KR102121551B1 - Complex Metal Oxides Catalyst for Removal of Volatile Organic Compounds - Google Patents

Abstract

The present invention relates to a method for preparing a composite oxide catalyst for removing volatile organic compounds, and more specifically, a waste a catalyst discharged from the FCC process is mixed with anatase type titanium dioxide, copper and manganese in a specific mixing ratio, and the casting waste By producing a composite oxide catalyst for the removal of volatile organic compounds by using the dust, which is a dust, as a binder, it has excellent price competitiveness compared to a conventional noble metal-based catalyst, and at the same time, improves the waste catalyst generated from the FCC process and waste generated from the foundry. The present invention relates to a method for preparing a composite oxide catalyst for removing volatile organic compounds, which can be used as an added value and can easily produce a catalyst for removing volatile organic compounds, which is excellent in performance and durability in a simple manufacturing process.

Description

Manufacturing method of complex oxide catalyst for removing volatile organic compounds{Complex Metal Oxides Catalyst for Removal of Volatile Organic Compounds}

The present invention relates to a method for preparing a composite oxide catalyst for removing volatile organic compounds, and more specifically, it has excellent price competitiveness compared to a catalyst for removing volatile organic compounds using a FCC process waste catalyst, and has simple performance and durability. The present invention relates to a method for preparing a composite oxide catalyst for removing volatile organic compounds, which can produce an excellent composite oxide catalyst for removing volatile organic compounds.

Volatile organic compounds (VOCs) produced in factories that perform petrochemical product manufacturing processes, production of various fine chemical products, or manufacturing, plating, and coating processes for textiles, plastics, or electronic parts materials are highly industrialized. Accordingly, its emissions are increasing and it is also known as a chemical harmful to the human body. The methods for removing these volatile organic compounds include direct combustion, adsorption, and catalytic oxidation, but catalytic oxidation is considered to be the most ideal method in terms of economy and environmental friendliness.

The catalytic oxidation method is mainly used for the removal of volatile organic compounds due to the advantage of operating in a small reactor made of a relatively inexpensive material, with an energy consumption of only 50% due to a significantly lower operating temperature compared to the thermal incineration method. A catalyst that provides excellent activity in the oxidation removal reaction of volatile organic compounds according to the catalytic oxidation method can be referred to as a noble metal catalyst.

As an example of such a catalytic oxidation method, U.S. Patent No. 4059675 and Republic of Korea Patent Publication No. 2016-0045689 disclose a reaction for decomposing a volatile organic compound using a catalyst containing one or more of noble metals alone. . In addition, there are other catalysts composed of a transition metal oxide and a rare earth metal oxide as having a non-noble metal as an active ingredient. Their catalytic activity is still significantly lower in oxidation reaction efficiency than a noble metal catalyst. to be.

In the case of the catalytic oxidation method using such a noble metal catalyst, it exhibits high activity at a relatively low temperature (150° C. to 450° C.), but since the noble metal is contained alone, the price competitiveness decreases depending on its content ratio, and the scarcity and demand of the metal Due to the increase, the price is increasing every year, and in particular, it has a disadvantage that it is easily agglomerated by heat during the reaction process due to low thermal stability, and thus, a new catalyst to replace it is required.

In this regard, nickel-containing catalysts are inexpensive compared to noble metal catalysts, but have similar catalytic activity, and are receiving attention as a substitute for noble metal catalysts. However, due to the low thermal stability of the nickel catalyst itself, research is being conducted on a complex oxide that can compensate for it.

On the other hand, in the fluidized catalytic cracking (FCC) process, light oil or diesel oil produced in a crude oil distillation process is contacted with a catalyst in a fluidized bed reactor to decompose it into gasoline or naphtha oil. As the demand for gasoline increases due to the increase in automobiles and the demand for naphtha increases due to the development of the petrochemical industry, the operation scale of the FCC process increases, and the FCC process is the largest among the petrochemical processes.

