KR20110117765A - The fabrication of deodorized concrete included with both surface-modified carbon ash and catalyst compound for the removal of voc and formaldehyde, simultaneously - Google Patents

Abstract

The present invention relates to a method for producing environmentally friendly organic-inorganic VOC-reduced concrete that can effectively remove VOC and formaldehyde by recycling waste resource carbon ash. More specifically, carbon ash, a by-product of carbon waste generated by by-products in thermal power plants, workplaces, and domestic boilers, is used to reduce raw material consumption and to reduce the cost of waste disposal, and also to remove VOC or formaldehyde. In order to remarkably improve the deodorization efficiency of the existing interior and exterior materials of this low structure, 1) in order to increase the VOC removal performance, coating surface-modified carbon ash using organic acid and steam, and 2) formaldehyde. In order to improve the removal performance, it is a method of manufacturing eco-friendly organic-inorganic VOC-reducing concrete with the interior and exterior materials for building to effectively remove the VOC and formaldehyde by coating the catalyst component.

Description

The fabrication of deodorized concrete included with both surface-modified Carbon Ash and catalyst compound for the removal, simultaneously containing both surface-modified waste carbon ash and a catalyst component to remove volatile organic compounds and formaldehyde. of VOC and Formaldehyde, simultaneously}

As living standards have improved recently, awareness of eco-friendly living space has increased. According to the 2004 survey on the status and management of indoor air quality in multi-use facilities in Seoul, apartment houses have increased interest in indoor air pollution. 84.8% were interested in the question and about 72% were interested in the recognition of indoor air quality in multi-use facilities. In response to the increasing interest in air quality and the enactment of laws of the Ministry of Environment and related organizations, domestic and foreign companies have recently launched air quality improvement products and new house syndromes for various types of multi-use facilities.

The functional aspects of these products include far-infrared radiation, antimicrobial, humidity control, and thermal insulation. Most of these products are imported into the market by developed countries such as Japan and provided to the market, and domestic companies are also making efforts to develop the market in accordance with the awareness of improving the living environment. However, most of the foreign products imported into Korea are products related to sick house syndrome, and there is a difference in price and function in applying them to multi-use facilities. Therefore, there is a need for a functional VOC-reducing concrete that can lower cost and improve deodorization and harmful gas removal performance to remove gaseous substances among various functions, and can express antibacterial properties.

Overseas Technology

The functional VOC-reduced concrete to be developed through the present invention is a product to be applied to the improvement of indoor air quality in a multi-use facility. Currently, the market and technology for multi-use facilities at home and abroad are not clearly defined. The technical status of products with similar functions is as follows.

1) Asahi-Kasei of Japan is a manufacturer of lightweight foam concrete panels and commercializes foam type insulation called Neoma. However, detailed information about the deodorizing function is difficult to confirm. 2) Japan's Okuda Survey, a construction company, introduces a product called “eco-mity” by mixing ocher, zeolite and activated carbon to remove formaldehyde, ammonia and toluene. 3) Japan's Daikin Industries is known to sell formaldehyde adsorption decomposing ceiling materials, but the exact information about the products and technical proofs regarding decomposition have not been confirmed.

Domestic Technology

In Korea, product development is progressing with interest in humidity control and insulation panels, and functional tiles using ocher products are known to be commercialized by domestic SMEs. This product is also functional clay tile that can be applied in living room or home room, which is very expensive, so it is difficult to apply to multi-use facility. In addition, according to the Ministry of Commerce, Industry and Energy (2003) report, "Development of environmentally friendly composite insulation" has been done, but research on panels with deodorizing function for improving indoor air quality has not been conducted. Product development is not reported.

Representative domestic patent status, the number 10-0559164 "titanium dioxide photocatalyst coated metal panel and its manufacturing method", 10-2004-0011200 "functional panel using volcanic rock material and its manufacturing method", 20-0402833 "Building composite insulation panel", 20-0374078 indoor adsorption sound insulation panel ", 20-0355351," Assembly structure of ceiling panel that can clean air using chaff charcoal mat ". "Humidification building material", "preparation method and humidity control tile" of JP2001-106564, "manufacture method and raw material for manufacturing a humidification tile" of JP2004-123497, "manufacturing method of a humidification tile" of JP2004-122639. .

