KR20110011858A - A depurator for harmfulness gas removal and its manufacturing method - Google Patents

Abstract

PURPOSE: An acidic cleaning agent for removing hazardous gases and a producing method thereof are provided to reduce the risk of fires by the combustion of activated charcoal and the production of the activated charcoal and metal materials into a pellet shape. CONSTITUTION: An acidic cleaning agent for removing hazardous gases contains the following: 60~99wt% of a main component selected from hydroxy iron, ferric oxide, calcium hydroxide, and magnesium hydroxide; and 1~40wt% of activated charcoal powder. The acidic cleaning agent is produced by mixing and kneading the components. The purifying agent additionally contains 1~10wt% of binder material selected from silica, diatomite, the activated charcoal, and active alumina.

Description

Purifying agent for acidic noxious gas removal and its manufacturing method {A Depurator for Harmfulness Gas Removal and Its Manufacturing Method}

In the present invention, in order to purify the acidic harmful gas generated in the semiconductor manufacturing process and industrial sites, as the neutralizing agent for treating the acidic harmful gas, at least one selected from iron hydroxide, iron oxide, calcium hydroxide and magnesium hydroxide as a main component, To 60% by weight to 99% by weight, 1% by weight to 40% by weight of the activated carbon powder is mixed with water and kneaded with water to remove the acidic harmful gas produced by using an extruder, one specific example of the acid The purifying agent for removing harmful gases is a mixture of FeCl ₃ 6H ₂ O and diatomaceous earth and neutralized with Na ₂ CO ₃ , followed by filtration of the precipitated sludge and washing of the filtered sludge, followed by drying the washed sludge. After the step of making, to prepare the iron hydroxide and to crush the dried iron hydroxide into a powder state, the powder To the womb hydroxide (metal) and the activated carbon powder, kneading with water, a step of using an extruder molding prepared by drying a pellet form.

In general, the targets for treating hazardous gases can be classified into Hazardous Gas Treatment Agents and Hazardous Gas Treatment Agents. Of these, Hazardous Gas Treatment Agents can be divided into air purification treatment agents and hazardous gas purification agents. Hazardous gas purifiers for treating harmful gases have been developed in a technical configuration consisting mainly of adsorbents. For this purpose, Korean Patent Publication No. 10-0905004, Korean Patent Publication No. 2002-0037609 and Patent Registration Publication No. 10 The technical configuration is disclosed in detail in -0412982.

The main technical configuration used in the prior art is made of a method of attaching a metal substance to activated carbon. Specifically, a method of adsorbing and removing harmful gas by attaching a metal salt or an alkali component to activated carbon and treating an inorganic metal salt with a neutralizing agent and then attaching it to activated carbon Therefore, it can be classified into two types by adsorption and removal of harmful gas.

When the metal is attached to the activated carbon and used as an industrial hazardous gas treatment agent, severe heat of reaction occurs during the reaction, desorption occurs near the saturation point, and the activated carbon is often burned by the generated heat of reaction. There is a risk of explosion at all times, and there is a problem that the use is limited because the explosion may occur in an actual industrial site.

In addition, although alkali metals such as Ca (OH) ₂ or Mg (OH) ₂ and iron oxides Fe (OH) ₃ have been considered for use as hazardous gas treating agents, these alkali metals and iron oxides have low specific surface areas and are not easily reacted. There is a problem that the purification efficiency is greatly lowered only occurs on the surface.

The problem to be solved by the present invention is adsorption by reacting acidic gases such as HCl, Cl ₂ , HBr, Br ₂ , AlCl ₃ , BCl ₃ , HF, F ₂ , OF ₂ , TiCl ₄ , NOx, SOx among industrial harmful gases To provide a purifying agent for removing acidic harmful gas to remove, but to greatly enhance the safety, adsorption capacity and reactivity of acidic harmful gas.

The reaction formula of the alkali metal and the iron oxide with acid gas is as follows.