In the FCC process, a spherical catalyst made of zeolite Y mixed with silica-alumina is used. Since the zeolite particles are contained in the large pores of silica-alumina, the large reactants are first decomposed first at the silica-alumina acid point, then diffused into the zeolite pores and converted into branched hydrocarbons having a high octane number. Recently, to improve the thermal stability of zeolites and to reduce carbon deposits in the decomposition process, catalysts for FCC processes are made with ultra-stable zeolite Y (USY) produced by eluting aluminum partially.

However, although the catalyst has only a few seconds of contact time, its activity is severely degraded by carbon deposition, and after the first use, it is recovered by cyclone, sent to a regenerator, and then air is removed to burn the deposited carbon, and then used again. In the fluidized bed catalytic reactor, a certain amount of used catalyst is supplied while a certain amount of new catalyst is supplied. The catalytic activity is kept constant by the removal method.

The FCC process catalyst discarded after use has almost no other components other than silica and alumina, so there is no fear of pollution, and it has excellent mechanical strength, so it is usually fired in the air to remove deposited carbon, or used as a raw material for cement production, or brick production. However, although recycling is considered as another raw material for zeolite synthesis, the added value of the waste catalyst of the FCC process is very low, such as disposing it by mixing it with limestone due to its large amount and low economic efficiency.

Therefore, there is a need for research and development that can be used at a high added value by using a large amount of waste catalyst discharged from the FCC process.

U.S. Patent No. 4059675 (Registration Date: 1977.11.22) Republic of Korea Patent No. 2016-0045689 (Publication date: 2016.04.27)

The main object of the present invention is a volatile organic using a FCC catalyst waste catalyst, which can easily produce a catalyst for removing a volatile organic compound, which is superior in price competitiveness and has excellent performance and durability in a simple process compared to a conventional noble metal catalyst for removing a volatile organic compound. Disclosed is a method for preparing a composite oxide catalyst for removing a compound.

In order to achieve the above object, an embodiment of the present invention (a) FCC process waste catalyst 100 parts by weight of titanium dioxide having an anatase (anatase) crystal structure 100 parts by weight to 400 parts by weight, copper precursor 1 part by weight to 20 parts by weight, 5 to 30 parts by weight of the manganese precursor and 50 parts to 200 parts by weight of the cast dust, and adding water to form a forming clay; (b) forming the forming clay; And (c) drying and firing the molding to form a catalyst, wherein the FCC process waste catalyst is 15 wt% to 60 wt% aluminum oxide, 35 wt% to 80 wt% silicon dioxide, based on the total weight of the waste catalyst. % And nickel oxide 0.1 wt% to 20 wt%.

In a preferred embodiment of the present invention, the method for preparing the volatile organic compound composite oxide catalyst comprises: (a) prior to step (i) heat treating the FCC process waste catalyst at 300°C to 400°C; (ii) washing the heat-treated FCC process waste catalyst with air bubbles; (iii) washing the washed waste catalyst using a bubble of an acidic solution or a basic solution; (iv) washing the washed waste catalyst using bubbles of 45°C to 85°C; And (v) may be characterized in that it further comprises a pre-treatment step comprising the step of drying the washed waste catalyst.

In a preferred embodiment of the present invention, the copper precursor is at least one selected from the group consisting of copper sulfate, cuprous chloride, cupric chloride, copper nitrate, copper acetate, copper carbonate, copper cyanide and copper iodide, The manganese precursor is characterized in that it is at least one member selected from the group consisting of first manganese chloride, first manganese chloride tetrahydrate, manganese chloride, manganese tetrachloride, manganese nitrate hexahydrate, manganese nitrate tetrahydrate and manganese nitrate monohydrate. can do.

In a preferred embodiment of the present invention, the drying of step (c) may be performed at 80°C to 120°C, and firing may be performed at 400°C to 700°C for 1 hour to 10 hours.

The method of manufacturing a composite oxide catalyst for removing volatile organic compounds according to the present invention uses a waste catalyst discharged from the FCC process as a main raw material, mixes anatase-type titanium dioxide with copper and manganese in a specific mixing ratio, and binds casting dust as a casting waste dust to a binder. By producing a composite oxide catalyst for removing volatile organic compounds by using as, it has excellent price competitiveness compared to a conventional noble metal catalyst, and at the same time, it is possible to use the waste catalyst generated from the FCC process and the waste generated from the foundry as a high added value. It has the effect of easily producing a catalyst for removing volatile organic compounds having excellent performance and durability through a simple manufacturing process.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless specifically stated to the contrary.