At present, both domestic and foreign technologies and products are focused on functional humidity control and insulation panels, such as living rooms, and are therefore vulnerable to differentiated technologies suitable for multi-use facilities. As existing products are focused on the development of products with humidity control and new house syndrome such as apartment houses, the technology of products applicable to multi-use facilities requiring gas phase substance removal is weak. Insufficient reliability of development technology. Due to the lack of systematic quality management and reliability evaluation of products, it is difficult to enter the market. Therefore, it is necessary to carry out systematic research activities through government-supported research projects and to realize commercialization early through new technology certification and reliability evaluation. It is difficult to secure differentiated technology with overseas advanced companies. Existing technological developments do not have a distinctive distinction from overseas products, and thus do not have technological and quality competitiveness of products. In addition, it is not competitive with foreign companies that dominate the market.

Autoclaved Lightweight Concrete (ALC) is a kind of lightweight concrete that reduces the consumption of natural resources by dispersing fine bubbles in the concrete using foaming agents to reduce the weight of natural resources. It is produced and sold as a form. In addition, it exhibits excellent performance in light weight, heat insulation, workability, etc. which are general advantages of light weight concrete. However, ALC is excellent in light weight, heat insulation, and workability, but has high hygroscopicity, and has disadvantages in mechanical properties such as compressive strength, tensile strength, and impact resistance. Complementing these shortcomings of mechanical properties while maintaining excellent inherent advantages of ALC, such as light weight, insulation, and workability, it is possible to manufacture excellent ALC and develop functional ALC panel that can remove deodorant and environmentally harmful substances. need.

Domestic carbon ash comes from coal-fired power plants and large boilers using heavy oil as fuel. At present, the annual output of thermal power plants is 15,000 tons (as of 2002), and only a few of them are used as desulfurization agents in the steelmaking process, and a considerable amount is treated as waste and consigned, and carbon generated from small and medium-sized boilers of private companies, etc. The ash content is about 10,000 tons, which is no different from the carbon ash of thermal power plants. Therefore, its active use is required.

So far, the recycling of carbon-ash as a way of recovering the desulfurizing agent and precious metals made, but ^{1) -5)} do not properly utilize the resource value of carbon ash. In particular, in the case of valuable metal recovery, the economical value of the recovery is not high because the content of valuable metals contained is not high.

Meanwhile, in Korean Laid-Open Patent Publication No. 10-2004-82094, a study applied to a hydraulic composition using unburned carbon, silica, and alumina contained in a large amount of carbon ash has been conducted. In addition, in Korean Patent Laid-Open Publication No. 10-2006-0104518, carbon ash is used as a composition for manufacturing lightweight foamed concrete to improve mechanical properties such as foaming performance and compressive strength of lightweight foamed concrete to solve the mechanical strength problem of lightweight foamed concrete. It was.

Therefore, by utilizing low utilization carbon ash as a circulating resource for developing various building materials, we develop new high value products that can reduce the use of natural resources and give functionality to existing building materials to control deodorization and environmentally harmful substances. It is necessary to do.

Prior Art Literature Information

[1] Ssangyong Cement: A Case of Carbon Ash Recycling, Cement Recycling of Waste.

http://www.sangyongcement.co.kr/kor/new/environment/environment03_1.htm)

[Reference 2] Korea Ceremony Industry Association: A Case of Carbon Ash Recycling, Recycling of Resources

(http://www.cement.or.kr/tech/resource.asp)

[3] Yoo, Tae-Tae and 3 others: Basic Studies on Leaching Vanadium and Nickel from Carbon Ash Incinerator J. of Korean Inst. of Resources Recycling, Vol 4, No. 3, pp. 32-39 (1995)

[4] S. Vitolo et al .: Recovery of vanadium from a previsouly burned heavy oil fly ash, Hydrometallurgy, Vol. 62, pp. 145-150 (2001)

[5] S.L. Tsai and M.S. Tsai: A study of the extraction of vanadium and nickel in oil-fired fly ash, Resources, Conservation and Recycling, Vol. 22, pp. 163-176 (1998)

The present invention uses carbon ash, which is a waste resource, as an additive for the production of ALC, which is used as an interior and exterior panel for building, to reduce the consumption of raw materials used in the existing ALC, to reduce the consumption of natural resources, and to increase VOC removal performance. In order to carry out carbon ash by surface modification treatment using organic acid and steam, and at the same time to remove aldehyde gases such as formaldehyde effectively and at the same time to improve the panel strength, a catalyst prepared by coating at least three catalysts on silica It aims to manufacture eco-friendly organic-inorganic and VOC-reduced concrete that can effectively remove VOC and formaldehyde simultaneously by supporting and firing components.

