KR20010100208A - Complex Catalysts Used For Removing Aromatic Halogen Compounds and Phenol Compounds Among Flue Gases and Method For Preparing The Sames - Google Patents

Abstract

The present invention relates to a composite catalyst used to remove aromatic halogen compounds such as dioxins and the like contained in exhaust gases discharged from various combustion facilities such as incinerators, and a method of manufacturing the same. The present invention provides a calcination catalyst in which a metal salt or a metal oxide 0.5-60 weight (in terms of oxide weight ratio) is supported on 40-99.5 weight of a support material; And an aromatic halogen compound contained in the exhaust gas, including alkali metal and / or alkaline earth metal supported on the calcining catalyst in an amount of 4-400 parts by weight based on 100 parts by weight of the calcining catalyst. To provide. The present invention removes the aromatic halogen compound contained in the exhaust gas with high energy efficiency without installing expensive catalyst tower and additional equipment by injecting the composite catalyst into the alkali absorption tower, the vibration isolator, or the front of the vibration isolator in powder form. In addition to this, phenols and sulfur oxides can be removed. In addition, by using the composite catalyst of the present invention, harmful substances such as aromatic halogen compounds can be removed from the soil and the like.

Description

Complex Catalysts Used For Removing Aromatic Halogen Compounds and Phenol Compounds Among Flue Gases and Method For Preparing The Sames}

The present invention relates to a complex catalyst used to remove an aromatic halogen compound such as dioxins contained in the exhaust gas, and a method for producing the same. Specifically, the present invention relates to dioxins contained in exhaust gases emitted from various combustion facilities such as boilers, power plants, and incinerators. The present invention relates to a composite catalyst used to remove an aromatic halogen compound, a phenol compound, an acidic substance such as sulfur oxide, and the like, and a method for producing the same. The composite catalyst of the present invention can be used to remove not only exhaust gases but also acidic substances such as aromatic halogen compounds such as dioxins, phenol compounds, and sulfur oxides contained in contaminated soil and contaminated waste. In addition, the present invention includes a method for removing an aromatic halogen compound, such as dioxin, phenolic compounds, sulfuric acid, such as sulfur oxides contained in the exhaust gas, contaminated soil or contaminated waste using the complex catalyst.

One conventional technique for removing aromatic halogen compounds such as dioxins contained in exhaust gases emitted from various combustion facilities is generally a catalyst prepared by reacting a transition metal material such as vanadium, tungsten, molybdenum, titanium, or the like with zeolite. It is bonded to a substrate such as a honeycomb-type cordierite, which is durable, and loaded into the catalyst column in multiple stages or granulated to fill the catalyst tower.

1 shows a conceptual diagram of a combustion facility for treating dioxins using such a catalyst tower. In general, since the exhaust gas contains not only aromatic halogen compounds such as dioxins but also nitrogen oxides, catalysts capable of decomposing nitrogen oxides and dioxins and catalysts capable of decomposing dioxins to remove nitrogen oxides and dioxins by means of a catalyst tower. It is installed as a separate catalyst tower or continuously installed in one catalyst tower. 1 is a process according to the so-called selective catalytic reduction method (SCR) and catalytic decomposition in which ammonia or ammonia water is injected into a catalyst heated to a high temperature using a reducing agent to selectively reduce only nitrogen oxides to convert to nitrogen gas. It is shown that the process of decomposing dioxins is simultaneously performed.

As shown in FIG. 1, first, the exhaust gas discharged from the combustion chamber passes through an alkali absorption tower, which is a device for removing sulfur oxides. At this time, an alkali substance such as slaked lime is administered to the alkali absorption tower. The exhaust gas passing through the alkali absorption tower is then passed through a dust removal device or dust collector to remove particles such as dust mixed in the exhaust gas. Typically, the honeycomb cordierite used in the catalyst tower is designed to be durable, but its design and manufacture are expensive, so it is necessary to prevent abrasion due to dust or the like in order to ensure maximum life. . Therefore, dust or the like in the exhaust gas is generally removed by a vibration suppression apparatus or a dust collector before entering the catalyst tower.

Next, the exhaust gas passing through the vibration damper or dust collector is passed through the catalyst tower to reduce nitrogen oxides in the exhaust gas to nitrogen. At this time, ammonia or ammonia water is usually injected into the catalyst tower as a reducing agent capable of reducing nitrogen oxides. In addition, since a high reaction temperature is required for nitrogen oxide to be reduced by the catalyst and the reducing agent of the catalyst tower, a preheating device is installed at the inlet side of the catalyst tower. The reaction temperature for reducing the nitrogen oxides should be 210 ° C. or higher, and the reaction is usually carried out at a temperature of 250 ° C. to 350 ° C. In general, nitrogen oxides are reduced to nitrogen in a catalyst tower for removing nitrogen oxides, but other aromatic halogen compounds such as dioxins are not removed from the catalyst tower. Therefore, in order to remove dioxin, a catalyst suitable for decomposing dioxin separately from the above-described catalyst tower or in the same catalyst tower is continuously installed separately from or in the same catalyst tower. In general, the decomposition reaction of dioxins also requires a high reaction temperature.

On the other hand, the reducing agent such as ammonia injected from the catalyst tower is a pollutant that should not be discharged to the atmosphere and should not be injected in excess of the amount necessary to reduce the nitrogen oxides. To this end, an apparatus for detecting the amount of ammonia in the exhaust gas discharged to the atmosphere should be installed at the outlet, and the amount of ammonia injected from the catalyst tower should be controlled while monitoring the amount of ammonia detected. In addition, it is necessary to install a separate facility for removing ammonia in preparation for excess ammonia is injected and ammonia is released into the atmosphere.

Nitrogen oxides contained in the exhaust gas are reduced to nitrogen by passing through two separate catalyst towers or catalyst towers including two different catalysts, and aromatic halogen compounds such as dioxins are removed from the catalyst tower. Since dioxins are difficult to remove even by the catalyst tower, exhaust gas is generally passed through an activated carbon adsorption tower to completely remove dioxins. Although the dioxin can be sufficiently removed by the above catalyst tower, since the dioxin is very toxic, this additional activated carbon adsorption tower is also used to reliably prevent the release of dioxin into the atmosphere. In fact, the catalyst tower is designed to remove only nitrogen oxides, and the removal of dioxins is usually achieved only by activated carbon adsorption towers. As described below, it is expensive to design and manufacture a catalyst tower, and additional difficulties exist when implementing a catalyst for removing nitrogen oxides and a catalyst for removing dioxins in the same catalyst tower. Because.

The use of such a catalyst tower for the removal of nitrogen oxides and aromatic halogen compounds has several problems as follows. In other words,

First, it is expensive to design and manufacture a durable honeycomb cordierite. That is, a large investment cost is required for the installation of the catalyst tower.

Second, since the reaction temperature required for the reduction reaction of nitrogen oxides and the decomposition reaction of dioxins is 210 ° C. or higher, typically 250 ° C. to 350 ° C., a facility for preheating the exhaust gas at the inlet side of the catalyst tower is required. Due to the demands, much energy is consumed.

Third, ammonia is injected into the catalyst tower as a reducing agent for reducing nitrogen oxides, so the burden of storing and managing ammonia is high.

Fourth, an apparatus for detecting the emission of ammonia discharged to the atmosphere and an apparatus for monitoring the discharge of the ammonia are additionally required, and a separate supplementary equipment for removing excess or unreacted ammonia gas is needed.

Fifth, there is a problem in that the pressure loss of the exhaust gas is very large when the particulate catalyst is packed in the catalyst tower.

Sixth, in the case of stacking a honeycomb catalyst, the honeycomb structure may be destroyed by dust or the like, and the life of the catalyst may be reduced.

Seventh, since different catalysts must be installed in separate catalyst towers or continuously installed in the same catalyst tower, the structure of the catalyst tower becomes complicated and the design of the catalyst tower becomes more complicated.