Ca (OH) ₂ + 2HCl-> CaCl ₂ + 2H ₂ O

Mg (OH) ₂ + 2HCl-> MgCl ₂ + 2H ₂ O

Fe (OH) ₃ + 3HCl-> FeCl ₃ + 3H ₂ O

Another problem to be solved by the present invention is the use of alkali metal or iron hydroxide for the removal of acidic harmful gas, but these have a problem that the specific surface area is low, the reaction occurs only on the surface and the reaction does not occur inside, so the purification efficiency is inferior To solve this problem, in order to increase specific surface area when manufacturing acidic noxious gas purifier, these metal materials and activated carbon are mixed at a certain ratio and manufactured in pellet form to reduce the risk of fire caused by burning of activated carbon, and to improve durability, reactivity and adsorption capacity. It is to raise.

Solution to Problem The present invention is composed of a main component by selecting one or more of iron hydroxide, iron oxide, calcium hydroxide and magnesium hydroxide as a neutralizing agent for treating acidic harmful gases in order to purify acidic harmful gases generated in semiconductor manufacturing processes and industrial sites. However, 60 to 99% by weight of the main component, 40 to 1% by weight of activated carbon powder is mixed and kneaded with water to form a pellet form using an extruder to produce a fire hazard by combustion of activated carbon It is to reduce the acidity, increase the reactivity with the acidic harmful gas and to achieve a purifying agent for removing the acidic harmful gas greatly improved adsorption capacity.

Another solution of the present invention is a mixture of FeCl ₃ 6H ₂ O and diatomaceous earth and then neutralized with Na ₂ CO ₃ to precipitate the sludge produced by the precipitate, and the step of washing the filtered sludge After drying the sludge washed with water or detergent, grinding the dried sludge into powder form, mixing and pulverizing the mixed metal hydroxide powder and activated carbon powder into water to form a pellet using an extruder Through the step of producing, to provide a method for producing a purifying agent for removing acidic harmful gas consisting of drying the prepared pellets.

Another solution to the problem of the present invention is Fe (OH) ₂ , FeO (OH) and Fe ₂ O ₃ , which are widely used as neutralizing metals, are manufactured using FeCl ₃ ㆍ 6H ₂ O as a main raw material, and FeCl ₃ ㆍ 6H ₂ O is widely used as an etching solution after nickel plating, and it is inexpensive to provide a purifying agent for removing acidic noxious gases and a method of manufacturing the same, which can enhance reactivity with acidic noxious gases, improve adsorption capacity, and lower production costs. .

Industrial toxic gas of the present invention can be classified into acid gas, alkali gas, flammable gas, etc., the acid gas is HCl, Cl ₂ , HBr, Br ₂ , AlCl ₃ , BCl ₃ , HF, F ₂ , OF ₂ , TiCl ₄ , NOx, SOx and the like, to provide a purifying agent for removing acidic harmful gas to remove the adsorption by reacting, but has the effect of significantly increasing the durability, adsorption capacity and reactivity.

The reaction formula of the alkali metal and the iron oxide with acid gas is as follows.

Ca (OH) ₂ + 2HCl-> CaCl ₂ + 2H ₂ O

Mg (OH) ₂ + 2HCl-> MgCl ₂ + 2H ₂ O

Fe (OH) ₃ + 3HCl-> FeCl ₃ + 3H ₂ O

Another effect of the present invention is the use of alkali metal or iron hydroxide for the removal of acidic harmful gas, but they have a specific surface area because the reaction occurs only on the surface and the reaction does not occur in the interior so as to solve the problem of lowering the purification efficiency In the manufacture of acid noxious gas purifier, in order to increase the specific surface, these metal materials and activated carbon are mixed in a certain ratio to make pellets, which reduces the risk of fire caused by the combustion of activated carbon and increases durability, reactivity and adsorption capacity. .

