Catalyst for removing halogen group element from organic compound containing halogen group element and manufacturing method thereof

Abstract

The present invention relates to: a catalyst for removing a halogen group element from an organic compound containing the halogen group element and contained in waste oil, a waste organic solvent, waste water, a semiconductor waste gas, a semiconductor process cleaning liquid, a pharmaceutical process cleaning liquid, or dyeing process effluent and pyrolysis oil; a method for manufacturing the catalyst; and a method for removing a halogen group element from an organic compound containing the halogen group element by using the catalyst. The catalyst of the present invention can effectively remove a halogen group element from an organic compound containing the halogen group compound. According to the manufacturing method of the present invention, the catalyst of the present invention can be manufactured at low cost and high productivity. The catalyst of the present invention is highly capable of removing a halogen element from an organic compound containing the halogen element.

Description

Catalyst for removing halogen elements from organic compounds containing halogen elements and method for producing the same

[0001] The present invention relates to a catalyst for removing halogen elements from an organic compound containing halogen elements, and a method for producing the same. The present invention particularly relates to a catalyst for removing halogen elements from an organic compound containing a high concentration of halogen elements, and a method for producing the same.

[0002] The various industrial processes that produce chemicals, electronics, and other products generate large quantities of organic compounds containing halogen elements (e.g., polychlorinated biphenyls, 2,3,7,8-tetrachlorodioxin), either in gaseous or liquid form. These organic compounds containing halogen elements are found in large quantities in waste oil, waste organic solvents, wastewater, semiconductor waste gases, semiconductor process cleaning solutions, pharmaceutical process cleaning solutions, and dyeing process effluent.

[0003] Most organic compounds containing halogen elements are toxic and cause environmental pollution. Representative examples of organic compounds containing halogen elements that can be removed using the present invention include polychlorinated biphenyls (PCBs) and dioxins. PCBs are organochlorine compounds containing two benzene rings. Their structure is shown in Chemical Formula 1 below.

[0004]

[0005] (n and m are integers from 1 to 5)

[0006] Polychlorinated biphenyls (PCBs) are potent neurotoxic substances. They are chemically stable and resistant to heat degradation. They are resistant to oxidation and are stable to acids and bases. Therefore, once PCBs are formed, they persist in the body and accumulate throughout the food chain. Another problem with PCBs is that even slight mishandling can lead to the production of dioxins, another environmental pollutant.

[0007] Dioxins are compounds containing chlorine atoms in a benzene ring. Dioxins are commonly produced when waste plastics are burned. The official name for dioxins is polychlorinated dibenzo-p-dioxin. The basic chemical structure of dioxins consists of two benzene rings with multiple chlorine atoms attached. These include dioxins (chemical formula 2), which have two oxygen atoms, and furans (chemical formula 3), which have one oxygen atom.

[0008]

[0009] (n and m are integers from 1 to 4)

[0010]

[0011] (n and m are integers from 1 to 4)

[0012] Dioxin is a colorless crystalline solid at room temperature (25℃). It is chemically stable, doesn't break down or combine easily with other substances, and thus doesn't disappear naturally. Because it's nonpolar, dioxin doesn't dissolve well in water, but rather in fat. Therefore, when dioxin enters a living organism, it isn't excreted in urine but accumulates in fatty tissue. Thus, once formed, dioxin doesn't disappear and continues to accumulate within the body through the food chain.

[0013] These organic compounds, which contain halogen elements, are also abundant in pyrolysis oil. Pyrolysis oil is an oil made by heating waste plastic at high temperatures in an oxygen-free environment. Pyrolysis oil technology is receiving significant attention as a technology that can prevent environmental pollution and petroleum resource depletion because it can extract petroleum resources from waste plastic. One of the factors hindering the spread of pyrolysis oil technology is the halogen elements contained in pyrolysis oil. Most countries regulate the use of pyrolysis oil as a resource only when the amount of halogen elements contained in pyrolysis oil is below a certain level. Therefore, it is necessary to remove organic compounds containing halogen elements from pyrolysis oil to a certain level.

[0014] Effectively removing halogen elements such as chlorine and fluorine from waste oil, waste organic solvents, wastewater, semiconductor waste gases, semiconductor process cleaning solutions, pharmaceutical process cleaning solutions, dyeing process effluent, and pyrolysis oil can reduce emissions of environmental pollutants. Furthermore, organic compounds from which halogen elements have been removed can be used to recycle gaseous or liquid carbon, contributing significantly to energy security and greenhouse gas reduction.

[0015] Conventional techniques for treating organic compounds containing halogen elements, which are environmental pollutants, include incineration, hydrogenation, oxidation using precious metal catalysts, and catalytic reactions. However, incineration requires high temperatures exceeding 1,500°C, requiring significant energy to create such a high-temperature environment. Furthermore, incineration emits large amounts of carbon dioxide, a major contributor to global warming, and its emissions are strictly controlled. Consequently, incineration's use is limited. Hydrogenation removes halogen elements by adding hydrogen. However, hydrogen is a flammable, high-pressure gas, so it can only be used in certain locations, and its supply is also very limited. Oxidation using precious metal catalysts offers the advantage of high halogen removal efficiency. However, the raw materials for precious metal catalysts, such as platinum, palladium, and gold, are very expensive and difficult to recycle once used. Therefore, its use in industrial settings is limited to very limited cases. Conventional catalytic reactions involve contacting a catalyst, manufactured using the method disclosed in Korean Patent No. 10-1523876, with an organic compound containing halogen elements to remove the halogen element. This catalytic reaction technology produces sulfuric acid wastewater as a byproduct, requiring its treatment. Furthermore, this catalytic reaction technology also requires an additional catalyst surface treatment process, which reduces catalyst production productivity.

[0016] Existing technologies for removing halogen elements from organic compounds containing halogen elements have aspects that make them difficult to apply on a large scale in industrial settings, such as operating at high temperatures, which requires high energy costs, using hydrogen gas with limited use environments, or using expensive catalysts. The present invention provides a catalyst capable of continuously and rapidly removing halogen substances from organic compounds by reacting an organic compound containing halogen elements with a catalyst in both a gaseous and liquid phase, a method for producing the catalyst, and a method for continuously and rapidly removing halogen substances from organic compounds by reacting an organic compound containing halogen elements with a catalyst in both a gaseous and liquid phase using the catalyst.

[0017] The manufacturing process of the catalyst of the present invention is simple, which can improve productivity and reduce the manufacturing cost of the catalyst.

[0018] One embodiment of the present invention comprises a first step of dissolving a metal salt precursor including one metal selected from non-precious metal transition metals V or Cr in distilled water;

[0019] A second process of obtaining a catalyst slurry by adding titanium dioxide (TiO2) powder as a support to the metal salt precursor solution and then stirring the metal salt precursor solution containing the titanium dioxide (TiO2) powder to impregnate the metal into the titanium dioxide (TiO2) powder.