On the other hand, Figure 2 is a conventional method for removing nitrogen oxides and dioxins contained in the exhaust gas of the combustion facility for removing nitrogen oxides using a selective non-catalytic reduction method (SNCR) Show the conceptual diagram. There is no special device for dioxin removal here, it only absorbs dioxin by the active tower absorption tower. As shown in FIG. 2, the selective non-catalytic reduction method directly injects ammonia or urea solution, which is a reducing agent for reducing nitrogen oxides, into a combustion site in a combustion chamber to reduce nitrogen oxides. Compared to the selective catalytic reduction method of FIG. 1, the difference in not only using a catalyst tower but also using no catalyst at all is directly injecting ammonia into the combustion chamber to reduce nitrogen oxides in the exhaust gas using the high temperature of the combustion chamber. have. In addition, there is a difference that there is no separate device for removing dioxins except the active tower absorption tower. However, this selective non-catalytic reduction method has the following problems.

First, since it must be injected directly into the combustion chamber to obtain a high temperature condition, there is a difficulty in the operation of the injection facility and maintenance of the combustion conditions.

Second, there is a limit to the removal rate of nitrogen oxides (typically 60 is the limit line).

In addition, as the same problem as the selective catalytic reduction method,

Third, since ammonia is used as a reducing agent for reducing nitrogen oxide in the combustion chamber, storage and management of ammonia is necessary.

Fourth, an apparatus for detecting the emission of ammonia discharged to the atmosphere and an apparatus for monitoring the discharge of the ammonia are additionally required, and a separate supplementary equipment for removing excess or unreacted ammonia gas is needed.

Fifth, removal of nitrogen oxides can be achieved by the reduction reaction of ammonia in the combustion chamber, but it is not possible to remove aromatic halogen compounds such as dioxins and the like, and thus additional apparatuses such as activated carbon adsorption towers are required to remove them.

Sixth, when dioxin is adsorbed by activated carbon adsorption column, dioxin is not decomposed and changed into a harmless substance, but only dioxin is adsorbed on activated carbon. Or dioxins in the waste activated carbon itself. At this time, it is difficult to completely dismantle dioxin even by the additional process that is difficult and additional process, and there is a problem that secondary contamination may occur by the organic solvent when extracted with the organic solvent.

On the other hand, techniques for removing aromatic halogen compounds, such as dioxins, remaining in powdered or particulate contaminated waste or soil, are among the world's starting stages, including glycogenated halogen removal and base-catalytic decomposition.

FIG. 3 shows a conceptual diagram of a method for removing aromatic halogen compounds such as dioxins remaining in powdered or particulate contaminated waste or soil by glycogenated halogen removal. As shown in FIG. 3, the glycogenated halogen removal method includes an APEG (Alkaline Polyethyleneglycol) agent in which an alkali metal base and polyethylene glycol (excess polyethylene glycol acts as a solvent) are combined with particulate or powdery waste or soil contaminated in a reactor. The mixture is heated at a temperature of 200 ° C. or more for 4 hours or more. At this time, the halogen element of an aromatic halogen compound such as dioxin is converted into a harmless base by reaction with an alkali metal, and polyethylene glycol is combined with an aromatic halogen compound instead of a halogen element to change into a relatively low toxic substance by the reaction. When the reaction is completed, the steam generated by the reaction is separated into water and gas in the condenser. The gas separated from the condenser may contain decomposition products of aromatic halogen compounds such as dioxins. Since there may be harmful substances, it is common to adsorb these harmful substances by activated carbon before discharge into the atmosphere. In addition, the mixture of APEG and waste or soil is transferred to a solvent separator where the solvent separated is recycled for use in the reaction. The purified waste or soil is transferred to a washer where it is washed with water. In this case, the water supplied may be water separated from a condenser, and may be replenished externally when it is insufficient. The purified or washed waste or soil is then transferred to a dehydration apparatus and dehydrated to complete the purification process. However, this method has the following problems.

First, the APEG agent is separated from the purified waste or soil in the solvent separation device, but the purified waste or soil is adsorbed with a viscous APEG agent, which is another contamination when washing the purified waste or soil with a large amount of water to remove it. This is caused. Second, the process of recycling APEG agent, the process of removing water from condenser from steam generated in the reactor and purifying the steam by passing it through activated carbon, washing and dehydration process are complicated and expensive for this process. This costs

4 shows a conceptual diagram of a method for removing aromatic halogen compounds such as dioxins remaining in powdered or particulate contaminated waste or soil by base-catalytic decomposition. As shown in FIG. 4, the base-catalyst decomposition method mixes sodium carbonate and contaminated soil or granular waste in a reactor at 1:10 (weight ratio) and heats it to 400 ° C. or more. When the reaction is complete, a purified granular material or soil is obtained. In addition, the aromatic halogen compound is discharged from the reactor in the form of steam, and the discharged steam is concentrated in a liquid state by a condenser, and this is treated with a halogen remover such as a strong base in a reactor at 400 ° C. or higher to replace the halogen element with an aromatic halogen compound. By removing the halogen element into a harmless compound form which is not substituted. However, this method solves problems such as waste water compared to the glycogenated halogen removal method, but has the following problems.

First, it requires a lot of energy costs because it has to be processed at high temperatures. Second, a large amount of chemicals (sodium carbonate, strong bases used as halogen removers, etc.) are required, and in particular, further post-treatment processes for the used strong bases are required, which can cause other contamination.

An object of the present invention is a complex catalyst used to remove aromatic halogen compounds from exhaust gases emitted by combustion, without the need for equipment that requires high equipment costs, such as a catalyst tower loaded with a durable honeycomb cordierite It is to provide a manufacturing method.

In addition, an object of the present invention is a complex catalyst used to remove aromatic halogen compounds from exhaust gases emitted by combustion, which does not require a separate preheating device because the reaction temperature is not high, and the energy cost required for the reaction is low. It is to provide a manufacturing method.

It is also an object of the present invention to provide a composite catalyst capable of removing not only aromatic halogen compounds such as dioxins contained in exhaust gas, but also phenol compounds and sulfur oxides, and a method for producing the same.

In addition, the object of the present invention, in addition to the above advantages, the amount of chemicals added without the use of a solvent that can cause secondary pollution, but also excellent in the decomposition efficiency of aromatic halogen compounds, phenol compounds and sulfur oxides, pollution The present invention provides a composite catalyst and a method for producing the same, which are used to remove the substances remaining in waste soil or contaminated waste.

It is also an object of the present invention to bury the purified waste or soil obtained by applying to contaminated soil or applying to contaminated waste as well as the benefit of removing aromatic halogen compounds from contaminated soil or contaminated waste. If so, to provide a composite catalyst and a method for producing the same that does not cause any other contamination or harmful. When the catalyst of the present invention is buried in the ground after use, it takes the form of metal hydroxide and metal oxide or complex metal salt oxide and its amount is very small compared to the soil to be purified. Landfilling has little environmental impact. Rather, in general, considering the tendency of acidification of the soil, the basicity of the metal hydroxide may be slightly helpful in preventing the acidification of the soil.

In addition, an object of the present invention is to remove the aromatic halogen compounds, phenol compounds and sulfur oxides contained in the exhaust gas having the above-mentioned advantages by using the complex catalyst and the above-mentioned residues remaining in contaminated soil or contaminated waste. It is to provide a method for removing substances.

FIG. 1 is a conceptual diagram of a combustion facility for treating an aromatic halogen compound such as nitrogen oxides, dioxins, and sulfur oxides by using a catalyst tower and an alkali absorption tower as a conventional method of removing dioxins and the like contained in exhaust gas.

Figure 2 is a conventional method for removing dioxin and the like contained in the exhaust gas, using a non-catalyst reduction method, an alkali absorption tower and activated carbon, a combustion facility for treating aromatic halogen compounds such as nitrogen oxides, sulfur oxides and dioxins Conceptual diagram.

FIG. 3 is a conceptual diagram of a glycogenated halogen decomposition method as one of the conventional methods for removing dioxins and the like contained in contaminated soil or contaminated waste.