Throughout the present specification, volatile organic compounds are liquid or gaseous organic compounds that are easily vaporized into the atmosphere due to high vapor pressure, and collectively refer to benzene, formaldehyde, toluene, xylene, ethylene, styrene, and acetaldehyde.

The present invention (a) FCC process 100 parts by weight of titanium dioxide having an anatase (anatase) crystal structure, 100 parts by weight to 400 parts by weight of copper waste catalyst, 1 part to 20 parts by weight of copper precursor, 5 to 30 parts of manganese precursor A raw material mixing step of mixing parts by weight and 50 parts by weight to 200 parts by weight of casting dust, and adding water to form a forming clay; (b) forming the forming clay; And (c) drying and firing the molding to form a catalyst, wherein the FCC process waste catalyst is 15 wt% to 60 wt% aluminum oxide, 35 wt% to 80 wt% silicon dioxide, based on the total weight of the waste catalyst. % And nickel 0.1% to 20% by weight relates to a method for producing a volatile organic compound catalyst.

More specifically, the method for producing a volatile organic compound composite oxide catalyst according to the present invention recycles the components contained in the waste catalyst discharged from the FCC process, useful for removing volatile organic compounds, and catalyzes waste dust generated during casting operations. Used as a binder and additionally mixed with a certain content to improve the efficiency of removing volatile organic compounds, it is superior in price competitiveness compared to a conventional noble metal-based catalyst, and at the same time, improves waste catalyst and casting waste dust discharged from the FCC process. It can be used as an added value, and a simple process can easily produce a composite oxide catalyst for removing volatile organic compounds with excellent performance and durability.

The FCC process waste catalyst is a waste catalyst that is discharged and discarded from the FCC process of an oil refinery, aluminum oxide 15 wt% ~ 60 wt%, silicon dioxide 35 wt% ~ 80 wt% and nickel oxide 0.1 wt% ~ 20 wt% Contains, and has a specific surface area of 5 m ² /g to 200 m ² /g, and a pore size of 100 mm ² to 180 mm ² . In addition, there are differences depending on the manufacturer, but some may include a Y-type or ZSM-5-type zeolite.

The aluminum oxide (Al ₂ O ₃ ) contained in the FCC process waste catalyst has a specific surface area of 100 m ² /g to 500 m ² /g, even at a firing temperature of 500° C., and a gamma difference between 700° C. and 800° C. ( There is an advantage of excellent thermal stability by changing from γ) to alpha (α).

In addition, nickel oxide (NiO) contained in the FCC process waste catalyst acts as an active material that acts as a major catalyst in the reaction of oxidizing volatile organic compounds by reacting with air.

On the other hand, the method of manufacturing a composite oxide catalyst for volatile removal according to the present invention may further perform a pretreatment step for removing various impurities bound to the surface of the FCC catalyst waste catalyst prior to mixing the raw materials. At this time, the pretreatment is (i) heat treatment of the waste catalyst at a temperature at which impurities such as oil components, carbon, and sulfur components can be effectively removed, preferably 300 °C to 400 °C ((i) step), and the heat treatment is performed. The waste catalyst is washed with pure water in a fine bubble (step (ii)), and then the washed waste catalyst is washed with bubbles of an acidic solution or a basic solution (step (iii)). The washed waste catalyst is washed with pure bubbles of 45°C to 85°C (step (iv)), and the washed waste catalyst is dried (step (v)).

In the step (ii), heat treated impurities deposited on the waste catalyst can be removed, and in the step (iii), alkali metals such as Na, K, alkaline earth metals such as Mg and Ca, and arsenic are reduced to reduce the catalytically active sites. Inactive substances such as heavy metals, sulfur compounds such as SO ₂ and SO ₃ can be removed. At this time, an aqueous solution of sulfuric acid may be used as the acidic solution, and ammonia water may be used as the basic solution, and the concentrations of the aqueous sulfuric acid solution and ammonia water may have a value in the range of 0.5% to 1.5%. When the concentration is less than 0.5%, the cleaning effect of the inactive material is deteriorated, and when it exceeds 1.5%, it is not preferable because active metals such as vanadium or tungsten contained in the waste catalyst can be removed together.