[0020] A third process of obtaining dried catalyst particles by drying the above catalyst slurry through a fluidized bed process or a reduced pressure distillation process;

[0021] A fourth process of adding aluminum oxide (Al2O3) sol or aluminum oxide (Al2O3) powder to the dried catalyst particles, and then processing the catalyst particles by extruding them into a pellet or spherical shape or coating them on the surface or pores of a ceramic monolith, metal foam, or ceramic material structure.

[0022] A fifth process including sintering the catalyst formed in the fourth process at 400-500°C,

[0023] This is a method for manufacturing a catalyst for removing halogen elements.

[0024] One embodiment of the present invention comprises a first step of dissolving a metal salt precursor comprising two metals selected from the group consisting of non-precious metal transition metals V, Cr, Mn, Fe, Co, Ni, and Cu in distilled water;

[0025] A second process of obtaining a catalyst slurry by adding titanium dioxide (TiO2) powder as a support to the metal salt precursor solution and then stirring the metal salt precursor solution containing the titanium dioxide (TiO2) powder to impregnate the titanium dioxide (TiO2) powder with the two types of metals.

[0026] A third process of obtaining dried catalyst particles by drying the above catalyst slurry through a fluidized bed process or a reduced pressure distillation process;

[0027] A fourth process of adding aluminum oxide (Al2O3) sol or aluminum oxide (Al2O3) powder to the dried catalyst particles, and then processing the catalyst particles by extruding them into a pellet or spherical shape or coating them on the surface or pores of a ceramic monolith, metal foam, or ceramic material structure.

[0028] Including the fifth process of sintering the catalyst formed in the fourth process at 400-500°C.

[0029] This is a method for manufacturing a catalyst for removing halogen elements.

[0030] In one embodiment of the present invention, anatase type titanium dioxide (TiO2) can be used as the titanium dioxide (TiO2) used in the method for producing the catalyst.

[0031] One embodiment of the present invention is titanium dioxide (TiO2) used in the method for producing the catalyst, which has a specific surface area of ​​95-350 m 2 / g and anatase type titanium dioxide (TiO2) with a purity of 95% or higher can be used.

[0032] In one embodiment of the present invention, in the first step of the method for producing the catalyst, 0.5 to 8.5 wt% of a metal salt precursor relative to the weight of the support in the second step can be dissolved in the distilled water.

[0033] In one embodiment of the present invention, in the second step of the method for producing the catalyst, the stirring can be performed for 4 to 10 hours.

[0034] In one embodiment of the present invention, VO(NO3)3, Ni(NO3)2, Co(NO3)2, Fe(NO3)3, Cu(NO3)2, Cr(NO3)3, or Mn(NO3)2 can be used as the metal salt precursor used in the method for producing the catalyst.

[0035] In one embodiment of the present invention, the fluidized bed process of the method for producing the catalyst may use a batch fluidized bed process, a continuous fluidized bed process, or a semi-continuous fluidized bed process.

[0036] One embodiment of the present invention is a catalyst for removing halogen elements, wherein a support including anatase type titanium dioxide (TiO2) and aluminum oxide (Al2O3) is impregnated with one metal selected from non-precious transition metals such as V or Cr.

[0037] One embodiment of the present invention comprises a first step of dissolving a metal salt precursor containing one metal selected from V or Cr, which are non-precious transition metals, in distilled water as a catalyst for removing the halogen group element.

[0038] A second process of obtaining a catalyst slurry by adding titanium dioxide (TiO2) powder as a support to the metal salt precursor solution and then stirring the metal salt precursor solution containing the titanium dioxide (TiO2) powder to impregnate the metal into the titanium dioxide (TiO2) powder.

[0039] A third process of obtaining dried catalyst particles by drying the above catalyst slurry through a fluidized bed process or a reduced pressure distillation process;

[0040] A fourth process of adding aluminum oxide (Al2O3) sol or aluminum oxide (Al2O3) powder to the dried catalyst particles, and then processing the catalyst particles by extruding them into a pellet or spherical shape or coating them on the surface or pores of a ceramic monolith, metal foam, or ceramic material structure.

[0041] It can be manufactured by a manufacturing method including a fifth process of sintering the catalyst formed in the fourth process at 400-500°C.

[0042] One embodiment of the present invention is a catalyst for removing halogen elements, wherein a support including anatase type titanium dioxide (TiO2) and aluminum oxide (Al2O3) is impregnated with two metals selected from the group consisting of non-precious transition metals such as V, Cr, Mn, Fe, Co, Ni, and Cu.

[0043] One embodiment of the present invention comprises a first step of dissolving a metal salt precursor containing two metals selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, and Cu, which are non-precious transition metals, in distilled water as a catalyst for removing the halogen group element.

[0044] A second process of obtaining a catalyst slurry by adding titanium dioxide (TiO2) powder as a support to the metal salt precursor solution and then stirring the metal salt precursor solution containing the titanium dioxide (TiO2) powder to impregnate the titanium dioxide (TiO2) powder with the two types of metals.

[0045] A third process of obtaining dried catalyst particles by drying the above catalyst slurry through a fluidized bed process or a reduced pressure distillation process;

[0046] A fourth process of adding aluminum oxide (Al2O3) sol or aluminum oxide (Al2O3) powder to the dried catalyst particles, and then processing the catalyst particles by extruding them into a pellet or spherical shape or coating them on the surface or pores of a ceramic monolith, metal foam, or ceramic material structure.

[0047] It can be manufactured by a manufacturing method including a fifth process of sintering the catalyst formed in the fourth process at 400-500°C.

[0048] One embodiment of the present invention is a catalyst support, wherein titanium dioxide (TiO2) has a specific surface area of ​​95-350 m 2 / g and may be anatase type titanium dioxide (TiO2) with a purity of 95% or higher.

[0049] One embodiment of the present invention is a method for removing a halogen element from a substance to be purified by contacting the substance containing an organic compound containing a halogen element in a liquid or gaseous state with a catalyst produced by the above production method.

[0050] One embodiment of the present invention is a method for removing a halogen element from a substance to be purified by contacting the substance containing an organic compound containing a halogen element with a catalyst in a liquid or gaseous state.

[0051] One embodiment of the present invention is a method for removing halogen elements from a material to be purified by passing a material to be purified including an organic compound including a halogen element and air through a reactor containing the catalyst, thereby contacting the material to be purified with the catalyst in a liquid or gaseous state.

[0052] In one embodiment of the method for removing halogen elements from a purified material of the present invention, the reactor may be composed of a portion containing the catalyst and a terminal portion having glass fibers.

[0053] In one embodiment of the method for removing halogen elements from a purified material of the present invention, the reactor may be composed of a portion containing the catalyst and a terminal portion having glass fibers.

[0054] In one embodiment of the method for removing halogen elements from a purified material of the present invention, a cooler may be provided at the rear end of the reactor to condense the purified material passing through the reactor.

[0055] In one embodiment of the method for removing halogen elements from a purified material of the present invention, the temperature of the reactor may be 300-500°C.