4 is a conceptual diagram of a base-catalyst decomposition method as one of the conventional methods for removing dioxins and the like contained in contaminated soil or contaminated waste.

5 is a conceptual diagram of a combustion facility for treating an aromatic halogen compound such as dioxins and sulfur oxides by using the composite catalyst of the present invention as an embodiment of the present invention.

FIG. 6 is a conceptual diagram illustrating a process of treating an aromatic halogen compound such as dioxins contained in contaminated soil and particulate or powdery waste using the composite catalyst of the present invention as another embodiment of the present invention.

FIG. 7 is a reaction tube used to react a gas containing an aromatic halogen compound with the complex catalyst of the present invention in an experiment for measuring the ability to remove the complex catalyst of the present invention with respect to an aromatic halogen compound such as dioxins contained in exhaust gas. It is shown.

8 is a reactor used for reacting a gas containing an aromatic halogen compound with the complex catalyst of the present invention in an experiment for measuring the ability to remove the complex catalyst of the present invention with respect to an aromatic halogen compound such as dioxins contained in exhaust gas. It is shown.

9 is a contaminated soil containing the composite catalyst of the present invention and an aromatic halogen compound in an experiment for measuring the removal ability of the composite catalyst of the present invention for an aromatic halogen compound such as dioxins contained in contaminated soil or contaminated waste. Or a reactor used to react contaminated waste.

The present invention provides a calcination catalyst in which a metal salt or a metal oxide of 0.5 to 60 weight (oxide equivalent weight ratio) is supported on 40 to 99.5 weight of a support material; And decomposing halogenated organic matter contained or remaining in exhaust gas, soil or contaminants, including alkali metal and / or alkaline earth metal supported on the calcining catalyst in an amount of 4-400 parts by weight based on 100 parts by weight of the calcining catalyst, It provides a composite catalyst used to remove.

In addition, the present invention comprises the steps of supporting a weight of the metal material, metal salt or metal oxide 0.5-60 (in terms of oxide equivalent weight) to 40-99.5 weight of the support material; Calcining the support material on which the metal, metal salt or metal oxide is supported to prepare a calcining catalyst; And melting and supporting an alkali metal and / or an alkaline earth metal in an amount of 4-400 parts by weight based on 100 parts by weight of the calcining catalyst, to prepare the complex catalyst in the exhaust gas, soil, or contaminant. Or it provides a method for producing a composite catalyst used to decompose, remove the residual halogenated organic material.

In addition, the present invention comprises the steps of supplying the exhaust gas generated by the combustion in the combustion chamber to the alkali absorption tower and / or dust collector; And decomposing and removing the halogenated organic material contained in the exhaust gas by spraying the complex catalyst in a powder state to the dust collector or the front of the dust collector or the alkali absorption tower in a temperature range of 100-500 ° C. It provides a method for removing the halogenated organic matter contained in the exhaust gas.

In addition, the present invention comprises the steps of adding a particulate or powdered contaminants or contaminated soil and the powdered or particulate composite catalyst to the reactor; Reacting the reaction mixture in a temperature range of 100-500 ° C .; Recovering the contaminant or soil purified from the reactor; And it provides a method for removing the halogenated organic matter contained in the contaminants or soil comprising the step of discharging the reaction product gas generated by the reaction from the reactor.

The calcination catalyst mentioned in the present specification is a catalyst used to remove aromatic halogen compounds such as dioxins, phenol compounds and sulfur oxides in exhaust gases emitted by combustion, and supports a metal, metal salt or metal oxide on a carrier material. The catalyst obtained by baking.

The complex catalyst referred to herein refers to a catalyst in which an alkali metal and / or an alkaline earth metal are supported on the above-mentioned calcining catalyst.

An aromatic halogen compound referred to herein may be understood as collectively referring to a compound in which one or more halogen elements are substituted in an aromatic ring, such as dichlorobenzene, trichlorobenzene, especially dioxins. In addition, although referred to herein as an aromatic halogen compound, it is exemplary and excludes aliphatic halogen compounds under conditions that may include aliphatic halogen compounds as well as aromatic halogen compounds contained in exhaust gas, contaminated soil or contaminated waste. It should not be understood as meaning.

Halogen compounds referred to in the present specification (including claims) refer to organic compounds including aromatic halogen compounds and aliphatic halogen compounds and having halogen elements as substituents.

The present inventors do not use a catalyst tower which requires a high installation cost and an operation cost separately, and use nitrogen oxides in the exhaust gas with high efficiency and low cost by using a minimum process commonly installed in the existing exhaust gas treatment facility. While searching for a reducing method, the composite catalyst of the present invention was prepared in consideration of the fact that there are alkali absorption facilities for removing sulfur oxides and dust collecting facilities for removing fine particles in exhaust gas treatment facilities of almost all combustion facilities. In addition, a simple method of spraying this into the exhaust gas as a powder and collecting the reaction catalyst powder into a dust collector has developed a technology capable of efficiently removing aromatic halogen compounds such as dioxins, phenol compounds and sulfur oxides.

In the present invention, 40.0% of the support material is first supported with 0.5% of metal salts or metal oxides, in particular, salts or oxides of transition metals, alkali metals, alkaline earth metals, or group 3B element materials, and then calcined at 300 ° C-1100 ° C. To prepare a calcined catalyst. Then, an alkali metal or alkaline earth metal is mixed with 4-400 weight of the calcined catalyst and the alkali metal and alkaline earth metal are melted at 29 ° C.-900 ° C. to prepare a carrier or mixture to prepare a granular composite catalyst including powder. Hydrophobic substances that are liquid or solid at room temperature, such as oils, waxes, animal or vegetable oils or hydrocarbons having 9 or more carbon atoms, are added to the catalysts at 5 to 200 parts by weight with respect to the composite catalyst, followed by stirring to coat the composite catalyst. To prepare a coated composite catalyst powder.

In preparing the catalyst by the above-described method, the support material is specifically or each of natural or artificial zeolite, natural or artificial bentonite, activated alumina, clay, activated carbon, activated silica, titanium dioxide, calcium carbonate, or Mixtures.

Further, salts or oxides of transition metals, alkali metals, alkaline earth metals, or group 3B elements are specifically Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ga, Mo, W One or more may be selected from salts of Rh, Pd, Pt, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, or oxides. These materials may be added in the form of salts, but after the addition, they are converted into such oxides or oxide salts through the calcination process, and thus the composition ratio of the metals described above may be in the form of oxides after firing in the preparation method of the present invention. We say composition ratio in case of conversion to mass of time. In supporting salts or oxides of these transition metals, alkali metals or alkaline earth metal materials, specifically, these materials are supported as ionic solutions or as colloids or slurries of oxides or salts.

In the complex catalyst of the present invention, salts or oxides of transition metals, alkalis and alkaline earth metals play a central role in catalysis. Generally, the lower the amount, the lower the activity and the lower the weight ratio in the form of oxide. In the case of the composite catalyst carrying only bay, the activity becomes very low. On the other hand, the more the activity is increased, but when it is supported more than 30, the increase in activity is not large compared to the case of using less than that amount.

The alkali metal or alkaline earth metal used in the present invention may be specifically composed of one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, or two or more thereof.

In the case where the alkali metal and the alkaline earth metal are added to the calcined product to be supported, specifically, a single or mixed composition may be supported on the calcining catalyst or the composite may be melted at a melting point or higher of each metal. At this time, the reaction atmosphere may be mixed while injecting unreacted nitrogen, argon, helium, and the like, which does not contain water, to eliminate the possibility of alkali or alkaline earth metal reacting with water, but the reaction may be performed under normal atmospheric conditions. At this time, when these metals fall below 4 with respect to the weight of the fired product, the reaction performance is very weak. When the metals are 400 or more, the metals cannot be dispersed properly in the firing catalyst, so agglomerates are formed instead of fine particles. When decomposing aromatic halogen compounds, such as the contact area that reacts with these harmful substances may not increase or decrease much, so the decomposition capacity does not increase significantly.