Hereinafter, the present invention will be described in detail. The present invention is composed of a main component by selecting one or more of iron hydroxide, iron oxide, calcium hydroxide and magnesium hydroxide as a neutralizing agent for treating the acidic harmful gas in order to purify the acidic harmful gas generated in the semiconductor manufacturing process and industrial sites. 60 to 99% by weight of the composition, and 1 to 40% by weight of the activated carbon powder is mixed and kneaded with water to produce a pellet shape using an extruder to increase the reactivity with acidic harmful gases and greatly adsorption capacity An improved purifying agent for removing acidic harmful gases.

The purifying agent for removing acidic harmful gases according to the present invention is selected from one of silica, diatomaceous earth, activated carbon and activated alumina as a binder material to prepare iron hydroxide, iron oxide, calcium hydroxide and magnesium hydroxide to add 1 wt% to 10 wt% It can manufacture.

In addition, the present invention is a mixture of FeCl ₃ ㆍ 6H ₂ O and diatomaceous earth to produce iron hydroxide, and then neutralized with Na ₂ CO ₃ to filter the precipitate produced sludge, washing the filtered sludge with water or washing agent After the step of drying, the dried sludge is dried, the dried sludge is pulverized to a powder state, the powdered iron hydroxide and activated carbon powder mixed and kneaded with water to form a pellet shape using an extruder It relates to a method for producing an acidic noxious gas purifying agent consisting of drying the pellets produced by the production step.

The main raw material for producing iron hydroxide or iron oxide is FeCl ₃ .6H ₂ O, and the neutralizing alkali is selected from Na ₂ CO ₃ , K ₂ CO ₃ , NaOH, CaOH, KOH.

Hereinafter, the configuration and operation of the embodiments of the present invention with reference to the accompanying drawings, the configuration and operation of the present invention shown and described in the drawings will be described in at least one or more embodiments, thereby The technical spirit of the invention and its core configuration and operation are not limited.

Look at the drawings to facilitate understanding of the present invention. Figure 1 shows a flow chart of the manufacturing method of the acidic noxious gas removal purifier according to the present invention, Figure 2 shows an apparatus for experimenting the performance of the acidic noxious gas removal purifier prepared in accordance with the present invention. Figure 3 is a bar graph showing the results of testing the ability to remove chlorine gas using an acidic harmful gas removal purifier prepared in accordance with the present invention. Figure 4 is a bar graph showing the results of testing the ability to remove hydrogen chloride gas using the acidic noxious gas removal purifier prepared in accordance with the present invention. A specific embodiment according to the present invention will be described.

EXAMPLES

It looks at a specific embodiment according to the present invention. Fe (OH) ₂ , FeO (OH), Fe ₂ O _3, and the like, which are widely used as the neutralizing metal used in the present invention, are manufactured using FeCl ₃ · 6H ₂ O as a main raw material.

FeCl ₃ · 6H ₂ O is used as an etching solution after nickel plating, and the price is low, and there is an advantage of lowering the production cost of the purifier for removing acidic harmful gases. The purifying agent for acidic harmful gas removal and a manufacturing method thereof will be described in detail. To 50 liters (ℓ) of 30% by weight FeCl ₃ solution, one of the neutralizing agents, Na ₂ CO ₃ , K ₂ CO ₃ , KOH and NaOH, was selected and added at a pH of 12 to form a neutral precipitate to form a neutral precipitate. Is about 9.

A binder material (nucleated material) necessary for forming a sludge by precipitation reaction to prepare Fe (OH) ₃ or FeO (OH), etc., using FeCl ₃ ㆍ 6H ₂ O as a main raw material. At least one selected from alumina, diatomaceous earth, and silica is used.

Preferably, it is preferable to use diatomaceous earth, and when diatomaceous earth is used, the process of filtering the precipitated sludge can be easily performed.