[0056] In one embodiment of the method for removing halogen elements from a purified material of the present invention, the purified material entering the reactor may be in a liquid or gaseous state.

[0057] Conventional catalysts require an additional process of adding distilled water and sulfuric acid and then stirring them to treat the surface of titanium dioxide (TiO2). This process requires the treatment of sulfuric acid wastewater, and the additional surface treatment process inevitably reduces productivity. In the present invention, the process of surface treatment with sulfuric acid is omitted, so the problem of treating sulfuric acid wastewater is eliminated. The present invention manufactures the catalyst by dissolving a metal salt precursor in distilled water, adding titanium dioxide to the solution, and stirring the solution to produce a wet impregnation method, thereby improving productivity and reducing costs. The catalyst of the present invention has excellent performance in removing halogen elements from organic compounds containing halogen elements.

[0058] Figure 1 is a schematic diagram of a reactor for removing a halogen element from an organic compound containing a halogen element using the catalyst of the present invention.

[0059] Any metal salt precursor may be used as the metal salt precursor of the present invention. Preferred metal salt precursors of the present invention are VO(NO3)3, Ni(NO3)2, Co(NO3)2, Fe(NO3)3, Cu(NO3)2, Cr(NO3)3, and Mn(NO3)2.

[0060] The support of the present invention is anatase titanium dioxide (TiO2). Titanium dioxide has a specific surface area of ​​95-350 m 2 / g and a purity of 95% or higher is desirable. This is because there is an optimal specific surface area that allows the metal salt to be evenly distributed and doped on the surface of the support during the process of reducing the metal to the metal.

[0061] In order to process the catalyst particles of the present invention into a certain shape by adhering them to each other, it is preferable to add an adhesive (binder). Any known adhesive may be used. In the present invention, it is preferable to use aluminum oxide (Al2O3) sol or aluminum oxide (Al2O3) powder as the adhesive.

[0062] The present invention uses anatase titanium dioxide (TiO2) as a support, but when aluminum oxide (Al2O3) is used as an additive, aluminum oxide (Al2O3) also attaches to titanium dioxide (TiO2). Thus, the support of the catalyst ultimately produced is a mixture of titanium dioxide (TiO2) and aluminum oxide (Al2O3).

[0063] The first step for producing the catalyst of the present invention is a step of dissolving the metal salt precursor in distilled water. The metal salt precursor of the present invention can be dissolved in distilled water in an amount of 0.5-10 wt%, 0.5-8.5 wt%, 0.5-7.5 wt%, 0.5-5 wt%, 1.5-10 wt%, 1.5-8.5 wt%, 1.5-7.5 wt%, 1.5-5 wt%, 2-10 wt%, 2-8.5 wt%, 2-7.5 wt%, 2-5 wt%, 3-10 wt%, 3-8.5 wt%, 3-7.5 wt%, 3-5 wt% relative to the weight of the support. This is because the performance of the catalyst varies depending on the content of the metal salt precursor, and when the amount is below a certain amount or above a certain amount, the reactivity drops sharply. The weight ratio of the support and the non-precious metal transition metal salt precursor may be 99.5-90:0.5-10, preferably 98.5-91.5:1.5-8.5, and more preferably 95-92.5:5-7.5.

[0064] The second process of the present invention is a process of adding anatase titanium dioxide (TiO2) powder, which is a catalyst support, to the metal salt precursor solution after the metal salt precursor has been dissolved in distilled water and stirring. In this way, a catalyst slurry in which the titanium dioxide (TiO2) powder is impregnated with the metal can be obtained. The titanium dioxide (TiO2) powder can be added in an amount of 70-95 wt%, preferably 75-90 wt%, and more preferably 80-90 wt%, based on the combined weight of the metal salt precursor, titanium dioxide (TiO2), and aluminum oxide (Al2O3). The stirring time can be 4-10 hours, 4-9 hours, 4-8 hours, 4-7 hours, 4-6 hours, or 4-5 hours.

[0065] The third step of the present invention is a step of drying the catalyst slurry. Any known drying means can be used in the present invention. Drying is preferably performed using a fluidized bed process or a reduced pressure distillation process. The fluidized bed process is a method of drying the catalyst by supplying hot air into a reactor containing the catalyst slurry. This fluidized bed process can be performed using a batch fluidized bed process, a continuous fluidized bed process, or a semi-continuous fluidized bed process. The reduced pressure distillation process is a method of drying the catalyst by reducing the pressure inside the reactor containing the catalyst slurry. In this way, dried catalyst particles can be obtained.

[0066] The fourth process of the present invention is a process of forming the catalyst particles into a certain shape. An adhesive may be used to allow the catalyst particles to adhere to each other. The present invention may use aluminum oxide (Al2O3) sol or aluminum oxide (Al2O3) powder as the adhesive. When coating the catalyst particles of the present invention on the surface or pores of a ceramic monolith, metal foam, or a structure made of ceramic material, an adhesive may not be used. The ceramic monolith is formed by forming sieve-shaped holes of various sizes through the interior of the ceramic. The metal foam is formed by forming a metal in a foamed form.

[0067] 0-30 parts by weight of aluminum oxide (Al2O3) sol or powder can be added to 100-70 parts by weight of dried catalyst. 0-20 parts by weight of aluminum oxide (Al2O3) sol or powder can be added to 100-80 parts by weight of dried catalyst. 1-30 parts by weight of aluminum oxide (Al2O3) sol or powder can be added to 99-70 parts by weight of dried catalyst. 1-20 parts by weight of aluminum oxide (Al2O3) sol or powder can be added to 99-80 parts by weight of dried catalyst. 5-20 parts by weight of aluminum oxide (Al2O3) sol or powder can be added to 95-80 parts by weight of dried catalyst.

[0068] The fifth step of the present invention is a step of sintering the molded catalyst. The sintering temperature may be 300-500°C, preferably 350-500°C, and more preferably 400-500°C.

[0069] The catalyst of the present invention produced by the above manufacturing method is a support comprising anatase type titanium dioxide (TiO2) and aluminum oxide (Al2O3), wherein one or two metals selected from the group consisting of non-noble transition metals V, Cr, Mn, Fe, Co, Ni, and Cu are impregnated. When the catalyst of the present invention contains one metal, it is preferable to contain V, Fe, Ni, or Cr. When the catalyst of the present invention contains one metal, it is more preferable to contain V or Cr. When the catalyst of the present invention contains two metals, it is preferable to contain a combination of V and Ni, V and Co, V and Cr, V and Fe, V and Cu, V and Mn, Cr and Ni, Cr and Co, Cr and Fe, Cr and Cu, Cr and Mn, Fe and Co, Fe and Ni, Fe and Cu, Ni and Co, Ni and Cu. When the catalyst of the present invention contains two kinds of metals, it is more preferable to contain a combination of V and Ni, V and Co, V and Cr, V and Fe, V and Cu, Cr and Ni, Cr and Co, Cr and Fe, Cr and Cu, Fe and Co, Fe and Ni, Ni and Co, Ni and Cu. When the catalyst of the present invention contains two kinds of metals, it is more preferable to contain a combination of Cr and Ni, Cr and Co, Cr and Fe.