In the preparation of the coating composite catalyst according to the present invention, it is not necessary to coat liquid or solid hydrophobic materials such as oils, waxes, animal or vegetable oils or hydrocarbons having 9 or more carbon atoms at room temperature. In this case, there is an advantage in maintaining the activity of the catalyst for a long time. The amount of the substance can be arbitrarily determined for the purpose of adding the substance for this purpose. However, although there are differences depending on the particle size of the composite catalyst powder, when the total weight of the composite catalyst powder is generally 5 wt. Or less, the coating is not properly achieved, and when the 200 or more is added, the amount less than that is added. Only the same effect as the case can be seen.

The hydrophobic material used in coating the composite catalyst powder according to the present invention can be used as long as it is a hydrophobic material, but in order to effectively achieve the purpose, it is easily removed during the process application while effectively blocking the contact between the outside and the catalyst powder during storage. It should be possible. Therefore, it can be said that a material which is easily liquefied or vaporized at the application temperature without showing volatility at room temperature.

Hydrophobic materials used in coating the composite catalyst powder according to the present invention can be used both liquid and solid materials at room temperature or low temperature, but there are advantages and disadvantages. When using a liquid material, it is possible to apply evenly at room temperature, and the coating process is simple, but there is a problem that volatilization during storage after manufacturing, compared to the solid material, there is no problem of volatilization when using a solid material, It should be used to melt the solid coating material by raising the temperature, and in application it should be used to disperse the melting point of the solid material.

The composite catalyst powder prepared by the above method not only effectively decomposes aromatic halogen compounds and phenol compounds such as dioxins contained in exhaust gas and soil or waste, but also causes air and soil pollution, as well as sulfur oxides and other acids in the exhaust gas. It is a multifunctional material that removes heavy metals and removes pollutants.

Now, a method for removing aromatic halogen compounds contained in exhaust gas, polluted soil or waste using the composite catalyst of the present invention will be described with reference to the drawings. 5 is a conceptual diagram of a combustion facility for treating an aromatic halogen compound such as dioxins and sulfur oxides by using the composite catalyst of the present invention as an embodiment of the present invention. As shown in Figure 5, the exhaust gas generated in the combustion chamber is discharged to the atmosphere through the alkali absorption tower, the vibration damper and the activated carbon absorption tower in sequence. At this time, the composite catalyst of the present invention is injected into the alkali absorption tower, the front end of the vibration suppression apparatus or the vibration suppression apparatus. As a vibration damper, a bag filter, a cyclone, an electrostatic precipitator, or the like may be used.

When the composite catalyst of the present invention is injected into the alkali absorption tower, the composite catalyst of the present invention contacts and decomposes the aromatic halogen compound in the exhaust gas while the exhaust gas flows along the turbulence formed in the alkali absorption tower.

In the case of using the bag filter as the vibration damping device, the composite catalyst of the present invention can be injected at the front end of the bag filter. In this case, the injected complex catalyst of the present invention moves together with the exhaust gas and remains trapped in the bag filter, and reacts with the aromatic halogen compound in the exhaust gas which is in contact during the movement or after being captured by the bag filter.

When using a cyclone as a vibration damping device, the composite catalyst of the present invention can be injected into the cyclone. In this case, it is determined that the composite catalyst of the present invention contacts the aromatic halogen compound in the exhaust gas and decomposes it while the exhaust gas flows along the turbulence formed in the cyclone.

In the case of using an electrostatic precipitator as the vibration suppression apparatus, the composite catalyst of the present invention may be injected in front of the electrostatic precipitator. In this case, the injected complex catalyst of the present invention moves with the exhaust gas and remains trapped in the electrostatic precipitator, and reacts with the aromatic halogen compound in the exhaust gas which is in contact with the electrostatic precipitator during transport or after being captured by the electrostatic precipitator.

As described above, the present invention can remove the aromatic halogen compound contained in the exhaust gas without installing expensive catalyst tower and additional equipment by injecting the composite catalyst into the alkali absorption tower, the vibration isolator, or the front of the vibration isolator in powder form. have. The complex catalyst of the present invention as well as the aromatic halogen compound can remove acidic contaminants such as sulfur oxides and heavy metals.

The composite catalyst of the present invention exhibits activity even at 120 ° C. or lower, and shows excellent activity even at a temperature of 140 ° C. or lower, thereby effectively removing the aromatic halogen compound contained in the exhaust gas causing air pollution. This is the best of the currently developed catalysts lowered the application temperature above 110 ℃ in view of requiring more than 250 ℃ in the field application, substantially eliminating the need to heat the exhaust gas to remove the aromatic halogen compounds. This is a breakthrough in energy efficiency.

Therefore, the method of removing the aromatic halogen compound and the like contained in the exhaust gas using the composite catalyst of the present invention shows excellent energy efficiency while having an efficiency higher than the aromatic halogen compound removal rate in the conventional method using a catalyst tower.

In removing the aromatic halogen compound and the like by using the composite catalyst powder of the present invention, the alkali metal and alkaline earth metal included in the composite catalyst powder of the present invention react with the exhaust gas and water absorbed by the catalyst itself to generate hydrogen gas. This hydrogen is decomposed by a metal oxide composed of a single or a mixture of transition metals, alkalis and alkaline earth metals bonded to the support to form radicals or ions or complexes thereof, which not only decomposes halogenated organics such as dioxins, but also sulfuric acid. It is also believed to react with cargo. In addition, the alkali metal and alkaline earth metal contained in the catalyst powder reacts strongly with acidic gases such as sulfur oxides, so that these substances are simultaneously removed. In addition, the composite catalyst powder of the present invention is removed by adsorbing contaminants such as heavy metals contained in the exhaust gas.

In the treatment of the exhaust gas by the composite catalyst powder of the present invention, the reaction site exhibits a removal effect when the temperature of the reaction site is 80 ° C. or more, and a certain effect even under 40 ° C. close to room temperature depending on the composition of the catalyst. However, when comparing input amounts and effects, a temperature of 110 ° C. or more is required to obtain good results compared to existing technologies. In addition, when the temperature is too high, the activity of the catalyst rapidly decreases with time, so a temperature of 500 ° C. or less and more preferably 350 ° C. or less is required.

Next, a method for removing an aromatic halogen compound from contaminated soil or waste will be described with reference to the drawings. FIG. 6 shows a conceptual diagram of a process of treating aromatic halogen compounds, such as dioxins, contained in contaminated soil and particulate or powdery waste using the composite catalyst of the present invention as another embodiment of the present invention.

As shown in Figure 6, contaminated soil or waste is mixed with the composite catalyst powder of the present invention and reacted in a reactor. At this time, the reaction temperature is preferably in the range of 110 ~ 500 ℃ for the same reason as above. However, since the aromatic halogen compound contained in the waste exists in an adsorbed state in the waste, in order to react it by contact with the complex catalyst of the present invention, a temperature condition capable of volatilizing it is required. It can be volatilized below the boiling point of the aromatic halogen compound to be removed, but the amount is so small that the reaction time must be long. Therefore, in order to efficiently carry out the reaction, it is preferable to perform the reaction above the boiling point of the aromatic halogen compound to be removed, and when the reaction is to be performed at a lower temperature, it is preferable to set the reaction pressure lower than the normal pressure. . In addition, the heating time in the reaction depends on the degree of contamination of the granular material, but the longer the heating is, the better the effect is. In general, in order to sufficiently remove the halogenated organic material, the aromatic halogen compound is sufficiently volatilized under conditions of 30 A heating time of at least minutes is required. In addition, it is possible to obtain a better effect when continuous stirring is performed at the same time as heating.

When the reaction is completed in the reactor, the purified waste can be obtained and the vapor generated by the reaction can be released to the atmosphere.