The present invention relates to a method for producing eco-friendly VOC-reduced concrete that can effectively remove VOC and formaldehyde by recycling waste ash carbon ash (Carbon Ash), and is currently produced as a by-product of thermal power plants, workplaces, and household boilers. Carbon ash, which is a waste, can reduce the consumption of raw materials in terms of waste resource recycling and reduce the cost added to waste disposal.

At the same time, the surface ash and formaldehyde removal efficiency, which is a pretreatment process to increase the VOC removal efficiency of carbon ash, can be improved to significantly improve the deodorization efficiency of existing building interior and exterior materials, which have low VOC or formaldehyde removal efficiency. The catalyst composition coating is used to provide an effective method for producing eco-friendly organic-inorganic VOC-reduced concrete with the interior and exterior materials for building to effectively remove VOC and formaldehyde at the same time.

Figure 1. Changes in Toluene Concentration in the Chamber by the Panels of Examples and Comparative Examples on Mixed Gas
Figure 2. Changes in Formaldehyde Concentration in the Chamber by Panels of Examples and Comparative Examples on Mixed Gas

In order to achieve the above technical problem, eco-friendly organic / inorganic VOC-reducing concrete manufacturing method adds 20-50% by weight of a catalyst component composed of three or more kinds of catalysts and surface-modified carbon ash to the existing ALC composition. And a manufacturing process for drying.

The main constituents are (a) 50 to 60% by weight of siliceous raw material (b) 10 to 20% by weight of Portland cement (c) 5 to 10% by weight of lime (d) 2 to 5% by weight of aluminum powder (e) surface modified 20 to 50% by weight of carbon ash. (F) Silica consists of 2 to 20% by weight of the catalyst composition consisting of three or more catalysts.

The raw materials are mixed, subjected to primary curing, and demoulding manufacturing, and through the step of secondary curing the autoclave at high temperature and high pressure to produce an eco-friendly organic-inorganic VOC-reduced concrete.

The organic / inorganic VOC-reduced concrete manufactured in the present invention is made of a slurry by mixing the main raw materials with water, and then through the autoclave steam curing at high temperature and high pressure (150 ° C., 12 bar). Tobermorite) is produced by the process of making crystals.

Tobermorite crystal is Ca (OH) ₄ as a continuous structure of SiO 4 tetrahedra to the _second layer, the Ca ^{2 +} ions or H ₂ O where a joint portion of the inter-layer silicate ion. Ca (OH) ₂ are OH ^- ions are usually charged and hexagonal highest density, enters a Ca ^{2 +} ions between the gap, OH ^- ions are in contact with surfaces in turn it is liable to cleavage weak bond. At this time, depending on the thickness of the interlayer is named tobermorite of 1.1 nm or 1.4 nm. The interlayer portion is reported to act as nano-sized micropores, which can contribute to moisture absorption and moisture absorption.

The composition of the carbon ash is about 80 to 90% of carbon and includes metals such as nickel, vanadium, copper, and chromium. Therefore, a sudden combustion reaction may occur during heat treatment, and leaching of harmful heavy metals may occur. Pre-treatment should be used.

The following confirmed the removal efficiency of toluene and formaldehyde when present simultaneously as a mixed gas according to the manufacturing method of organic-inorganic VOC-reduced concrete to be achieved in the present invention.

Hereinafter, the present invention will be described through comparison and examples of the present invention.

Comparative Example 1 4

Comparative Example 1

In Comparative Example 1, 2990 g of Sand slurry, 2040 g of Return slurry, 480 g of Lime, 1060 g of cement, and 690 g of water were first mixed and stirred for about 5 minutes, and then 4 g of aluminum powder, a blowing agent, was added and stirred for 1 minute. It was. The mixed mixture of raw materials was put in a 0.01 m ³ stainless steel mold and cured in a curing chamber at 50 ℃ for 6 hours. The cured panel was placed in an autoclave maintained at 150 ° C. and 12 bar to cure for 12 hours to prepare Comparative Example 1.

Comparative Example 2

In Comparative Example 2, 2990 g of Sand slurry, 2040 g of Return slurry, 480 g of Lime, 1060 g of cement, 1330 g of water, and 1582 g of carbon ash were first mixed and stirred for about 5 minutes, and then 4 g of aluminum powder, which is a blowing agent, was added. Stirred for 1 more minute. The mixed mixture of raw materials was put in a 0.01 m ³ stainless steel mold and cured in a curing chamber at 50 ℃ for 6 hours. The cured panel was placed in an autoclave maintained at 150 ° C. and 12 bar to cure for 12 hours to prepare Comparative Example 2.