By filtering the sludge produced by precipitation of the FeCl ₃ 6H ₂ O solution and the neutralizing agent neutralized with each other, and washing the produced sludge with water or a washing agent, the water content of the sludge is 5% to 20% Drying step as possible. Dry sludge is pulverized and prepared into a metal hydroxide (iron) powder such as Fe (OH) ₃ or FeO (OH). The specific surface area of the metal hydroxide (iron) powder at this time is about 50 to 150 m 2 / gr. In the drying step, but dried in a dryer for 1 hour to 3 hours at less than 110 ℃ under safe conditions that activated carbon does not burn.

Purifying agent for removing acidic harmful gas according to the present invention is selected from one or more of the main components iron hydroxide, iron oxide, calcium hydroxide, magnesium hydroxide powder to 60 to 99% by weight, and activated carbon powder 40 to 1% by weight After mixing and mixing and kneading with water using a stirrer, an extruder is used to make a pellet into a pellet shape having a diameter of about 0.5 mm to 7 mm. At this time, the moisture content of the pellet is about 30% to 70%, so that it is dried with a dryer and dried to a moisture content of 5% to 20%. The size of the activated carbon powder mixed with the metal hydroxide (iron) powder is about 50 to 400 mesh (mesh), the specific surface area is about 500 to 1,200 m 2 / gr.

The specific surface area of the molded acidic purifying agent for removing harmful gas is about 100 to 300 m 2 / gr. The acidic harmful gas includes HCl, Cl ₂ , HF, BCl ₃ , AlCl ₃ , TiCl ₃ , SO ₃ , NO ₂ and the like. Purifying agent (process) for acidic harmful gas removal according to the present invention is as shown in the flowchart of FIG.

Example 1

As shown in the flowchart of FIG. 1, FeCl ₃ · 6H ₂ O and diatomaceous earth are mixed, followed by neutralization with Na ₂ CO ₃ to produce precipitated sludge (iron hydroxide), and the produced sludge (iron hydroxide) is filtered and then washed with water or a washing agent. After washing, the washed sludge (iron hydroxide) is dried, and then pulverized in a powder state to prepare a powder of Fe (OH) ₃ or FeO (OH).

① Inject 200 gr of Fe (OH) ₃ or FeO (OH) powder (particle size: 50 ~ 400 mesh) to 95% by weight.

② Inject 10 gr of activated carbon powder (particle size: 50 to 400 mesh), mix and knead it to 5% by weight, and shape it into pellet shape with diameter of 1mm using extruder, and then dry it safely to prevent combustion of activated carbon in the dryer. In order to dry for 1 to 3 hours at less than 110 ℃. 100 cc of the dried pellet-shaped acidic noxious gas removal purifier was filled in a reactor (D: 36mm L: 150mm) and passed through the reactor by controlling with a Mass Flow Controller (MFC) such that HCl or Cl ₂ concentration was 1%. Experiments were performed to treat acidic noxious gases. Figure 2 shows a schematic diagram of an apparatus for filling the reactor with an acidic noxious gas removal purifier and testing the performance of the acidic noxious gas removal purifier by passing chlorine gas or hydrogen chloride gas through the reactor.

Table 1 shows the conditions of the reactor for testing the performance of the purifying agent for removing acidic harmful gases prepared according to Examples 1 to 7.

Table 1: Conditions of Reactor for Performing Examples 1-7

Example 2

Experimental method of Example 2 was the same as in Example 1, except that the sample was prepared by adjusting the weight ratio of the activated carbon powder to 10% and the acid harmful gas purification experiment was performed.

Example 3

The experimental method of Example 3 was the same as in Example 1, except that the sample was prepared by adjusting the weight ratio of activated carbon powder to 15%, and the acid harmful gas purification experiment was performed.

Example 4

Experimental method of Example 4 was the same as in Example 1, except that the sample was prepared by adjusting the weight ratio of the activated carbon powder to 20% and the acid harmful gas purification experiment was performed.

Example 5

Experimental method of Example 5 was the same as in Example 1, except that the sample was prepared by adjusting the weight ratio of the activated carbon powder to 25% to perform an acid harmful gas purification experiment.

