium sulfate, iron oxide, iron hydroxide, iron nitrate and iron chloride, hydrates thereof,
Wherein the zinc salt is at least one selected from the group consisting of zinc sulfate, zinc ammonium sulfate, zinc oxide, zinc hydroxide, zinc nitrate and zinc chloride, hydrates thereof, and mixtures thereof, Way. The method of claim 3,
In the step a), the first basic metal compound comprises any one or a mixture of two or more selected from sodium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide. The method of claim 3,
In the step a), the weight ratio of the iron salt and the zinc salt to the iron salt: zinc salt is 1: 9 to 9: 1,
Wherein the first basic metal compound comprises 10 to 100 parts by weight based on 100 parts by weight of the sum of the iron salt and the zinc salt. The method of claim 3,
Wherein the silicate is contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of activated carbon powder in the step b). The method of claim 3,
In the step b), the powdered activated carbon mixture further comprises a second basic metal compound including any one or a mixture of two or more selected from sodium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide, to prepare an activated carbon adsorbent for acidic gas removal Way. The method of claim 3,
The method for producing an activated carbon adsorbent for acidic degassing according to claim 1, wherein, in step (c), 20 to 200 parts by weight of a powdered activated carbon mixture is added to 100 parts by weight of the iron-zinc composite metal oxide. The method of claim 3,
The method for producing an activated carbon adsorbent for acidic degassing according to claim 1, wherein the iron-zinc composite metal oxide is heated and mixed with water and then cooled.

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