Comparative Example 3

In Comparative Example 3, 2990 g of Sand slurry, 2040 g of Return slurry, 480 g of Lime, 1060 g of cement, 1330 g of water, and 1582 g of pretreated carbon ash were first mixed and stirred for about 5 minutes, and then aluminum powder, a foaming agent, was added to 4 g was added and stirred for a further minute. Pretreatment methods to elute harmful heavy metals from carbon ash and improve VOC removal performance are as follows. 1) A leaching solution of pH 3-4 was made using organic acids such as acetic acid, oxalic acid, palmitic acid and benzoic acid, and 2) carbon ash was dispersed and leaching was carried out for 1 hour. 3) After the leaching reaction is completed, the carbon ash is recovered from the solution, and the recovered carbon ash is recovered to neutral pH using distilled water. 4) At 80 to 100 ° C. in an autoclave supplied with superheated steam. After pressurizing for ˜ 10 hours, and dried at room temperature was used as a composition for producing VOC-reduced concrete. The mixed mixture of raw materials was put in a 0.01 m ³ stainless steel mold and cured in a curing chamber at 50 ℃ for 6 hours. The cured panel was placed in an autoclave maintained at 150 ° C. and 12 bar to cure for 12 hours to prepare Comparative Example 3.

Comparative Example 4

In Comparative Example 4, 2990 g of Sand slurry, 2040 g of Return slurry, 480 g of Lime, 1060 g of cement, 1330 g of water, and 395.5 g of catalyst component were mixed first, stirred for about 5 minutes, and then 4 g of aluminum powder, which is a blowing agent, was added. Stirred for more minutes. Catalyst composition is 80 to 90% by weight of silica (SiO ₂ ), ₃ to 6% by weight of aluminum oxide (Al ₂ O ₃ ), 1 to 3% by weight of iron oxide (Fe ₂ O ₃ ), 1 to 4% by weight of calcium oxide (CaO) The mixture of ethanol and water in 50% of the mixture at 50% by weight was uniformly mixed and stirred for at least 6 hours while incubating at 60-80 ℃. The solids were filtered using a filter and then dried at 110 ℃ in a drying oven. After drying for 5 hours, it was produced by firing at 500 to 600 ° C. for 5 hours. The mixed mixture of raw materials was put in a 0.01 m ³ stainless steel mold and cured in a curing chamber at 50 ℃ for 6 hours. The cured panel was placed in an autoclave maintained at 150 ° C. and 12 bar to cure for 12 hours to prepare Comparative Example 4.

Example 1 5

Example 1

Example 1, 2990 g of Sand slurry, 2040 g of Return slurry, 480 g of Lime, 1060 g of cement, 1330 g of water, 395.5 g (5 wt%) of pretreated carbon ash and 395.5 g (5 wt%) of catalyst component After mixing and stirring for about 5 minutes, 4 g of aluminum powder, which is a blowing agent, was added, and the mixture was further stirred for 1 minute. Pretreatment methods to elute harmful heavy metals from carbon ash and improve VOC removal performance are as follows. 1) A leaching solution of pH 3-4 was made using organic acids such as acetic acid, oxalic acid, palmitic acid and benzoic acid, and 2) carbon ash was dispersed and leaching was carried out for 1 hour. 3) After the leaching reaction is completed, the carbon ash is recovered from the solution, and the recovered carbon ash is recovered to neutral pH using distilled water. 4) At 80 to 100 ° C. in an autoclave supplied with superheated steam. After pressurizing for ˜ 10 hours, and dried at room temperature was used as a composition for producing VOC-reduced concrete. Catalyst composition is 80 to 90% by weight of silica (SiO ₂ ), ₃ to 6% by weight of aluminum oxide (Al ₂ O ₃ ), 1 to 3% by weight of iron oxide (Fe ₂ O ₃ ), 1 to 4% by weight of calcium oxide (CaO) The mixture of ethanol and water in 50% of the mixture at 50% by weight was uniformly mixed and stirred for at least 6 hours while incubating at 60-80 ℃. The solids were filtered using a filter and then dried at 110 ℃ in a drying oven. After drying for 5 hours, it was produced by firing at 500 to 600 ° C. for 5 hours. The mixed mixture of raw materials was put in a 0.01 m ³ stainless steel mold and cured in a curing chamber at 50 ℃ for 6 hours. The cured panel was placed in an autoclave maintained at 150 ° C. and 12 bar to cure for 12 hours to prepare Example 1.