Example 6

Experimental method of Example 6 was the same as in Example 1, except that the sample was prepared by adjusting the weight ratio of the activated carbon powder to 30% was carried out acidic harmful gas purification experiment.

Example 7

Experimental method of Example 7 was the same as in Example 1, except that the sample was prepared by adjusting the weight ratio of the activated carbon powder to 40% was carried out acidic harmful gas purification experiment.

FIG. 3 shows the results of conducting acid hazardous gas treatment experiments while adjusting the concentration of Cl ₂ to 1% by using a MFC (Mass Flow Controller) in the experimental apparatus of FIG. It is shown as a bar graph.

As can be seen from Figure 3, it can be seen that the larger the amount of activated carbon powder added, the more time it can be processed. The removal efficiency of chlorine gas was excellent as more than 99.9% by the analysis by FT-IR (11) of Midac.

However, when increasing the amount of activated carbon powder added in order to increase the treatment time, it is preferable to mix at 40% by weight or less because of the high risk of explosion due to reaction heat as in the prior art.

4 is HCl gas in the experimental apparatus of FIG. The concentration is 1% by using a Mass Flow Controller (MFC) is shown in the bar graph shows the results of conducting the acidic hazardous gas treatment experiment while passing through the reactor filled with an acidic harmful gas removal purifier.

As can be seen from Figure 4, in the case of HCl gas, even if the ratio of the amount of activated carbon powder added does not change significantly, the removal efficiency of the hydrogen chloride gas is confirmed by the FT-IR (11) of Midac 99.9% or more Was excellent.

Example 1 to Example 7 was used for the experiment to prepare a purifying agent for removing acidic harmful gas using metal hydroxide (iron), but also in the case of calcium hydroxide or magnesium hydroxide can be prepared under the same conditions as the manufacturing method of the iron hydroxide. have.

The present invention is a neutralizing agent for treating acidic harmful gases, the main component is selected from one or more of iron hydroxide, iron oxide, calcium hydroxide and magnesium hydroxide to 60% to 99% by weight, and mixed activated carbon powder 1% to 40% by weight It is a purifying agent for removing acidic harmful gas, and the main raw material used to prepare the iron hydroxide is FeCl ₃ ㆍ 6H ₂ O, and the neutralizing alkali is at least one of Na ₂ CO ₃ , K ₂ CO ₃ , NaOH, CaOH, KOH Select to use.

When one or more of the neutralizing agents for treating acidic harmful gases are selected from 60% to 99% by weight of iron hydroxide, iron oxide, calcium hydroxide, and magnesium hydroxide, one or more selected from silica, diatomaceous earth, activated carbon, and activated alumina It can be added between 1% and 10% by weight. The size of the activated carbon powder is preferably in the range of 50 to 400 mesh (mesh), the specific surface area is preferably made between 200 to 1,200 m 2 / gr.

In the method for preparing an acidic harmful gas purifying agent according to the present invention, to prepare iron hydroxide, FeCl ₃ ㆍ 6H ₂ O is mixed with diatomaceous earth, and then neutralized with Na ₂ CO ₃ to precipitate sludge (iron hydroxide) produced by precipitation. After passing through the step of washing the filtered sludge (iron hydroxide) with water or a washing agent, drying the washed sludge (iron hydroxide), the dried sludge (iron hydroxide) powder between 50 to 400 mesh (mesh) After the step of pulverizing in a state, the step of mixing and kneading the powdered iron hydroxide and activated carbon powder into water, and the step of manufacturing the mixed kneaded mixture in the form of pellets using an extruder, molding Drying the pellets.

Mixing and kneading the powdered iron hydroxide and activated carbon powder comprises 60 wt% to 99 wt% of powdered iron hydroxide, 1 wt% to 40 wt% of activated carbon powder, mixed with water and kneaded with an extruder Molded, pelletized and dried.