The waste catalyst washed with an acidic or basic solution is washed with pure water (step (iv)). The acidic or basic solution remaining in the waste catalyst and the residual inert material may be removed by the washing. At this time, the water washing can efficiently remove the remaining acidic or basic solution and residual inactive substances using hot water at 45°C to 85°C. When the temperature of the hot water is less than 45°C, the removal efficiency of the inert material is low, and when it exceeds 85°C, NH ₃ , alkali metal or alkaline earth metals that may remain in the waste catalyst react with water to generate salt. Can be.

In the above-described pretreatment step, it may be performed using microbubbles of pure water and microbubbles of an acidic or basic solution. The microbubbles can effectively remove the inert substances deposited in micropores of the waste catalyst by generating microbubbles (average diameter of 200 μm or less) in the cleaning solution by passing compressed air through a porous body having a large number of pores. .

Thereafter, in the step (v), the waste catalyst may be dried using hot air at 40°C to 90°C, and then pulverized. NH ₃ , alkali metals or alkaline earth metals that may remain in the waste catalyst may react with water to generate salt, and thus it is preferable to completely remove water on the waste catalyst through the drying process.

As described above, the pre-processed FCC process waste catalyst is mixed with titanium dioxide, a copper precursor, a manganese precursor, and a casting dust, and water is added thereto to perform a raw material mixing step of forming a forming clay (step (a)). .

The titanium dioxide may be in the form of an anatase type or a mixture of anatase and rutile, but it is preferable to use an anatase type in terms of reducing side reactions. 100 parts by weight to 400 parts by weight based on 100 parts by weight of the FCC catalyst waste catalyst, Preferably, 150 parts by weight to 350 parts by weight are mixed. If the titanium dioxide is mixed with less than 100 parts by weight based on 100 parts by weight of the FCC process waste catalyst, it is difficult to form into a desired shape when forming a catalyst, and the removal efficiency of volatile organic compounds may decrease, and it may be mixed in excess of 400 parts by weight. In the case, the efficiency of removing volatile organic compounds compared to the amount of titanium dioxide added is insignificant, and a problem of high manufacturing cost may occur.

In addition, the present invention relates to 1 part by weight to 20 parts by weight of a copper precursor, preferably 2 parts by weight to 15 parts by weight, and a manganese precursor with respect to 100 parts by weight of the FCC process waste catalyst to improve the performance of removing volatile organic compounds at low temperatures. 5 parts by weight to 30 parts by weight, preferably 10 parts by weight to 25 parts by weight are mixed. At this time, when the copper precursor and the manganese precursor are mixed with less than 1 part by weight and 5 parts by weight, respectively, with respect to 100 parts by weight of the FCC process waste catalyst, the removal of volatile organic compounds is insufficient at low temperatures, and the weight exceeds 20 parts by weight and 30 parts by weight. When mixed, a side reaction may proceed, or a specific surface area may be small, resulting in a problem that catalyst performance is deteriorated.

In this case, the copper precursor may be at least one selected from the group consisting of copper sulfate, cupric chloride, cupric chloride, copper nitrate, copper acetate, copper carbonate, copper cyanide and copper iodide, and the manganese precursor may be first chloride. It may be one or more selected from the group consisting of manganese, first manganese chloride tetrahydrate, manganese chloride, manganese tetrachloride, manganese nitrate hexahydrate, manganese nitrate tetrahydrate, and manganese nitrate monohydrate. However, the copper precursor and the manganese precursor are not limited to the materials listed above, and can be applied as long as they are soluble in water.