Example 2

Example 2 mixes 2990 g of Sand slurry, 2040 g of Return slurry, 480 g of Lime, 1060 g of cement, 1330 g of water, 791 g (10 wt%) of pretreated carbon ash and 395.5 g (5 wt%) of catalyst component. After stirring for about 5 minutes, 4 g of aluminum powder, which is a blowing agent, was added, and the mixture was further stirred for 1 minute. Carbon ash pretreatment and catalyst compositions were carried out as in Example 1. The mixed mixture of raw materials was put in a 0.01 m ³ stainless steel mold and cured in a curing chamber at 50 ℃ for 6 hours. The cured panel was placed in an autoclave maintained at 150 ° C. and 12 bar to cure for 12 hours to prepare Example 2.

Example 3

Example 3 was prepared using 2990 g of Sand slurry, 2040 g of Return slurry, 480 g of Lime, 1060 g of cement, 1330 g of water, 1186.5 g (15 wt%) of pretreated carbon ash and 395.5 g (5 wt%) of catalyst component. After mixing and stirring for about 5 minutes, 4 g of aluminum powder, which is a blowing agent, was added, and the mixture was further stirred for 1 minute. Carbon ash pretreatment and catalyst compositions were carried out as in Example 1. The mixed mixture of raw materials was put in a 0.01 m ³ stainless steel mold and cured in a curing chamber at 50 ℃ for 6 hours. The cured panel was placed in an autoclave maintained at 150 ° C. and 12 bar to cure for 12 hours to prepare Example 3.

Example 4

Example 4 mixes 2990 g of Sand slurry, 2040 g of Return slurry, 480 g of Lime, 1060 g of cement, 1330 g of water, 791 g (10 wt%) of pretreated carbon ash and 79.1 g (1 wt%) of catalyst component. After stirring for about 5 minutes, 4 g of aluminum powder, which is a blowing agent, was added, and the mixture was further stirred for 1 minute. Carbon ash pretreatment and catalyst compositions were carried out as in Example 1. The mixed mixture of raw materials was put in a 0.01 m ³ stainless steel mold and cured in a curing chamber at 50 ℃ for 6 hours. The cured panel was placed in an autoclave maintained at 150 ° C. and 12 bar to cure for 12 hours to prepare Example 4.

Example 5

Example 5 mixes 2990 g of Sand slurry, 2040 g of Return slurry, 480 g of Lime, 1060 g of cement, 1330 g of water, 791 g of pretreated carbon ash (10 wt%) and 158.2 g (2 wt%) of catalyst component. After stirring for about 5 minutes, 4 g of aluminum powder, which is a blowing agent, was added, and the mixture was further stirred for 1 minute. Carbon ash pretreatment and catalyst compositions were carried out as in Example 1. The mixed mixture of raw materials was put in a 0.01 m ³ stainless steel mold and cured in a curing chamber at 50 ℃ for 6 hours. The cured panel was placed in an autoclave maintained at 150 ° C. and 12 bar to cure for 12 hours to prepare Example 5.

In order to determine the VOC removal performance of the prepared Comparative Examples and Examples, toluene standard gas was used, and the formaldehyde removal performance was performed using formaldehyde standard gas. Deodorization performance test was carried out as follows. The prepared panel sample was pulverized into a sample having a uniform size of 4 to 6 mesh, and then 30 g was mounted in a 30 L volume chamber made of acrylic material. Thereafter, a standard gas was injected into the chamber for a predetermined time, and a mixed gas was formed to form an initial concentration of 10 ppm of formaldehyde and 40 ppm of toluene, and then an internal fan was operated to measure the concentration of the gas according to the elapsed time. Concentration measurement was carried out using a gas chromatogram (GC) equipped with a flame ion detector tube (FID). At this time, the temperature in the chamber was 25 ℃ and relative humidity was carried out at 50 to 60%.

Figure 1 shows the toluene concentration change in the chamber by the panels of the Examples and Comparative Examples on the mixed gas.