[0070] The catalyst of the present invention can be used to remove halogen elements from a material to be refined (waste oil, waste organic solvent, waste water, semiconductor waste gas, semiconductor process cleaning solution, pharmaceutical process cleaning solution, dyeing process effluent, etc. containing halogen elements). When the material to be refined is brought into contact with the catalyst of the present invention in a liquid or gaseous state under a supply of air, the halogen elements can be removed from the halogen element compounds contained in the material to be refined. The temperature at which the material to be refined and the catalyst of the present invention come into contact and react can be 300-500°C, 350-500°C, 400-500°C, 450-500°C, 300-450°C, 350-450°C, 400-450°C, 300-400°C, or 350-400°C.

[0071] The purified material that has come into contact with the catalyst of the present invention can be passed through a filter. The filter serves to filter out impurities contained in the purified material. The filter can be made of glass fiber. The purified material that has passed through the filter can be liquefied by cooling with a cooler. The temperature of the cooler can be -20∼10℃, -20∼5℃, -20∼0℃, -10∼10℃, -10∼5℃, -10∼0℃, -5∼10℃, -5∼5℃, -5∼0℃.

[0072] FIG. 1 schematically illustrates a reactor for removing halogen elements from organic compounds containing halogen elements using the catalyst of the present invention. The reactor (8) is covered with a refractory jacket (7). Electricity (11) is connected to the refractory jacket (7) so that the temperature of the reactor can be raised to 300-500°C. The upper part of the reactor (8) is filled with the catalyst of the present invention so that the substance to be purified can come into contact with the catalyst of the present invention. The lower part of the reactor (8) is filled with glass fiber (9) so as to filter out impurities mixed in the substance to be purified. The glass fiber (9) also prevents the catalyst from leaking out. The substance to be purified (1) is injected into the reactor using a pump (2). Before being injected into the reactor, a preheater may be installed to raise the temperature of the substance to be purified so that the substance to be purified is injected into the reactor in a gaseous state. Alternatively, the substance to be purified may be injected into the reactor in a liquid state without a preheater. The reactor (8) has an air inlet (5) through which air is continuously supplied into the reactor (8). Air is required for the automatic regeneration of the catalyst. The amount of air supplied must be adjusted depending on the amount of the purified substance and the amount of catalyst to be purified.

[0073] Example

[0074] In this example, the term "Y / TiO2 catalyst" at X wt% means a catalyst in which a TiO2 support is impregnated with metal Y, made using X wt% of a Y metal precursor for the TiO2 support. In this example, 10 g of aluminum oxide (Al2O3) powder is added to the dried catalyst particles, so the support contains Al2O3 in addition to TiO2. However, for convenience, it is simply referred to as "Y / TiO2 catalyst."

[0075] Preparation of the catalyst of the present invention

[0076] 1-1. Preparation of 1.5 wt% V / TiO2 catalyst

[0077] 0.75 g of VO(NO3)3, corresponding to 1.5 wt% of 50 g of titanium dioxide (TiO2), was dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the VO(NO3)3 precursor solution and stirred for about 1 hour to obtain a V / TiO2 catalyst slurry. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the V / TiO2 catalyst slurry. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0078] Preparation of 1-2.5 wt% V / TiO2 catalyst

[0079] A 5 wt% V / TiO2 catalyst was prepared in the same manner as in Example 1-1, except that 2.5 g of VO(NO3)3, corresponding to 5 wt% of 50 g of titanium dioxide (TiO2), was dissolved in distilled water.

[0080] 1-3. Preparation of 7.5 wt% V / TiO2 catalyst

[0081] A 7.5 wt% V / TiO2 catalyst was prepared in the same manner as in Example 1-1, except that 3.75 g of VO(NO3)3, corresponding to 7.5 wt% per 50 g of titanium dioxide (TiO2), was dissolved in distilled water.

[0082] 2-1. Preparation of 1.5 wt% V-Ni / TiO2 catalyst

[0083] 0.375 g of VO(NO3)3 and 0.375 g of Ni(NO3)2, corresponding to 0.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the VO(NO3)3 and Ni(NO3)2 precursor solution and stirred for about 1 hour to obtain a V-Ni / TiO2 catalyst slurry. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the V-Ni / TiO2 catalyst slurry. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0084] 2-2. Preparation of 5 wt% V-Ni / TiO2 catalyst

[0085] A 5 wt% V-Ni / TiO2 catalyst was prepared in the same manner as in Example 2-1, except that 1.25 g of VO(NO3)3 and 1.25 g of Ni(NO3)2, corresponding to 2.5 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0086] 2-3. Preparation of 7.5 wt% V-Ni / TiO2 catalyst

[0087] A 7.5 wt% V-Ni / TiO2 catalyst was prepared in the same manner as in Example 2-1, except that 1.875 g of VO(NO3)3 and 1.875 g of Ni(NO3)2, corresponding to 3.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0088] 3-1. Preparation of 1.5 wt% V-Co / TiO2 catalyst

[0089] 0.375 g of VO(NO3)3 and 0.375 g of Co(NO3)2, corresponding to 0.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the VO(NO3)3 and Co(NO3)2 precursor solution and stirred for about 1 hour to obtain a V-Co / TiO2 catalyst slurry. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the V-Co / TiO2 catalyst slurry. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0090] 3-2. Preparation of 5 wt% V-Co / TiO2 catalyst

[0091] A 5 wt% V-Co / TiO2 catalyst was prepared in the same manner as in Example 3-1, except that 1.25 g of VO(NO3)3 and 1.25 g of Co(NO3)2, corresponding to 2.5 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0092] 3-3. Preparation of 7.5 wt% V-Co / TiO2 catalyst

[0093] A 7.5 wt% V-Co / TiO2 catalyst was prepared in the same manner as in Example 3-1, except that 1.875 g of VO(NO3)3 and 1.875 g of Co(NO3)2, corresponding to 3.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0094] 4-1. Preparation of 1.5 wt% V-Fe / TiO2 catalyst

[0095] 0.375 g of VO(NO3)3 and 0.375 g of Fe(NO3)3, corresponding to 0.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the VO(NO3)3 and Fe(NO3)3 precursor solution and stirred for about 1 hour to obtain a V-Fe / TiO2 catalyst slurry. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the V-Fe / TiO2 catalyst slurry. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0096] 4-2. Preparation of 5 wt% V-Fe / TiO2 catalyst

[0097] A 5 wt% V-Fe / TiO2 catalyst was prepared in the same manner as in Example 4-1, except that 1.25 g of VO(NO3)3 and 1.25 g of Fe(NO3)3, corresponding to 2.5 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0098] 4-3. Preparation of 7.5 wt% V-Fe / TiO2 catalyst