On the other hand, the vapor discharged from the reactor includes a decomposition product of the aromatic halogen compound, and when the reaction is not fully progressed, may include the aromatic halogen compound itself is not decomposed. When an aromatic halogen compound is decomposed, the decomposition products are not only completely harmless to the environment, but also incomplete decomposition products may be present. This incomplete digest is less toxic than the original aromatic halogen compound but can still contain environmentally harmful substances. Therefore, additional processes can be carried out to prevent the release of these harmful substances into the atmosphere.

The additional process may be similar to the process of treating the exhaust gas mentioned above, as shown in FIG. 6. That is, for example, in discharging the vapor discharged from the reactor to the atmosphere after passing through a dust collector such as a bag filter, the composite catalyst powder of the present invention by spraying the composite catalyst powder of the present invention in front of the bag filter to the composite catalyst of the present invention React with powder to cause further decomposition reactions (Method 1).

In addition, as an additional process, the steam discharged from the reactor is discharged to the atmosphere after passing through the reaction tube or the reaction column filled with the complex catalyst of the present invention (method 2). At this time, an additional decomposition reaction occurs by the complex catalyst of the present invention filled in an additional reaction tube or reaction tower.

Figure 6 shows the use of the complex catalyst of the present invention as an additional process, but other catalysts known to decompose aromatic halogen compounds such as dioxins, for example catalyst towers constructed in the form of honeycomb cordierite as described above. You can also use

Only the removal of aromatic halogen compounds from contaminated soil or waste is described here, but as described above, acidic substances such as sulfur oxides, phenolic compounds and heavy metal materials may also be removed.

Hereinafter, specific examples of the present invention will be presented through examples. However, the following examples are only intended to show specific examples of the present invention, it should not be understood that the scope of the present invention is limited by the examples.

Example 1

1.460 g of natural zeolite (Wangyo Chemical CLINOPTILOLITE) and an aqueous solution of 0.927 g of ferrous chloride tetrahydrate were sufficiently mixed and dried at 110 ° C. for 2 hours. The mixture was placed in an electric furnace, gradually heated up, and calcined at 800 ° C for 30 minutes. 0.3 g of Li was added to the fired product and mixed in a state of heating at 200 ° C to obtain a granular composite catalyst containing powder. In this catalyst, 1.84 g of paraffin (Namyoung Emulsification, 135P) was placed in a reactor at 80 ° C. and coated with continuous stirring.

50 mg of powder having a particle size of 100 mesh or less was aliquoted from the coated composite catalyst and mixed with 850 mg of granular silica powder having a diameter of 125 μm. This was filled in a reaction tube as shown in FIG. 7, while maintaining a constant temperature, a gas containing nitrogen oxides and halogenated organics was passed at a flow rate of 100 ml / min to measure the ability to reduce sulfur oxides and remove halogenated organics.

The gas containing sulfur oxide and halogenated organic matter is NO 400ppm, SO ₂ 600ppm, halogenated organic 0.1 ng / ml, helium gas containing 4, H ₂ O 7 as O ₂ mass ratio and the temperature of the reaction tube is maintained at 130 ℃ It was. The halogenated organic material used was a 1: 1 mixture of dichlorobenzene and chlorophenol, which are widely used as dioxin analogues.

In order to measure the ability to remove sulfur oxides, 200 μl of gas that had passed through the catalyst was aliquoted, and the halogenated organic concentration was measured using a gas chromatography system equipped with a thermal conductivity detector. .

Sulfur oxide removal rate () = (inlet SO ₂ concentration-outlet SO ₂ concentration) / (inlet SO ₂ concentration) X 100 ()

In order to measure the ability to remove halogenated organic matter, 200 μl of gas that had passed through the catalyst was collected and the concentration of aromatic halogen compounds was measured using a gas chromatography system equipped with an electron trap detector. .

Halogenated organic removal rate () = (Halogenated organic concentration before treatment-Halogenated organic concentration after treatment) / (Halogenated organic concentration before treatment) X 100 ()

The results are shown in Table 1.

Example 2

1.4 g of a 3: 1 mixture of kaolin (Daeming) and activated carbon (Samcheonli SG100) and 1.094 g of a mixture of ferrous chloride tetrahydrate and titanium trichloride 9:10 were thoroughly mixed and dried at 110 ° C. for 2 hours. It was. The mixture was placed in an electric furnace, gradually heated up, and calcined at 500 ° C for 10 minutes. 1.9 g of a 1: 1 mixture of Mg and Na was added to the calcined product and mixed under a nitrogen atmosphere heated at 680 ° C. to obtain a granular catalyst including powder. 2.34 g of wax (Namyoung Emulsification No. 4) was added to the catalyst, and the mixture was stirred with constant stirring at 80 ° C. and coated.

The sample was tested for activity in the same manner as in Example 1 except that the reaction temperature was 145 ° C. and the results are shown in Table 1.

Example 3

A mixture of 1.9 g of 3: 1 mixture of activated alumina and calcium carbonate (Omiya Korea) and 0.156 g of a mixture of 6: 5 of hexahydrate of copper (II) chloride and cobalt (II) chloride was mixed well at 110 ° C. Dried at 2 h. The mixture was placed in an electric furnace, gradually heated up, and calcined at 550 ° C. for 20 minutes. 4.0 g of Ca was added to the calcined product, and mixed in a state of heating at 850 ° C. in a helium atmosphere to obtain a granular catalyst including powder. 1.2 g of kerosene was added to the catalyst, followed by stirring and coating.

The sample was tested for activity in the same manner as in Example 1 except that the reaction temperature was 160 ° C. and the results are shown in Table 1.

Example 4

An aqueous solution of 1.96 g of a 3: 1 mixture of zeolite (zeolite Y) and calcium carbonate (Omiya Korea) and a mixture of 0.068 g of a mixture of zinc chloride and tetrahydrate 1: 1 of zinc chloride was sufficiently mixed and dried at 110 ° C. for 2 hours. . The mixture was placed in an electric furnace, gradually heated up, and calcined at 600 ° C for 30 minutes. 3.6 g of Li was added to this calcined product, and it mixed in the state heated at 200 degreeC, and obtained the granular catalyst containing powder. 3.92 g of palm hardened oil (Japanese sowawa) was added to the catalyst, followed by coating with continuous stirring.

The sample was tested for activity in the same manner as in Example 1 except that the reaction temperature was 180 ° C. and the results are shown in Table 1.

Example 5

An aqueous solution of 0.232 g of a mixture of 1.840 g of titanium dioxide, a monohydrate of molybdenum oxydichloride, and a 4.5: 2 mixture of sodium metavanadate was sufficiently mixed and dried at 110 ° C. for 2 hours. The mixture was placed in an electric furnace, gradually heated up, and calcined at 800 ° C for 30 minutes. 3 g of a 1: 2 mixture of K and Ca was added to the calcined product, and mixed in a state of being heated at 850 ° C. in a helium atmosphere to obtain a granular catalyst including powder. 2.5 g of kerosene was added to the catalyst and the mixture was continuously stirred and coated.

The sample was tested for activity in the same manner as in Example 1 except that the reaction temperature was 180 ° C. and the results are shown in Table 1.

Example 6

110 ° C after mixing 1.780 g of a 1: 1 mixture of kaolin (Daemyung) and natural zeolite (Kwangyop Chemical CLINOPTILOLITE) and 0.536 g of a 2.2: 1 mixture of heptahydrate and hexaamine rhodium chloride of manganese sulfate (II) Dried at 2 h. The mixture was placed in an electric furnace, gradually heated up, and calcined at 900 ° C for 30 minutes. 5.4 g of Sr was added to the calcined product, and the mixture was mixed in a nitrogen atmosphere heated at 780 ° C. to obtain a granular catalyst including powder. 8.9 g of wax (Namyoung Emulsification No. 4) was added to the catalyst, and the mixture was stirred while stirring at 80 ° C.

The sample was tested for activity in the same manner as in Example 1 except that the reaction temperature was 110 ° C. and the results are shown in Table 1.