As shown in Figure 1, Examples 1 to 5 all exhibited excellent performance of removing 95% or more of toluene. In Comparative Example, only Comparative Example 3 showed excellent performance, which shows that the carbon ash pretreated in the manufacturing process is effective in removing VOC such as toluene. However, Comparative Example 3 was found to significantly reduce the strength of the panel as shown in Table 1. The examples prepared to compensate for this have been shown to be an effective way to maintain the strength of the panel and at the same time maintain the performance of the pretreated carbon ash with excellent toluene removal efficiency.

Figure 2 shows the change in formaldehyde concentration in the chamber by the panels of the Examples and Comparative Examples on the mixed gas.

As shown in Figure 2, all of the examples showed a removal performance of 85% or more, and in particular, Examples 2 and 3 showed high removal efficiency of 93% or more. In the case of the comparative example, the removal efficiency of Examples 1 and 2 was considerably lower than 40%, and in Comparative Example 4, the catalyst component was prepared in Comparative Example 1, and the removal efficiency was 76%. Removal efficiency is rapidly increasing. This shows that the catalyst component prepared in the present invention is an effective material for removing formaldehyde. In case of Comparative Example 3, it is shown that it is effective for removing formaldehyde, but the pretreated carbon ash is effective for removing not only toluene but also aldehyde. However, as shown in Table 1, the strength of panel is considerably lowered. It can be seen that the manufacturing method in the manufactured embodiment is well applied to the technical problem to be achieved in the present invention.

Example Removal efficiency (%) burglar Comparative example Removal efficiency (%) burglar Formaldehyde Toluene [kgf / cm ^{2 ]} Formaldehyde
Hide Toluene [kgf / cm ² ] Example 1 85 97 17 Comparative Example 1 41 32 17 Example 2 93 97 17 Comparative Example 2 35 35 17 Example 3 93 97 17 Comparative Example 3 86 97 5 Example 4 87 97 17 Comparative Example 4 76 85 17 Example 5 91 97 17

Table 1 shows the removal efficiency and panel strength of each gas according to Examples and Comparative Examples in a mixed gas in which toluene and formaldehyde are present at the same time.

Comparing the case of the comparative example in the table, in the case of the comparative example 3, the pretreated carbon ash has a good removal performance of toluene and formaldehyde, which is a reference material of VOC, but has a disadvantage of lowering the strength of the panel product itself. Comparative Example 4 is produced by applying the catalyst component to Comparative Example 1 shows the characteristics of increasing formaldehyde removal efficiency and maintaining the strength of the panel.

Looking at the examples in the table, the catalyst component applied in the examples improves formaldehyde removal capacity without compromising the inherent performance of toluene removal possessed by the pretreated carbon ash while maintaining the strength of the panel containing the pretreated carbon ash. It is showing effect to let.

As mentioned above, the organic-inorganic VOC-reduced concrete prepared by simultaneously carrying the pretreated carbon ash and the catalyst component on the existing panel can effectively remove toluene, which is a VOC reference material, and formaldehyde, a representative substance of sick house syndrome. It is shown that the excellent VOC-reduced concrete, which is in good agreement with the technical task to be achieved in the present invention.

Claims (3)

ALC panel used as interior and exterior materials for construction is coated with 5 ~ 20% by weight of waste carbon ash treated to improve VOC removal performance and 1 ~ 5% by weight of catalyst component prepared to improve formaldehyde removal performance. Eco-friendly organic-inorganic VOC reducing concrete and manufacturing method. The method for preparing waste carbon ash pretreated in claim 1 is a leaching reaction step of preparing a leaching solution having a pH of 3 to 4 using organic acids such as acetic acid, oxalic acid, palmitic acid and benzoic acid, and then dispersing and stirring the carbon ash. 2) recovering carbon ash from the solution after the leaching reaction is completed, and recovering the carbon ash to neutrality using distilled water; and 3) at 80 to 100 ° C. in an autoclave supplied with superheated steam. After pressurizing for 5 to 10 hours consists of drying at room temperature. The method for preparing a catalyst composition in claim 1 is 1) 80 to 90% by weight of silica (SiO ₂ ), ₃ to 6% by weight of aluminum oxide (Al ₂ O ₃ ), 1 to 3% by weight of iron oxide (Fe ₂ O ₃ ), oxidation Uniformly mixing each 50% of ethanol and water at a ratio of 1 to 4% by weight of calcium (CaO), 2) stirring at least 60 hours at a constant temperature of 60 to 80 ℃ and using a filter The solid content is filtered and then dried in a drying oven at 110 ° C. for 12 hours, and 3) firing at 500 to 600 ° C. for 5 hours in a kiln.

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