[0099] A 7.5 wt% V-Fe / TiO2 catalyst was prepared in the same manner as in Example 4-1, except that 1.875 g of VO(NO3)3 and 1.875 g of Fe(NO3)3, corresponding to 3.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0100] 5-1. Preparation of 1.5 wt% V-Cu / TiO2 catalyst

[0101] 0.375 g of VO(NO3)3 and 0.375 g of Cu(NO3)2, corresponding to 0.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the VO(NO3)3 and Cu(NO3)2 precursor solution and stirred for about 1 hour to obtain a V-Cu / TiO2 catalyst slurry. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the V-Cu / TiO2 catalyst slurry. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0102] 5-2. Preparation of 5 wt% V-Cu / TiO2 catalyst

[0103] A 5 wt% V-Cu / TiO2 catalyst was prepared in the same manner as in Example 5-1, except that 1.25 g of VO(NO3)3 and 1.25 g of Cu(NO3)2, corresponding to 2.5 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0104] 5-3. Preparation of 7.5 wt% V-Cu / TiO2 catalyst

[0105] A 7.5 wt% V-Cu / TiO2 catalyst was prepared in the same manner as in Example 5-1, except that 1.875 g of VO(NO3)3 and 1.875 g of Cu(NO3)2, corresponding to 3.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0106] 6-1. Preparation of 1.5 wt% Cr / TiO2 catalyst

[0107] 0.75 g of Cr(NO3)3, corresponding to 1.5 wt% of 50 g of titanium dioxide (TiO2), was dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the Cr(NO3)3 precursor solution and stirred for about 1 hour to obtain a Cr / TiO2 catalyst slurry. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the Cr / TiO2 catalyst slurry. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0108] 6-2. Preparation of 5 wt% Cr / TiO2 catalyst

[0109] A 5 wt% Cr / TiO2 catalyst was prepared in the same manner as in Example 6-1, except that 2.5 g of Cr(NO3)3, corresponding to 5 wt% of 50 g of titanium dioxide (TiO2), was dissolved in distilled water.

[0110] 6-3. Preparation of 7.5 wt% Cr / TiO2 catalyst

[0111] A 7.5 wt% Cr / TiO2 catalyst was prepared in the same manner as in Example 6-1, except that 3.75 g of Cr(NO3)3, corresponding to 7.5 wt% per 50 g of titanium dioxide (TiO2), was dissolved in distilled water.

[0112] 7-1. Preparation of 1.5 wt% Cr-Ni / TiO2 catalyst

[0113] 0.375 g of Cr(NO3)3 and 0.375 g of Ni(NO3)2, corresponding to 0.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the Cr(NO3)3 and Ni(NO3)2 precursor solution and stirred for about 1 hour to obtain a slurry of Cr-Ni / TiO2 catalyst. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the slurry of Cr-Ni / TiO2 catalyst. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0114] 7-2. Preparation of 5 wt% Cr-Ni / TiO2 catalyst

[0115] A 5 wt% Cr-Ni / TiO2 catalyst was prepared in the same manner as in Example 7-1, except that 1.25 g of Cr(NO3)3 and 1.25 g of Ni(NO3)2, corresponding to 2.5 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0116] 7-3. Preparation of 7.5 wt% Cr-Ni / TiO2 catalyst

[0117] A 7.5 wt% Cr-Ni / TiO2 catalyst was prepared in the same manner as in Example 7-1, except that 1.875 g of Cr(NO3)3 and 1.875 g of Ni(NO3)2, corresponding to 3.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0118] 8-1. Preparation of 1.5 wt% Cr-Co / TiO2 catalyst

[0119] 0.375 g of Cr(NO3)3 and 0.375 g of Co(NO3)2, corresponding to 0.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the Cr(NO3)3 and Co(NO3)2 precursor solution and stirred for about 1 hour to obtain a Cr-Co / TiO2 catalyst slurry. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the Cr-Co / TiO2 catalyst slurry. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0120] 8-2. Preparation of 5 wt% Cr-Co / TiO2 catalyst

[0121] A 5 wt% Cr-Co / TiO2 catalyst was prepared in the same manner as in Example 8-1, except that 1.25 g of Cr(NO3)3 and 1.25 g of Co(NO3)2, corresponding to 2.5 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0122] 8-3. Preparation of 7.5 wt% Cr-Co / TiO2 catalyst

[0123] A 7.5 wt% Cr-Ni / TiO2 catalyst was prepared in the same manner as in Example 8-1, except that 1.875 g of Cr(NO3)3 and 1.875 g of Co(NO3)2, corresponding to 3.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0124] 9-1. Preparation of 1.5 wt% Cr-Fe / TiO2 catalyst

[0125] 0.375 g of Cr(NO3)3 and 0.375 g of Fe(NO3)3, corresponding to 0.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the Cr(NO3)3 and Fe(NO3)3 precursor solution and stirred for about 1 hour to obtain a slurry of Cr-Fe / TiO2 catalyst. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the slurry of Cr-Fe / TiO2 catalyst. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0126] 9-2. Preparation of 5 wt% Cr-Fe / TiO2 catalyst

[0127] A 5 wt% Cr-Fe / TiO2 catalyst was prepared in the same manner as in Example 9-1, except that 1.25 g of Cr(NO3)3 and 1.25 g of Fe(NO3)3, corresponding to 2.5 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0128] 9-3. Preparation of 7.5 wt% Cr-Fe / TiO2 catalyst

[0129] A 7.5 wt% Cr-Fe / TiO2 catalyst was prepared in the same manner as in Example 9-1, except that 1.875 g of Cr(NO3)3 and 1.875 g of Fe(NO3)3, corresponding to 3.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0130] 10-1. Preparation of 1.5 wt% Cr-Cu / TiO2 catalyst

[0131] 0.375 g of Cr(NO3)3 and 0.375 g of Cu(NO3)2, corresponding to 0.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the Cr(NO3)3 and Cu(NO3)2 precursor solution and stirred for about 1 hour to obtain a slurry of Cr-Cu / TiO2 catalyst. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the slurry of Cr-Cu / TiO2 catalyst. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0132] Preparation of 10-2.5 wt% Cr-Cu / TiO2 catalyst

[0133] A 5 wt% Cr-Cu / TiO2 catalyst was prepared in the same manner as in Example 10-1, except that 1.25 g of Cr(NO3)3 and 1.25 g of Cu(NO3)2, corresponding to 2.5 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0134] 10-3. Preparation of 7.5 wt% Cr-Cu / TiO2 catalyst

[0135] A 7.5 wt% Cr-Cu / TiO2 catalyst was prepared in the same manner as in Example 10-1, except that 1.875 g of Cr(NO3)3 and 1.875 g of Cu(NO3)2, corresponding to 3.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0136] 11-1. Preparation of 1.5 wt% Ni-Cu / TiO2 catalyst

[0137] 0.375 g of Ni(NO3)2 and 0.375 g of Cu(NO3)2, corresponding to 0.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the Ni(NO3)2 and Cu(NO3)2 precursor solution and stirred for about 1 hour to obtain a slurry of Ni-Cu / TiO2 catalyst. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the slurry of Ni-Cu / TiO2 catalyst. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0138] 11-2. Preparation of 5 wt% Ni-Cu / TiO2 catalyst