Foundry dust is dust collected from a foundry factory collected through a dust collector. In general, the foundry usually produces 80% by weight to 85% by weight of sand, 8% to 10% by weight of bentonite, 3.5% to 6% by weight of charcoal, and 3% to 4% by weight of water to make raw sand. Mold the raw sand and melt it in the green sand molding, cool it after melting, remove sand, and finish casting. During this process, dust is generated during cooling and sand removal, which is collected through a dust collecting hood and filtered through a filter to prevent contamination of the environment. The dust filtered by the filter mainly contains bentonite, silicon oxide, aluminum oxide, and iron oxide, and contains impurities. When collected and discarded, environmental pollution is prevented, but there is a problem in that resources are continuously wasted because they cannot be recycled as a compound. In addition, due to this, there was a problem in that industrial resources were wasted and the consumption of bentonite increased, leading to an increase in manufacturing cost.

On the other hand, in the past, in the extrusion molding of a catalyst for removing volatile organic compounds, kaolin, zeolite, clay, etc. are used as inorganic binders to increase the mechanical strength, but when these raw materials are added in large quantities, the mechanical strength is improved, but the efficiency of removing volatile organic compounds rapidly Will decrease.

Thus, in the present invention, as a binder of the catalyst, by manufacturing the catalyst using the waste dust generated in the casting process, it is possible to recycle the waste as a useful resource and improve the efficiency of removing volatile organic compounds.

Specifically, the silicon oxide and aluminum oxide contained in the casting dust have similar components to the FCC process waste catalyst, and thus have affinity with the FCC process waste catalyst, and improve catalyst durability, as well as the bentonite contained in the casting dust is water. When mixed with can form a dough having a high viscosity. As a result, it is not possible to make clay dough with the FCC process waste catalyst alone, and a viscosity that can be molded only when casting dust is added as a binder occurs. In addition, the casting dust has a high drying strength during molding and drying, and may also serve as a strengthening agent for increasing the strength of the catalyst.

The casting dust is separated from foreign substances by contact with water before being mixed with the FCC process waste catalyst. For example, dust can be produced by passing aluminum waste dust into water. As such, the casting dust from which the foreign matter has been removed can be used by drying at room temperature to 80°C.

In the method of preparing a composite oxide catalyst for removing volatile organic compounds of the present invention, the content of the mixed casting dust is 50 parts by weight to 200 parts by weight, preferably 80 to 150 parts by weight with respect to 100 parts by weight of the FCC catalyst waste catalyst. You can mix parts. If the casting dust is mixed with less than 50 parts by weight with respect to 100 parts by weight of the FCC process waste catalyst, the catalyst cannot function properly, and if it exceeds 200 parts by weight, the efficiency of removing volatile organic compounds may decrease. have.

At this time, the above-described FCC process waste catalyst, titanium dioxide, copper precursor, manganese precursor and casting dust may be further included a step of grinding the average particle diameter to 100 mesh ~ 200 mesh size to be uniformly blended before or after blending. . The grinding method may be used without limitation as long as it is a known grinding method such as a ball mill.

Thereafter, when the FCC process waste catalyst is mixed with titanium dioxide, copper precursor, manganese precursor and casting dust, a raw material mixing step is performed by adding water to form a forming clay. The water may be mixed with a raw material mixture while controlling to have suitable fluidity according to a molding method to form a forming clay, preferably 10% to 40% by weight based on the total weight of forming clay. It is not limited to this.

In addition, the raw material mixing step may further contain generally known additives added when preparing a catalyst, and these additives can be selected without difficulty by those skilled in the art to which the present invention pertains, for example, methyl Inorganic and organic binders such as cellulose, grease fibers, and clay, dispersants, plasticizers, lubricants, neutralizing agents, and the like.

The forming step according to the present invention is a step of forming a catalyst having a desired shape from the forming clay obtained in the raw material mixing step, and the shape of the catalyst according to the present invention is a particle type or monolith by extrusion molding the forming clay. monlith), or can be used in various forms such as slate, plate, pellet.

Alternatively, when the composite oxide catalyst according to the present invention is actually applied, it may be used by coating on structures such as a honeycomb, a metal plate, a metal fiber, a ceramic filter, and a metal foam.