Example 7

1.5 g of natural bentonite (BEH Natural, Wyoming), and 0.832 g of a mixture of 1.5: 2 pentahydrate of palladium (II) chloride and platinum tetrachloride were sufficiently mixed and then dried at 110 ° C. for 2 hours. The mixture was placed in an electric furnace, gradually heated up, and calcined at 900 ° C for 30 minutes. 2.4 g of Mg and Li were added to this calcined product and mixed in the state heated at 680 degreeC by nitrogen atmosphere, and the granular catalyst containing powder was obtained. 3.08 g of paraffin (Namyoung Emulsification 135P) was added to the catalyst and coated with constant stirring at 80 ° C.

The sample was tested for activity in the same manner as in Example 1 except that the reaction temperature was 210 ° C. and the results are shown in Table 1.

Example 8

An aqueous solution of 1.24 g of a 5: 1 mixture of bentonite (Wyoming HYG2000) and titanium dioxide and a mixture of 1.41 g of chromium (II) chloride and calcium chloride 5: 2 was sufficiently mixed and dried at 110 ° C. for 2 hours. The mixture was placed in an electric furnace, gradually heated up, and calcined at 800 ° C for 30 minutes. 1.5 g of Mg was added to the calcined product, and the mixture was mixed in a nitrogen atmosphere heated at 680 ° C to obtain a granular catalyst.

The sample was tested for activity in the same manner as in Example 1 except that the reaction temperature was 250 ° C. and the results are shown in Table 1.

Example 9

An aqueous solution of 1.740 g of a 1: 1 mixture of bentonite (Wyoming HYG2000) and activated silica and 0.489 g of platinum tetrachloride was sufficiently mixed and dried at 110 ° C. for 2 hours. The mixture was placed in an electric furnace, gradually heated up, and calcined at 600 ° C for 30 minutes. Mg 2.8g was added to this calcined product, and it mixed in the state heated at 680 degreeC by nitrogen atmosphere, and obtained the granular catalyst containing powder. 2.88 g of wax (Namyoung Emulsification No. 4) was added to the catalyst, and the resultant was coated with constant stirring.

The sample was tested for activity in the same manner as in Example 1 except that a composite catalyst powder of 0.1 g per minute was injected into the reactor as shown in FIG. 8 without using a reaction tube, and the reaction temperature was 200 ° C. The results are shown in Table 1 below. Marked on.

Example 10

1.7 g of a 3: 1 mixture of activated alumina and activated carbon (Samchully SG100) and an aqueous solution of 0.507 g of copper (II) chloride were sufficiently mixed and dried at 110 ° C. for 2 hours. The mixture was placed in an electric furnace, gradually heated up, and calcined at 500 ° C for 10 minutes. 1.2 g of Na was added to the calcined product and mixed in a state of heating to 110 ° C. to obtain a granular catalyst containing powder. 4 g of paraffin (Namyoung Emulsification 135P) was added to the catalyst and coated with a continuous stirring at 80 ° C.

The sample was tested for activity in the same manner as in Example 9 except that the reaction temperature was 150 ° C. and the results are shown in Table 1.

Example 11

1.66 g of a 7: 1 mixture of active silicate and activated alumina and 0.656 g of titanium trichloride were sufficiently mixed and then dried at 110 ° C. for 2 hours. The mixture was placed in an electric furnace, gradually heated up, and calcined at 550 ° C. for 30 minutes. 2.1 g of a 2: 1 mixture of Li and Na was added to the calcined product, and the mixture was heated and heated at 200 ° C. to obtain a granular catalyst containing powder. 2.34 g of wax (Namyoung Emulsification No. 4) was added to the catalyst, and the resultant was dried and coated with constant stirring at 80 ° C.

The sample was tested for activity in the same manner as in Example 9 except that the reaction temperature was 220 ° C. and the results are shown in Table 1.

Example 12

1.6 g of a 3: 1 mixture of zeolite (zeolite Y) and titanium dioxide, a mixture of 1.353 g of nickel (II) hexahydrate and platinum tetrachloride pentahydrate (4.4: 1) were thoroughly mixed, followed by 2 Dried for hours. The mixture was placed in an electric furnace, gradually heated up, and calcined at 900 ° C for 30 minutes. 1 g of Mg was added to the calcined product and mixed under a nitrogen atmosphere heated at 680 ° C. to obtain a granular catalyst including powder. 1.2 g of kerosene was added to the catalyst and coated with continuous stirring.

The sample was tested for activity in the same manner as in Example 9 except that the reaction temperature was 270 ° C. and the results are shown in Table 1.

Example 13

0.94 g of bentonite (WH HYG2000), an aqueous solution of 2.27 g of a mixture of titanium trichloride (II), and magnesium chloride at 5: 4 were sufficiently mixed, and then dried at 110 ° C. for 2 hours. The mixture was placed in an electric furnace, gradually heated up, and calcined at 800 ° C for 30 minutes. Ba 2g was added to the calcined product and mixed under a nitrogen atmosphere heated at 740 ° C. to obtain a granular catalyst.

The sample was tested for activity in the same manner as in Example 9 except that the reaction temperature was 310 ° C. and the results are shown in Table 1.

Test result for removing pollutant causes in exhaust gas for the composite catalyst powder of the present invention Halogenated organic residue Removal rate Sulfur oxide residue (ppm) Removal rate Example 1 trace 99.9 or more 35 94 Example 2 trace 99.9 or more 27 96 Example 3 trace 99.9 or more 42 93 Example 4 trace 99.9 or more 21 97 Example 5 trace 99.9 or more 32 95 Example 6 trace 99.9 or more 38 94 Example 7 trace 99.9 or more 28 95 Example 8 trace 99.9 or more 31 95 Example 9 trace 99.9 or more 41 93 Example 10 trace 99.9 or more 48 92 Example 11 trace 99.9 or more 39 94 Example 12 trace 99.9 or more 26 96 Example 13 trace 99.9 or more 24 96

* In the above table, the trace is measured by a measuring device having a measurement limit of 1 ppt (part per trillion), which means 1 ppt or less.

As shown in Table 1, it can be seen that the removal of halogenated organic matter and sulfur oxide was effectively performed by the use of the composite catalyst powder of the present invention, in particular, the removal of the substances even at a low temperature of about 110 ℃ It became.

Example 14

1.460 g of natural zeolite (Wangyo Chemical CLINOPTILOLITE) and an aqueous solution of 0.927 g of ferrous chloride tetrahydrate were sufficiently mixed and dried at 110 ° C. for 2 hours. The mixture was placed in an electric furnace, gradually heated up, and calcined at 600 ° C for 30 minutes. 0.3 g of Li was added to this fired product and mixed in the state heated at 200 degreeC, and the granular catalyst containing powder was obtained. After leaving the catalyst in the air for 1 month, the activity was tested in the same manner as in Example 1.

In addition, 1.84 g of paraffin (Namyoung Emulsification 135P) was added to the prepared catalyst in a reactor at 80 ° C., and then coated with continuous stirring to stand for 1 month in the air, and then tested for activity in the same manner as in Example 1.

Table 2 compares the two results.

Example 15

1.4 g of a 3: 1 mixture of kaolin (Daeming) and activated carbon (Samcheonli SG100) and 1.094 g of a mixture of ferrous chloride tetrahydrate and titanium trichloride 9:10 were thoroughly mixed and dried at 110 ° C. for 2 hours. It was. The mixture was placed in an electric furnace, gradually heated up, and calcined at 500 ° C for 10 minutes. 1.9 g of a 1: 1 mixture of Mg and Na was added to the calcined product and mixed under a nitrogen atmosphere heated at 680 ° C. to obtain a granular catalyst including powder.

After leaving the catalyst in the air for 1 month, the activity was tested in the same manner as in Example 1 except that the reaction temperature was 145 ° C.

In addition, 2.34 g of wax (Namyoung Emulsification No. 4) was added to a catalyst prepared in the same manner as above, and then coated with a continuous stirring at 80 ° C., and then left to stand in air for 1 month.

Table 2 compares the two results.

