KR100336449B1 - The ceramic media using pottery stone and making method thereof - Google Patents

Abstract

The present invention relates to a ceramic carrier using a pottery stone, 30-50 parts by weight of aluminum oxide (Al ₂ O ₃ ) or aluminum hydroxide, 5-10 parts by weight of bentonite (BENTONITE), 5-15 parts by weight of pottery (POTTERY STONE), It is characterized by consisting of 5-15 parts by weight of talc (TALC), 10-30 parts by weight of water and 20-35 parts by weight of the pore-forming carbon.

Description

The ceramic media using pottery stone and making method

The present invention relates to a ceramic carrier using a stone and a method for manufacturing the same, and more particularly, to a ceramic carrier using a stone for fixing the deodorization and microorganisms and a method for producing the same.

Due to the rapid development of industrialization, wastewater and air odor problems are emerging as social problems. Currently, not only in Korea but also in the world, we are devoting economic losses to preparing countermeasures to solve these problems.

At present, the most widely used method for treating general industrial wastewater, domestic sewage, and livestock wastewater is activated sludge method which is aerobic treatment and suspension method. The activated sludge method mixes the wastewater with the activated microbial group (activated sludge) and aeration in the aeration tank to make the microorganisms suspended, then precipitates and separates the activated sludge from the wastewater, and returns some of the separated activated sludge to the aeration tank for reuse. Discard the rest. However, this activated sludge method requires a slower treatment rate and a longer treatment time due to the low microbial concentration in the treatment reaction tank (aeration tank), which requires an enlargement of the treatment facility and swelling the sludge and generating a large amount of excess sludge. There is a problem that enormous costs such as secondary treatment costs are generated, there is a limit to the removal of nitrogen, phosphorus in the BOD, COD regulation.

In order to solve this problem, biofilm methods using adherent microorganisms have been developed in Western countries. This biological nutrient treatment process is used for the removal, denitrification and stabilization of carbon organic matter represented by BOD, TOC, COD. Overseas, microbiological water treatment systems have become commonplace, and in Korea, it is time to replace this method for advanced water treatment. This is due to the high concentration of nutrients such as nitrogen and phosphorus, which causes eutrophication of rivers, lakes, and coastal seas.In this system, the contact media that adhere microorganisms include plastic contact media and ciliated polymer contact media. Since the quality is poor in adhesion and does not have an ion exchange capacity of its own, environmentally friendly porous ceramic carriers have recently been developed and used.

However, carriers that have been developed up to now have a high porosity when the mechanical strength increases and conversely, when the porosity increases, the strength is weak, and the wear and erosion does not exceed the limit of the contrary characteristics.

Accordingly, an object of the present invention is to provide a ceramic carrier having a high porosity and maintaining excellent mechanical strength and a method of manufacturing the same.

The object of the present invention is aluminum oxide (Al ₂ O ₃ ) or 30-50 parts by weight of aluminum hydroxide, 5-10 parts by weight of bentonite (BENTONITE), 5-15 parts by weight of pottery (POTTERY STONE), talc (TALC) 5- 15 parts by weight, 10-30 parts by weight of water and 20-35 parts by weight of the pore-forming carbohydrate.

The object of the present invention is also characterized by including 45-60 parts by weight of talc, 40-55 parts by weight of aluminum oxide, 5-15 parts by weight of pottery stone, 20-40 parts by weight of water and 20-35 parts by weight of pore former carbon. It is also achieved by a ceramic carrier. In this case, the ceramic carrier of the present invention may further include 10-20 parts by weight of 3-5% aqueous solution of carbonylmethylcellulose (CMC), which is an organic binder, and 5-10 parts by weight of vega mol.

The method for producing a ceramic carrier of the present invention is 30-50 parts by weight of aluminum oxide (Al ₂ O ₃ ), 5-10 parts by weight of BENTONITE, 5-15 parts by weight of pottery (POTTERY STONE), talc (TALC) 5- Mixing and pulverizing a raw material consisting of 15 parts by weight, 20-30 parts by weight of water, and 20-35 parts by weight of pore former carboborn; Applying physical external force to impart plasticity to the raw material and relieve residual stress; Molding the raw material; And firing the molded body.