[0139] A 5 wt% Ni-Cu / TiO2 catalyst was prepared in the same manner as in Example 11-1, except that 1.25 g of Ni(NO3)2 and 1.25 g of Cu(NO3)2, corresponding to 2.5 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0140] 11-3. Preparation of 7.5 wt% Ni-Cu / TiO2 catalyst

[0141] A 7.5 wt% Ni-Cu / TiO2 catalyst was prepared in the same manner as in Example 11-1, except that 1.875 g of Ni(NO3)2 and 1.875 g of Cu(NO3)2, corresponding to 3.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0142] 12-1. Preparation of 1.5 wt% Ni-Co / TiO2 catalyst

[0143] 0.375 g of Ni(NO3)2 and 0.375 g of Co(NO3)2, corresponding to 0.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the Ni(NO3)2 and Co(NO3)2 precursor solution and stirred for about 1 hour to obtain a slurry of Ni-Co / TiO2 catalyst. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the slurry of Ni-Co / TiO2 catalyst. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0144] 12-2. Preparation of 5 wt% Ni-Co / TiO2 catalyst

[0145] A 5 wt% Ni-Co / TiO2 catalyst was prepared in the same manner as in Example 12-1, except that 1.25 g of Ni(NO3)2 and 1.25 g of Co(NO3)2, corresponding to 2.5 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0146] 12-3. Preparation of 7.5 wt% Ni-Co / TiO2 catalyst

[0147] A 7.5 wt% Ni-Co / TiO2 catalyst was prepared in the same manner as in Example 12-1, except that 1.875 g of Ni(NO3)2 and 1.875 g of Co(NO3)2, corresponding to 3.75 wt% of 50 g of titanium dioxide (TiO2), were dissolved in distilled water.

[0148] 13-1. Preparation of 1.5 wt% Ni / TiO2 catalyst

[0149] 0.75 g of Ni(NO3)2, corresponding to 1.5 wt% of 50 g of titanium dioxide (TiO2), was dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the Ni(NO3)2 precursor solution and stirred for about 1 hour to obtain a Ni / TiO2 catalyst slurry. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the Ni / TiO2 catalyst slurry. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0150] 13-2. Preparation of 5 wt% Ni / TiO2 catalyst

[0151] A 5 wt% Ni / TiO2 catalyst was prepared in the same manner as in Example 13-1, except that 2.5 g of Ni(NO3)2, corresponding to 5 wt% of 50 g of titanium dioxide (TiO2), was dissolved in distilled water.

[0152] 13-3. Preparation of 7.5 wt% Ni / TiO2 catalyst

[0153] A 7.5 wt% Ni / TiO2 catalyst was prepared in the same manner as in Example 13-1, except that 3.75 g of Ni(NO3)2, corresponding to 7.5 wt% per 50 g of titanium dioxide (TiO2), was dissolved in distilled water.

[0154] 14-1. Preparation of 1.5 wt% Cu / TiO2 catalyst

[0155] 0.75 g of Cu(NO3)2, corresponding to 1.5 wt% of 50 g of titanium dioxide (TiO2), was dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the Cu(NO3)2 precursor solution and stirred for about 1 hour to obtain a Cu / TiO2 catalyst slurry. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the Cu / TiO2 catalyst slurry. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to remove all nitrides.

[0156] 14-2. Preparation of 5 wt% Cu / TiO2 catalyst

[0157] A 5 wt% Cu / TiO2 catalyst was prepared in the same manner as in Example 14-1, except that 2.5 g of Cu(NO3)2, corresponding to 5 wt% of 50 g of titanium dioxide (TiO2), was dissolved in distilled water.

[0158] 14-3. Preparation of 7.5 wt% Cu / TiO2 catalyst

[0159] A 7.5 wt% Cu / TiO2 catalyst was prepared in the same manner as in Example 14-1, except that 3.75 g of Cu(NO3)2, corresponding to 7.5 wt% per 50 g of titanium dioxide (TiO2), was dissolved in distilled water.

[0160] 15-1. Preparation of 1.5 wt% Fe / TiO2 catalyst

[0161] 0.75 g of Fe(NO3)3, corresponding to 1.5 wt% of 50 g of titanium dioxide (TiO2), was dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the Fe(NO3)3 precursor solution and stirred for about 1 hour to obtain a slurry of Fe / TiO2 catalyst. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the Fe / TiO2 catalyst slurry. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0162] 15-2. Preparation of 5 wt% Fe / TiO2 catalyst

[0163] A 5 wt% Fe / TiO2 catalyst was prepared in the same manner as in Example 15-1, except that 2.5 g of Fe(NO3)3, corresponding to 5 wt% of 50 g of titanium dioxide (TiO2), was dissolved in distilled water.

[0164] 15-3. Preparation of 7.5 wt% Fe / TiO2 catalyst

[0165] A 7.5 wt% Fe / TiO2 catalyst was prepared in the same manner as in Example 15-1, except that 3.75 g of Fe(NO3)3, corresponding to 7.5 wt% per 50 g of titanium dioxide (TiO2), was dissolved in distilled water.

[0166] 16-1. Preparation of 1.5 wt% Mn / TiO2 catalyst

[0167] 0.75 g of Mn(NO3)2, corresponding to 1.5 wt% of 50 g of titanium dioxide (TiO2), was dissolved in distilled water. 50 g of titanium dioxide (TiO2) powder was added to the Mn(NO3)2 precursor solution and stirred for about 1 hour to obtain a slurry of Mn / TiO2 catalyst. Rotary evaporation was performed at 80°C to completely evaporate the distilled water from the slurry of Mn / TiO2 catalyst. 10 g of aluminum oxide (Al2O3) powder was added to the dried catalyst particles. The catalyst thus formed was calcined at 500°C to completely remove nitrides.

[0168] 16-2. Preparation of 5 wt% Mn / TiO2 catalyst

[0169] A 5 wt% Mn / TiO2 catalyst was prepared in the same manner as in Example 16-1, except that 2.5 g of Mn(NO3)2, corresponding to 5 wt% of 50 g of titanium dioxide (TiO2), was dissolved in distilled water.

[0170] 16-3. Preparation of 7.5 wt% Mn / TiO2 catalyst

[0171] A 7.5 wt% Mn / TiO2 catalyst was prepared in the same manner as in Example 16-1, except that 3.75 g of Mn(NO3)2, corresponding to 7.5 wt% per 50 g of titanium dioxide (TiO2), was dissolved in distilled water.

[0172] Method for removing halogen elements from halogen compounds using the catalyst of the present invention

[0173] The performance of the catalyst of the present invention for removing halogen elements from halogen compounds was tested as follows with 7.5 wt% of the catalyst.