Example 16

A mixture of 1.9 g of 3: 1 mixture of activated alumina and calcium carbonate (Omiya Korea) and 0.156 g of a mixture of 6: 5 of hexahydrate of copper (II) chloride and cobalt (II) chloride was mixed well at 110 ° C. Dried at 2 h. The mixture was placed in an electric furnace, gradually heated up, and calcined at 550 ° C. for 20 minutes. Ca 4.0g was added to the calcined product, mixed in a state of heating at 850 ° C. in a helium atmosphere to obtain a granular catalyst including powder.

The catalyst was packed in a polyethylene bag, sealed, and left to stand for one month, after which the activity was tested in the same manner as in Example 1, but the reaction temperature was 160 ° C.

In addition, 1.2g of kerosene was added to the catalyst prepared in the same manner as above, stirred, coated, sealed in a polyethylene bag, and left to stand for one month, and then tested for activity in the same manner as above.

Table 2 compares the two results.

Example 17

An aqueous solution of 1.96 g of a 3: 1 mixture of zeolite (zeolite Y) and calcium carbonate (Omiya Korea) and a mixture of 0.068 g of a mixture of zinc chloride and tetrahydrate 1: 1 of zinc chloride was sufficiently mixed and dried at 110 ° C. for 2 hours. . The mixture was placed in an electric furnace, gradually heated up, and calcined at 600 ° C for 30 minutes. 3.6 g of Li was added to this calcined product, and it mixed in the state heated at 200 degreeC, and obtained the granular catalyst containing powder.

After leaving the granular catalyst in the air for 1 month, the activity was tested in the same manner as in Example 1, but the reaction temperature was 180 ° C.

In addition, a solution prepared by dissolving 3.92 g of palm hardened oil (Japanese sowawa) in hexane was added to the catalyst prepared in the same manner as above, followed by coating with constant stirring.

Table 2 compares the two results.

Storage test results for the composite catalyst of the present invention according to the coating treatment Coated Sample Uncoated sample Halogenated Organic Removal Rate Sulfur oxide removal rate Halogenated Organic Removal Rate Sulfur oxide removal rate Example 14 99.9 or more 91 37 41 Example 15 99.9 or more 94 32 29 Example 16 99.9 or more 96 71 78 Example 17 99.9 or more 93 28 5

As shown in Table 2, when the composite catalyst powder of the present invention was coated with a hydrophobic material, the catalyst activity was not significantly reduced even after 1 month of standing, but the composite catalyst powder of the present invention was left without coating with a hydrophobic material for 1 month. After this, the degradation of the catalytic activity was very serious. This is believed to be due to the fact that the alkali metal or alkaline earth metal contained in the composite catalyst powder of the present invention cannot react with the water in the atmosphere to become a metal hydrate or an oxide so that the catalyst cannot exhibit its activity. On the other hand, in the composite catalyst powder of the present invention coated with a hydrophobic material, the coating of the hydrophobic material prevents the contact between moisture in the atmosphere and the alkali metal or alkaline earth metal contained in the composite catalyst powder of the present invention. It appears to maintain the activity of the catalyst by allowing it to remain as it is.

Example 18

An aqueous solution of 1.266 g of a mixture of 1.680 g of zeolite (zeolite Y), hexahydrate of nickel (II) chloride, and magnesium chloride in 15.8: 1 was sufficiently mixed, and then dried at 110 ° C. for 2 hours. The mixture was placed in an electric furnace, gradually heated up, and calcined at 900 ° C for 30 minutes. Sr 1.05g and 0.55g of Li were added to the calcined product and mixed under a nitrogen atmosphere heated at 780 ° C. to obtain a granular catalyst including powder.

200 mg of the catalyst was mixed with 1 kg of clay adsorbed with 0.5 mg of halogenated organic matter, placed in a reactor as shown in FIG. 9, and 300 mg of the catalyst and 800 mg of glass beads of diameter were filled into a reaction tube on an exhaust line. After the reaction was carried out for 2 hours while maintaining the ℃ was measured the ability to remove the halogenated organic matter. In this reaction, a halogenated organic substance was used as a dioxin analogue, a mixture of dichlorobenzene and chlorophenol, which is widely used in a 1: 1 ratio. 0.5 mg of this substance was diluted in 200 ml of hexane solution, injected into clay, stirred and adsorbed, Clay dried at 80 ° C. for 30 minutes was used.

In order to measure the ability to remove the halogenated organic matter, 2 g of clay was aliquoted after the reaction, and extracted with Soxhlet using dichloromethane as an extraction solvent. The extracted solution was concentrated to 0.5 ml, and then 10 µl was aliquoted and injected into the gas chromatography system equipped with an electron trap detector to measure the amount of residual halogenated organic matter. This measurement was then quantified by substituting the calibration curve prepared using a standard sample.

Halogenated organic removal rate () = (Halogenated organic concentration before treatment-Halogenated organic concentration after treatment) / (Halogenated organic concentration before treatment) X 100 ()

The results are shown in Table 3.

Example 19

1.760 g of 3: 1 mixture of activated silicate and titanium dioxide, 0.416 g of a mixture of ferrous chloride tetrahydrate and calcium chloride 12: 1 were sufficiently mixed and then dried at 110 ° C. for 2 hours. The mixture was placed in an electric furnace, gradually heated up, and calcined at 500 ° C for 30 minutes. 1.8 g of K was added to the calcined product, and the mixture was mixed at a temperature of 70 ° C. to obtain a granular catalyst containing powder. 2.9 g of wax (Namyoung Emulsification No. 4) was added to the catalyst in a reactor at 80 ° C. and coated with continuous stirring.

The sample was tested for activity in the same manner as in Example 18 except that the reaction temperature was 130 ° C. and the results are shown in Table 3.

Example 20

1.80 g of a 3: 1 mixture of natural zeolite (Wangyo Chemical CLINOPTILOLITE) and activated carbon (Samcheonli SG100) and 0.0.268 g of sodium metavanadate were sufficiently mixed and then dried at 110 ° C. for 2 hours. The mixture was placed in an electric furnace, gradually heated up, and calcined at 500 ° C for 10 minutes. 2.2 g of Na was added to the calcined product, and the mixture was mixed at a temperature of 110 ° C. to obtain a granular catalyst containing powder.

The sample was tested for activity in the same manner as in Example 18 except that the reaction temperature was 150 ° C. and the results are shown in Table 3.

Example 21

An aqueous solution of 1.620 g of activated silicate and 0.653 g of ferrous chloride tetrahydrate was sufficiently mixed and dried at 110 ° C. for 2 hours. The mixture was placed in an electric furnace, gradually heated up, and calcined at 550 ° C. for 30 minutes. 1.4 g of Li was added to this fired product and mixed in the state heated at 190 degreeC, and the granular catalyst containing powder was obtained. 2.8 g of paraffin (Namyoung Emulsification 135P) was added to this catalyst and coated with constant stirring.

The sample was tested for activity in the same manner as in Example 18 except that the reaction temperature was 210 ° C. and the results are shown in Table 3.

Performance test results of the composite catalyst of the present invention on contaminated soil Halogenated organic residue Removal rate Example 18 trace 99.9 or more Example 19 trace 99.9 or more Example 20 trace 99.9 or more Example 21 trace 99.9 or more

* In the above table, the trace is measured by a measuring device having a measurement limit of 1 ppt (part per trillion), which means 1 ppt or less.

As shown in Table 3, it can be seen that the composite catalyst of the present invention has excellent performance in removing halogenated organic matter remaining in contaminated soil.

In order to remove aromatic halogen compounds such as dioxins from exhaust gases by conventional methods, a separate facility is required.However, a method of removing aromatic halogen compounds from exhaust gases using a complex catalyst of the present invention is a vibration suppression apparatus or a vibration suppression method. Since the composite catalyst of the present invention is injected into a powder and injected into the sulfur oxide removal device by the front end of the device or the alkali absorption method, the following advantages are obtained.

First, the process is greatly simplified.

Second, installation costs are greatly reduced.