In the molding step, the molded article molded into a predetermined shape is dried and then fired to prepare a catalyst. At this time, drying is performed at 80°C to 120°C for 10 to 24 hours, and then calcined at 400°C to 700°C for 1 to 10 hours to finally prepare a catalyst for removing volatile organic compounds.

The composite oxide catalyst prepared by the manufacturing method of the present invention has a specific surface area (BET) of 200 m ² /g to 300 m ² /g and a pore size of 100 Å to 300 Å, which is excellent in removing volatile organic compounds. Of course, it is excellent in thermal stability and chemical stability at high temperatures, and as a selective oxidation catalyst, it is possible to maintain volatile organic compound removal performance for a long time. In addition, the waste catalyst, which is a by-product of the refinery, and the casting dust, which is a by-product of the foundry, are used, which is advantageous in terms of cost used for catalyst production.

Hereinafter, the present invention will be described in more detail through examples. Since these examples are only for illustrating the present invention, it should not be construed that the scope of the present invention is limited by these examples.

< Example 1 to 7 and Comparative example 1 and 4>

The waste catalyst of the FCC process used in Examples and Comparative Examples of the present invention [SK Chemical Co., Ltd.] performed a pre-treatment step, and the main component contents of the waste catalyst subjected to the pre-treatment step are shown in Table 1 below. . On the other hand, the casting dust discharged from the foundry factory in Namdong Industrial Complex was also washed with water to remove impurities. 100 parts by weight of the waste catalyst was mixed with anatase-type titanium dioxide, cuprous chloride, manganese chloride, and the casting dust having the main components shown in Table 2 in the contents shown in Table 3 below, and their average particle size was 150 mesh. The ball mill was pulverized as much as possible, and the pulverized mixture was added to a conventional pressurized kneader (kneader) together with water and kneaded to obtain a molding clay. The obtained clay was directly extruded in the form of a monolith (150 mm × 150 mm × 150 mm, partition wall thickness: 0.7 mm, partition wall pitch 4.0 mm) by a screw type extrusion machine, dried at 110° C. for 15 hours to completely remove moisture. Next, a composite oxide catalyst was prepared by firing in an air atmosphere at a temperature of 550° C. for 3 hours.

ingredient SiO ₂ Al ₂ O ₃ V ₂ O ₅ NiO MoO ₃ Fe ₂ O ₃ Other Content (average weight %) 36.0 20.0 5.5 10.0 2.5 0.5 25.5

ingredient SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ Bentonite Other Content (average weight %) 8.0 54.0 1.20 28.0 8.80

division Waste catalyst
(Parts by weight) Titanium dioxide
(Parts by weight) Cuprous chloride
(Parts by weight) Manganese Chloride
(Parts by weight) Casting dust
(Parts by weight) Example 1 100 200 10 10 100 Example 2 100 200 10 10 180 Example 3 100 200 10 10 70 Example 4 100 120 10 10 100 Example 5 100 380 10 10 100 Example 6 100 200 1.5 10 100 Example 7 100 200 20 10 100 Comparative Example 1 100 - 10 10 100 Comparative Example 2 100 200 - 10 100 Comparative Example 3 100 200 10 - 100 Comparative Example 4 100 200 10 10 -

[ Experimental Example 1: Measurement of the mechanical strength of the catalyst]

Instron device (Instron Universal Testing Instrument Model 4201, used for strength measurement by preparing a catalyst of 25.4 mm × 25.4 mm × 25.4 mm sized tetrahedron in order to find out the mechanical strength of the composite oxide catalyst prepared in Examples and Comparative Examples) Instron) was used to measure and analyze the intensity at least 10 times per sample, and the results are shown in Table 4 below. At this time, the use A catalyst of Table 4 is a catalyst for removing volatile organic compounds of company A currently on sale.