According to the present invention, the acid noxious gas removal purifying agent manufactured by using an extruder by the method for preparing the acid noxious gas purifying agent is also within the protection scope of the present invention.

The purifying agent for removing acidic harmful gases according to the present invention reacts with and removes the adsorptions by reacting with acidic gases HCl, Cl ₂ , HBr, Br ₂ , AlCl ₃ , BCl ₃ , HF, F ₂ , OF ₂ , TiCl ₄ , NOx, SOx and the like. It has good adsorption capacity and reactivity, and has excellent durability and safety, and thus has high industrial applicability.

1 is a flowchart of a method of preparing a purifying agent for removing acidic harmful gas according to the present invention.

2 is an apparatus for experimenting the performance of the acidic harmful gas removal purifier prepared in accordance with the present invention

Figure 3: A graph showing the results of testing the ability to remove chlorine gas using an acidic harmful gas removal purifier prepared according to the present invention

4 is a graph showing the results of testing the ability to remove hydrogen chloride gas using the acidic noxious gas removal purifier prepared according to the present invention.

Claims (10)

In order to process acidic harmful gas, the main component is selected from at least one of iron hydroxide, iron oxide, calcium hydroxide and magnesium hydroxide to form 60% to 99% by weight, and mixing and kneading activated carbon powder at 1% to 40% by weight Purifier for removing acidic harmful gases. The method according to claim 1, The iron hydroxide is used as FeCl ₃ ㆍ 6H2O as the main raw material, neutralizing agent is prepared by using one selected from Na ₂ CO ₃ , K ₂ CO ₃ , NaOH, CaOH and KOH. The method according to claim 1, When one or more of the iron hydroxide, iron oxide, calcium hydroxide and magnesium hydroxide is selected to form 60% to 99% by weight, 1% by weight to 10% by weight of one or more selected from silica, diatomaceous earth, activated carbon, activated alumina as a binder material Purifying agent for the removal of acidic harmful gases, characterized in that prepared by adding between. The method according to any one of claims 1 to 3, The acidic noxious gas is HCl, Cl ₂ , HF, BCl ₃ , AlCl ₃ , TiCl ₃ , SO ₃ , NO ₂ gas purifier for removing acidic noxious gases. The method according to any one of claims 1 to 3, The activated carbon powder has a size of 50 to 400 mesh, specific surface area is 200 to 1,200 m 2 / gr characterized in that the purifier for acidic harmful gas removal. In the manufacturing method of the purifying agent for acidic harmful gas removal, Filtering FeCl ₃ 6H ₂ O with diatomaceous earth and neutralizing it with Na ₂ CO ₃ to precipitate and precipitate the resulting iron hydroxide; Washing the filtered iron hydroxide; Drying the washed iron hydroxide; Grinding the dried iron hydroxide into a powder state; Mixing and kneading the powdered iron hydroxide and activated carbon powder; Preparing the kneaded mixture into pellets with an extruder; And Method for producing a purifying agent for removing acidic harmful gas comprising the step of drying the prepared pellets. The method according to claim 6, In the step of mixing and kneading the powdered iron hydroxide and activated carbon powder, the powdered iron hydroxide is 60 wt% to 99 wt%, and the activated carbon powder is injected at 1 wt% to 40 wt% to mix and knead with water. Method of producing a purifying agent for removing acidic harmful gas. The method according to claim 6, Drying the sludge and drying the pellets are acidic harmful gas, characterized in that the drying temperature is dried at less than 110 ℃ so that the activated carbon can be safely dried without burning, drying between 5% and 20% water content Method for preparing a purifying agent for removal. The method according to claim 6, In the step of producing the kneaded mixture into pellets by an extruder, a specific surface area of the acidic noxious gas removal purifying agent is prepared between 100 and 300 m 2 / gr. A purifying agent for removing an acidic noxious gas prepared by the method for preparing an purifying agent for removing an acidic noxious gas according to any one of claims 6 to 9.

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