When the dioxins are to be removed by the conventional method, the temperature of the exhaust gas should be at least 250 ° C. or more, but it is also performed at 140 ° C. or less when using the method specified in the present invention.

Third, energy costs are greatly reduced because preheating of the exhaust gas is not necessary.

Fourth, in the case of adsorbing dioxin by activated carbon, there may be a problem of secondary pollution caused in the process of adsorbed dioxin, but in the present invention, there is no fear by decomposing dioxin.

In addition, the present invention has the advantages mentioned above as compared to conventional methods of treating contaminated soil or waste.

Claims (29)

A calcination catalyst having a weight of a metal salt or a metal oxide of 0.5-60 weight (in terms of weight in terms of oxide) supported by 40-99.5 weight of the support material; And An alkali metal and / or an alkaline earth metal supported on the calcining catalyst in an amount of 4-400 parts by weight based on 100 parts by weight of the calcining catalyst, A composite catalyst used to decompose and remove halogenated organic matter contained or remaining in exhaust gas, soil or contaminants. The method of claim 1, The composite catalyst is a coating composite catalyst coated with a hydrophobic material that is liquid or solid at room temperature. A composite catalyst used to decompose and remove halogenated organic matter contained or remaining in exhaust gas, soil or contaminants. The method of claim 2, The hydrophobic material coated on the complex catalyst is selected from the group consisting of oils, waxes, animal and vegetable oils, hydrocarbons having 9 or more carbon atoms, and mixtures thereof. A composite catalyst used to decompose and remove halogenated organic matter contained or remaining in exhaust gas, soil or contaminants. The method of claim 3, The amount of the hydrophobic material to be coated is 5 to 200 parts by weight based on 100 parts by weight of the uncoated composite catalyst. A composite catalyst used to decompose and remove halogenated organic matter contained or remaining in exhaust gas, soil or contaminants. The method according to claim 1 or 2, The carrier material is selected from the group consisting of natural or artificial zeolites, natural or artificial bentonite, activated alumina, clay, fly ash, activated carbon, activated silica, titanium dioxide, calcium carbonate and mixtures thereof. A composite catalyst used to decompose and remove halogenated organic matter contained or remaining in exhaust gas, soil or contaminants. The method according to claim 1 or 2, The metal salt or metal oxide is a salt or oxide of a transition metal, an alkali metal, an alkaline earth metal or a group 3B element, or a complex salt or complex oxide containing two or more of these metals. A composite catalyst used to decompose and remove halogenated organic matter contained or remaining in exhaust gas, soil or contaminants. The method according to claim 1 or 2, The metal salt or metal oxide may be selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, Rh, Pd, Pt, Li, Na, K, Cs, Rb, Mg or Ca Salt or oxide, or a complex salt or complex oxide comprising two or more of these metals A composite catalyst used to decompose and remove halogenated organic matter contained or remaining in exhaust gas, soil or contaminants. The method according to claim 1 or 2, The alkali metal and / or alkaline earth metal is selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, alloys thereof and mixtures thereof. A composite catalyst used to decompose and remove halogenated organic matter contained or remaining in exhaust gas, soil or contaminants. The method according to claim 1 or 2, The complex catalyst is capable of removing phenol compounds in addition to decomposing and removing halogenated organic materials. A composite catalyst used to decompose and remove halogenated organic matter contained or remaining in exhaust gas, soil or contaminants. The method according to claim 1 or 2, The complex catalyst may remove sulfur oxides in addition to decomposing and removing halogenated organic materials. A composite catalyst used to decompose and remove halogenated organic matter contained or remaining in exhaust gas, soil or contaminants. The method according to claim 1 or 2, The composite catalyst is characterized in that the powder form A composite catalyst used to decompose and remove halogenated organic matter contained or remaining in exhaust gas, soil or contaminants. Supporting 0.5-60 weight (in terms of oxide weight) of metal, metal salt or metal oxide to 40-99.5 weight of the support material; Calcining the support material on which the metal, metal salt or metal oxide is supported to prepare a calcining catalyst; And Preparing a complex catalyst by melting and supporting an alkali metal and / or an alkaline earth metal in an amount of 4-400 parts by weight based on 100 parts by weight of the calcining catalyst. A process for producing a composite catalyst used to decompose and remove halogenated organic matter contained or remaining in exhaust gas, soil or contaminants. The method of claim 12, It characterized in that it further comprises the step of coating a hydrophobic material in the liquid or solid phase at room temperature to the composite catalyst Method for producing a composite catalyst. The method of claim 13, The hydrophobic material coated on the complex catalyst is selected from the group consisting of oils, waxes, animal and vegetable oils, hydrocarbons having 9 or more carbon atoms, and mixtures thereof. Method for producing a composite catalyst. The method of claim 12, The firing step is characterized in that carried out in a temperature range of 300-1100 ℃ Method for producing a composite catalyst. The method of claim 12, The step of supporting the metal, metal salt or metal oxide is characterized in that the metal is supported in a ionic solution, a colloidal state or a slurry dispersed in a liquid state and dried Method for producing a composite catalyst. The method of claim 12, The carrier material is selected from the group consisting of natural or artificial zeolites, natural or artificial bentonite, activated alumina, clay, fly ash, activated carbon, activated silica, titanium dioxide, calcium carbonate and mixtures thereof. Method for producing a composite catalyst. The method of claim 12, The metal salt or metal oxide may be selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, Rh, Pd, Pt, Li, Na, K, Cs, Rb, Mg or Ca Salt or oxide, or a complex salt or complex oxide comprising two or more of these metals Method for producing a composite catalyst. The method of claim 12, The alkali metal and / or alkaline earth metal is selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, alloys thereof and mixtures thereof. Method for producing a composite catalyst. Supplying exhaust gas generated by combustion in a combustion chamber to an alkali absorption tower and / or a dust collector; And The method of claim 1 or 2 comprising the step of injecting the complex catalyst of claim 1 or 2 in the powder state to the dust collector or the front end of the dust collector or the alkali absorption tower to decompose, remove the halogenated organic matter contained in the exhaust gas; A method for removing halogenated organic matter contained in exhaust gas. The method of claim 20, The temperature of the alkali absorption tower, the dust collector or the front end of the dust collector is sprayed with the complex catalyst is characterized in that less than 100 ~ 500 ℃ How to remove halogenated organics in exhaust gas The method of claim 20, The temperature of the alkali absorption tower, the dust collector or the front end of the dust collector to which the complex catalyst is injected is 150 ° C or less. How to remove halogenated organics in exhaust gas The method of claim 20, In addition to the removal of the halogenated organic matter contained in the exhaust gas by the complex catalyst characterized in that to remove the phenol compounds and / or sulfur oxides A method for removing halogenated organic matter contained in exhaust gas. Adding particulate or powdered contaminants or contaminated soil and the powdered or particulate composite catalyst of claim 1 or 2 into a reactor; Reacting the reaction mixture; Recovering the contaminant or soil purified from the reactor; And Discharging the reaction product gas generated by the reaction from the reactor. A method for removing halogenated organics contained in contaminants or soil. The method of claim 24, The reaction temperature is characterized in that the range of 100 ~ 500 ℃ How to remove halogenated organics contained in contaminants or soil The method of claim 24, The reaction temperature is characterized in that less than 150 ℃ How to remove halogenated organics contained in contaminants or soil The method of claim 24, In addition to removing the halogenated organic matter contained in the contaminants or soil by the complex catalyst, it is characterized in that to remove phenol compounds and / or sulfur oxides A method for removing halogenated organics contained in contaminants or soil. The method of claim 24, Passing the reaction product gas discharged from the reactor through a dust collector; And Injecting the composite catalyst of claim 1 or claim 2 in the form of a powder on the front of the dust collector or the dust collector. A method for removing halogenated organics contained in contaminants or soil. The method of claim 24, Passing the reaction product gas discharged from the reactor through a reaction tube or a reaction column filled with the complex catalyst of claim 1 or claim 2 characterized in that it further comprises A method for removing halogenated organics contained in contaminants or soil.