[ Experimental Example 2: Measurement of removal efficiency of volatile organic compounds]

Toluene removal experiments were performed to measure the removal efficiency of volatile organic compounds of the composite oxide catalysts prepared in Examples and Comparative Examples. In the toluene removal experiment, the catalyst was filled in a fixed bed reactor at a normal pressure made of Inconel, and the toluene was passed through a space velocity of 100,000 h ^-1 into the reactor to determine the concentration of reactants before and after the reaction using FID-gas chromatography equipment. 150 ℃ ~ 250 ℃). Toluene conversion according to temperature was analyzed using a heating furnace for an Inconel reactor, and the results are shown in Table 4. At this time, the use A catalyst of Table 4 is a catalyst for removing volatile organic compounds of company A currently on sale.

division Mechanical strength Volatile organic compound removal rate (%) Axial strength
(kg/cm ² ) Lateral strength
(kg/cm ² ) 150 ℃ 200 ℃ 250 ℃ Example 1 41 32 78.1 96.2 98.0 Example 2 54 48 68.4 92.4 91.3 Example 3 33 12 80.1 97.0 98.6 Example 4 38 18 71.2 94.4 97.5 Example 5 43 35 70.8 93.2 94.7 Example 6 42 30 60.6 87.6 91.1 Example 7 39 30 68.5 96.5 98.8 Comparative Example 1 29 11 59.5 85.0 87.2 Comparative Example 2 39 33 61.0 81.0 84.4 Comparative Example 3 40 33 31.2 71.8 79.0 Comparative Example 4 - - - - - Commercial A catalyst 32 12 62.2 89.0 92.5

As shown in Table 4, the catalysts prepared in Examples 1 to 7 were found to have better mechanical strength and volatile organic compound efficiency than the catalysts prepared in Comparative Examples 1 to 4, and in particular, in Comparative Example 4, the extruded catalyst Was broken and mechanical strength and removal rate of volatile organic compounds could not be measured.

Accordingly, the composite oxide catalyst for removing volatile organic compounds prepared by the manufacturing method according to the present invention has superior price competitiveness compared to the catalyst for removing volatile organic compounds and can use waste catalyst discharged from the FCC process with high added value, and simple production. It was confirmed that the process can easily produce a catalyst for removing volatile organic compounds having excellent performance and durability.

As described above, although the present invention has been described by a limited embodiment, the present invention is not limited by this, and is described hereinafter and the technical idea of the present invention by a person skilled in the art to which the present invention pertains. Of course, various modifications and variations are possible within the scope of the equivalent claims.

Claims (4)

(a) 100 parts by weight of titanium dioxide having an anatase type crystal structure, 100 parts by weight to 400 parts by weight of copper precursor, 1 part to 20 parts by weight of copper precursor, 5 to 30 parts by weight of manganese precursor, and A raw material mixing step of mixing 50 parts by weight to 200 parts by weight of casting dust and adding water to form a forming clay;
(b) forming the forming clay; And
(c) drying and firing the molding to form a catalyst,
The FCC process waste catalyst is volatile organic, characterized in that it contains 15% to 60% by weight of aluminum oxide, 35% to 80% by weight of silicon dioxide, and 0.1% to 20% by weight of nickel oxide based on the total weight of the spent catalyst. Method for preparing compound composite oxide catalyst.
According to claim 1,
The method for preparing the volatile organic compound composite oxide catalyst may include (i) heat treatment of the FCC process waste catalyst at 300°C to 400°C before step (a); (ii) washing the heat-treated FCC process waste catalyst with air bubbles; (iii) washing the washed waste catalyst using a bubble of an acidic solution or a basic solution; (iv) washing the washed waste catalyst using bubbles of 45°C to 85°C; And (v) drying the washed waste catalyst, further comprising a pre-treatment step of removing the volatile organic compound.
According to claim 1,
The copper precursor is at least one selected from the group consisting of copper sulfate, cupric chloride, cupric chloride, copper nitrate, copper acetate, copper carbonate, copper cyanide and copper iodide, and the manganese precursor is first manganese chloride, chloride A complex oxide catalyst for removing volatile organic compounds, characterized in that at least one member selected from the group consisting of first manganese tetrahydrate, manganese chloride, manganese tetrachloride, manganese nitrate hexahydrate, manganese nitrate tetrahydrate and manganese nitrate monohydrate Method of manufacturing.
According to claim 1,
The drying of step (c) is performed at 80°C to 120°C, and firing is performed at 400°C to 700°C for 1 hour to 10 hours.