[0174] 1. Removal of chlorine from dichloromethane (DCM) using V / TiO2 catalyst

[0175] Dichloromethane (DCM) was used as a standard sample to evaluate the performance of the catalyst of the present invention. Standard samples were prepared by diluting dichloromethane (DCM) to 100 ppm, 1,000 ppm, and 10,000 ppm. The chlorine concentration of each standard sample was measured using a gas chromatography-electron capture detector (GC-ECD). The chlorine concentrations of each standard sample were 100 ppm, 1,000 ppm, and 10,000 ppm. The chlorine removal performance of the catalyst of Example 1 was evaluated by passing each standard sample through a chlorine removal reactor containing the catalyst prepared in Example 1. The configuration of the chlorine removal reactor is shown in Figure 1. The standard sample was moved to the chlorine removal reactor by a pump. A preheater was installed between the pump and the chlorine removal reactor to vaporize the dichloromethane and then introduce it into the chlorine removal reactor. In addition to the standard sample, air was also introduced into the chlorine removal reactor. The air serves to regenerate the catalyst. The chlorine removal reactor was composed of a section containing the catalyst of the present invention and an end section containing glass fiber. The section containing the catalyst of the present invention was covered with a refractory jacket and the temperature was maintained at 350-400°C. The flow rate of the standard sample was maintained at 30 cc / min. The flow rate of air was maintained at 100 cc / min. A cooler was installed at the rear end of the chlorine removal reactor to condense the reaction gas and recover the standard sample that had completed the reaction with the catalyst of the present invention. The recovered standard sample was passed through a GC-ECD to measure the chlorine concentration.

[0176] 2. Removal of chlorine from dichloromethane (DCM) using V-Ni / TiO2 catalyst

[0177] The dichloromethane (DCM) removal performance of the catalyst of Example 2 was evaluated in the same manner as Example 1, except that V-Ni / TiO2 of Example 2 was used instead of V / TiO2 of Example 1 as the catalyst.

[0178] 3. Removal of chlorine from dichloromethane (DCM) using V-Fe / TiO2 catalyst

[0179] The dichloromethane (DCM) removal performance of the catalyst of Example 4 was evaluated in the same manner as in Example 1, except that V-Fe / TiO2 of Example 4 was used instead of V / TiO2 of Example 1 as the catalyst.

[0180] 4. Removal of chlorine from dichloromethane (DCM) using V-Cu / TiO2 catalyst

[0181] The dichloromethane (DCM) removal performance of the catalyst of Example 5 was evaluated in the same manner as in Example 1, except that V-Cu / TiO2 of Example 5 was used instead of V / TiO2 of Example 1 as the catalyst.

[0182] 5. Removal of chlorine from dichloromethane (DCM) using Cr / TiO2 catalyst

[0183] The dichloromethane (DCM) removal performance of the catalyst of Example 6 was evaluated in the same manner as Example 1, except that Cr / TiO2 of Example 6 was used instead of V / TiO2 of Example 1 as the catalyst.

[0184] 6. Removal of chlorine from dichloromethane (DCM) using Cr-Ni / TiO2 catalyst

[0185] The dichloromethane (DCM) removal performance of the catalyst of Example 7 was evaluated in the same manner as in Example 1, except that Cr-Ni / TiO2 of Example 7 was used instead of V / TiO2 of Example 1 as the catalyst.

[0186] 7. Removal of chlorine from dichloromethane (DCM) using Cr-Co / TiO2 catalyst

[0187] The dichloromethane (DCM) removal performance of the catalyst of Example 8 was evaluated in the same manner as in Example 1, except that Cr-Co / TiO2 of Example 8 was used instead of V / TiO2 of Example 1 as the catalyst.

[0188] 8. Removal of chlorine from dichloromethane (DCM) using Cr-Fe / TiO2 catalyst

[0189] The dichloromethane (DCM) removal performance of the catalyst of Example 9 was evaluated in the same manner as in Example 1, except that Cr-Fe / TiO2 of Example 9 was used instead of V / TiO2 of Example 1 as the catalyst.

[0190] 9. Removal of chlorine from dichloromethane (DCM) using Cr-Cu / TiO2 catalyst

[0191] The dichloromethane (DCM) removal performance of the catalyst of Example 10 was evaluated in the same manner as in Example 1, except that Cr-Cu / TiO2 of Example 10 was used instead of V / TiO2 of Example 1 as the catalyst.

[0192] The performance of the catalyst of the present invention manufactured above for removing chlorine from dichloromethane (DCM) is summarized in Table 1 below.

[0193] Concentration of DCM in the standard sample before reaction with the catalyst (ppm) 100.0 1,000.0 10,000.0 Concentration of DCM in the standard sample after reaction with the catalyst of Example 1 (ppm) 48.05 89.05 230.0 Concentration of DCM in the standard sample after reaction with the catalyst of Example 2 (ppm) 32.04 52.04 210.0 Concentration of DCM in the standard sample after reaction with the catalyst of Example 4 (ppm) 38.03 95.04 185.0 Concentration of DCM in the standard sample after reaction with the catalyst of Example 5 (ppm) 42.05 32.05 725.0 Concentration of DCM in the standard sample after reaction with the catalyst of Example 6 (ppm) 0.5 0.5 0.5 Concentration 0.50.50.5 Concentration of DCM in the standard sample (ppm) after reacting with the catalyst of Example 8 5.025.0320.0 Concentration of DCM in the standard sample (ppm) after reacting with the catalyst of Example 9 12.0167.01.850.0 Concentration of DCM in the standard sample (ppm) after reacting with the catalyst of Example 10 28.0116.02,120.0

[0194] As shown in Table 1, the catalyst of the present invention was sufficiently functioning even with only 7.5 wt% of the metal salt precursor added to the support. While increasing the content of non-precious transition metals improves catalytic performance, the relationship between the content and catalytic performance is not proportional. Increasing the content of non-precious transition metals also increases the catalyst manufacturing cost. Therefore, it is necessary to select the optimal catalyst for each application by considering both price and performance.

[0195] [Explanation of symbols]

[0196] 1: Purified substance

[0197] 2: Pump

[0198] 3: Preheater

[0199] 4: Temperature sensor

[0200] 5: Air inlet

[0201] 6: Purified substance injection port

[0202] 7: Fireproof jacket

[0203] 8: Reactor

[0204] 9: Glass fiber

[0205] 10: Cooler

[0206] 11: Electricity

Claims

1. A first step of dissolving a metal salt precursor containing one metal selected from non-precious metal transition metals V or Cr in distilled water; A second step of obtaining a catalyst slurry by adding titanium dioxide (TiO2) powder as a support to the metal salt precursor solution and then stirring the metal salt precursor solution containing the titanium dioxide (TiO2) powder to impregnate the metal into the titanium dioxide (TiO2) powder. A third process of obtaining dried catalyst particles by drying the above catalyst slurry through a fluidized bed process or a reduced pressure distillation process; A fourth process of adding aluminum oxide (Al2O3) sol or aluminum oxide (Al2O3) powder to the dried catalyst particles, and then processing the catalyst particles by extruding them into a pellet or spherical shape or coating them on the surface or pores of a ceramic monolith, metal foam, or ceramic material structure. Including the fifth process of sintering the catalyst formed in the fourth process at 400-500°C. A method for producing a catalyst for removing halogen elements.

2. A first step of dissolving a metal salt precursor containing two metals selected from the group consisting of non-precious metal transition metals V, Cr, Mn, Fe, Co, Ni, and Cu in distilled water; A second step of obtaining a catalyst slurry by adding titanium dioxide (TiO2) powder as a support to the metal salt precursor solution and then stirring the metal salt precursor solution containing the titanium dioxide (TiO2) powder to impregnate the titanium dioxide (TiO2) powder with the two types of metals. A third process of obtaining dried catalyst particles by drying the above catalyst slurry through a fluidized bed process or a reduced pressure distillation process; A fourth process of adding aluminum oxide (Al2O3) sol or aluminum oxide (Al2O3) powder to the dried catalyst particles, and then processing the catalyst particles by extruding them into a pellet or spherical shape or coating them on the surface or pores of a ceramic monolith, metal foam, or ceramic material structure. Including the fifth process of sintering the catalyst formed in the fourth process at 400-500°C. A method for producing a catalyst for removing halogen elements.

3. In the first or second paragraph, the titanium dioxide (TiO2) has a specific surface area of ​​95-350 m 2 / g and a method for producing a catalyst for removing halogen elements, the catalyst being titanium dioxide (TiO2) of the anatase type having a purity of 95% or higher.

4. A method for producing a catalyst for removing a halogen element, wherein in the first or second paragraph, a metal salt precursor is dissolved in distilled water in an amount of 0.5 to 8.5 wt% relative to the weight of the support in the second process in the first process.

5. A method for producing a catalyst for removing a halogen element, wherein in the second process, the stirring is performed for 4 to 10 hours in the first or second paragraph.

6. A method for producing a catalyst for removing a halogen element, wherein the metal salt precursor in claim 1 or 2 is VO(NO3)3, Ni(NO3)2, Co(NO3)2, Fe(NO3)3, Cu(NO3)2, Cr(NO3)3, or Mn(NO3)2.

7. A method for producing a catalyst for removing halogen elements, wherein the fluidized bed process in claim 1 or 2 is a batch fluidized bed process, a continuous fluidized bed process, or a semi-continuous fluidized bed process.

8. A catalyst for removing halogen elements, wherein a support comprising anatase type titanium dioxide (TiO2) and aluminum oxide (Al2O3) is impregnated with one metal selected from non-precious transition metals such as V or Cr.

9. A catalyst for removing halogen elements, wherein a support comprising anatase type titanium dioxide (TiO2) and aluminum oxide (Al2O3) is impregnated with two metals selected from the group consisting of non-precious transition metals such as V, Cr, Mn, Fe, Co, Ni, and Cu.

10. A catalyst for removing a halogen element, in claim 8, wherein the catalyst is manufactured by a manufacturing method including the following process. A first step of dissolving a metal salt precursor containing one metal selected from non-precious metal transition metals V or Cr in distilled water; A second step of obtaining a catalyst slurry by adding titanium dioxide (TiO2) powder as a support to the metal salt precursor solution and then stirring the metal salt precursor solution containing the titanium dioxide (TiO2) powder to impregnate the metal into the titanium dioxide (TiO2) powder. A third process of obtaining dried catalyst particles by drying the above catalyst slurry through a fluidized bed process or a reduced pressure distillation process; A fourth process of adding aluminum oxide (Al2O3) sol or aluminum oxide (Al2O3) powder to the dried catalyst particles, and then processing the catalyst particles by extruding them into a pellet or spherical shape or coating them on the surface or pores of a ceramic monolith, metal foam, or ceramic material structure. The fifth process of sintering the catalyst formed in the fourth process above at 400-500℃.

11. A catalyst for removing a halogen element, wherein the catalyst is manufactured by a manufacturing method including the following process in the 9th paragraph. A first step of dissolving a metal salt precursor containing two metals selected from the group consisting of non-precious metal transition metals V, Cr, Mn, Fe, Co, Ni, and Cu in distilled water; A second step of obtaining a catalyst slurry by adding titanium dioxide (TiO2) powder as a support to the metal salt precursor solution and then stirring the metal salt precursor solution containing the titanium dioxide (TiO2) powder to impregnate the titanium dioxide (TiO2) powder with the two types of metals. A third process of obtaining dried catalyst particles by drying the above catalyst slurry through a fluidized bed process or a reduced pressure distillation process; A fourth process of adding aluminum oxide (Al2O3) sol or aluminum oxide (Al2O3) powder to the dried catalyst particles, and then processing the catalyst particles by extruding them into a pellet or spherical shape or coating them on the surface or pores of a ceramic monolith, metal foam, or ceramic material structure. The fifth process of sintering the catalyst formed in the fourth process above at 400-500℃.

12. In the 8th or 9th clause, the titanium dioxide (TiO2) has a specific surface area of ​​95-350 m 2 / g and a catalyst for removing halogen elements, which is titanium dioxide (TiO2) of the anatase type with a purity of 95% or higher.

13. A method for removing halogen elements from a substance to be purified by contacting the substance to be purified, which includes an organic compound containing a halogen element, with a catalyst produced by the production method of claim 1 or 2 in a liquid or gaseous state.

14. A method for removing halogen elements from a substance to be purified by contacting the substance to be purified, which includes an organic compound containing a halogen element, with the catalyst of claim 8 or 9 in a liquid or gaseous state.

15. A method for removing halogen elements from a purified material by passing air and a purified material containing an organic compound including a halogen element through a reactor containing the catalyst in accordance with paragraph 13.

16. A method for removing halogen elements from a purified material by passing air and a purified material containing an organic compound including a halogen element through a reactor containing the catalyst in accordance with paragraph 14.

17. A method for removing halogen elements from a purified material, wherein the reactor comprises a portion containing the catalyst and a terminal portion having glass fibers in the 13th paragraph.

18. A method for removing halogen elements from a purified material, wherein the reactor comprises a portion containing the catalyst and a terminal portion having glass fibers in the 14th paragraph.

19. A method for removing halogen elements from a purified material, wherein a cooler is provided at the rear end of the reactor in clause 13 to condense the purified material passing through the reactor.

20. A method for removing halogen elements from a purified material, wherein a cooler is provided at the rear end of the reactor in clause 14 to condense the purified material passing through the reactor.

21. A method for removing halogen elements from a purified material in claim 13, wherein the temperature of the reactor is 300-500°C.

22. A method for removing halogen elements from a purified material in claim 14, wherein the temperature of the reactor is 300-500°C.

23. A method for removing halogen elements from a purified material in the 13th paragraph, wherein the purified material entering the reactor is in a liquid or gaseous state.

24. A method for removing halogen elements from a purified material in the 14th paragraph, wherein the purified material entering the reactor is in a liquid or gaseous state.

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