By the method for producing a ceramic carrier of the present invention, a porous ceramic carrier having a fine concavo-convex structure on its surface is produced. When the extrusion molding according to the molding method is a carrier for fixing the microorganisms, the carrier for deodorization is produced when molding with a roll mill rather than the extrusion process.

The characteristics of the ceramic carrier raw material are as follows.

Aluminum oxide is used by heating synthetic aluminum hydroxide or using natural alumina. Aluminum hydroxide is changed to α-Al ₂ O ₃ through heating, and the primary particle size is changed depending on the firing conditions, and changes to α-Al ₂ O ₃ at about 1000 ° C. through several phase changes. Since many phase changes occur during heating, they are not used much in ceramics because of their high reactivity, lower density than alumina, and high shrinkage during sintering. Alumina is the most widely used raw material in the ceramic field, and it is widely used throughout the industry, and its application is wide because its phase is stable and its price is lower than that of other ceramic materials. Table 1 below is a composition table of alumina and aluminum hydroxide used in the present invention and is a product produced by Korea General Chemical.

Table 1.

Classification Unit Aluminum Hydroxide Alumina

Moisture (%) 0.1 0.001

Al (OH) ₃ / Al ₂ O ₃ (%) 99.7 99.7

Na ₂ O (%) 0.2 0.3

Si (ppm) 0.01 0.02

Ti (ppm) 0.01 0.001

Fe (ppm) 0.012 0.02

Average particle size (㎛) 60 60

The inorganic natural raw material used in the present invention is bentonite belonging to the kind of clay, and the main mineral of bentonite is Montmorillonite, which is a very viscous strong material produced by decomposition of the glass component of volcanic ash. In particular, it has excellent cation exchange properties and generally contains components such as quartz, zeolite and feldspar. Table 2 below is the chemical composition of bentonite used in the present invention.

Table 2.

Raw material name Structural formula composition ratio (%)

Silicon Dioxide SiO ₂ 56.4-60

Aluminum Oxide Al ₂ O ₃ 17.0-23

Iron oxide (III) Fe ₂ O ₃ 1.0-4.3

Magnesium Oxide MgO 2.6-4.0

Calcium Oxide CaO 4.3-5.0

Potassium Oxide K ₂ O 1.0-1.5

Phosphate anhydride P ₂ O ₅ 0.05

Crystalline H2O (+) 7.0-9.0

Pottery Stone is not a mineralogy name. It is a mineral that can be molded into a simple rice. It is an ore that can make porcelain by magnetization when it is fired. The pottery deposit is generally an acidic volcanic rock or semi-central rock due to hydrothermal alteration. Part of the feldspar is denatured to the biotite and kaolin minerals, and has the property of preventing deformation of the molded body during firing and having the properties of a binder (BINDER) in the present invention. The types of pottery are roughly divided into mica, kaolin, feldspar, and feldspar. In Korea, minerals are evenly distributed throughout the country. The main chemical composition of the coating used in the present invention is shown in Table 3.

Table 3.

Raw material name Structural formula composition ratio (%)

Silicon Dioxide SiO ₂ 75.66

Aluminum Oxide Al ₂ O ₃ 18.7

Iron oxide (III) Fe ₂ O ₃ 0.04

Magnesium Oxide MgO 0.04

Calcium Oxide CaO 0.11

Potassium Oxide K ₂ O 0.11

Phosphoric Anhydride P ₂ O ₅ 0.14

Crystalline H2O (+) 6.23

The talc (TALC) used in the present invention is a trioctahedral mineral having a basic formula of Mg ₃ Si ₄ (OH) ₂ , in which a small amount of Al may be substituted for Si, and a specific gravity of about 2.7-2.83 is weak. Has strength. It is used for the purpose of MgO addition in FINE ceramics and the main chemical composition is shown in Table 4 below.

Table 4

Raw material name Structural formula composition ratio (%)

Silicon Dioxide SiO ₂ 61.7

Aluminum Oxide Al ₂ O ₃ 0.2

Iron oxide (III) Fe ₂ O ₃ 0.004

Magnesium Oxide MgO 31.8

Calcium Oxide CaO 0.48

Potassium Oxide K ₂ O 0.03

Phosphate anhydride P ₂ O ₅ 0.001

As described above, the raw materials other than the bentonite are classified as general CLAY, but are less viscous than general clay. Due to the low bond strength and not enough plasticity, the raw material mixing and firing process was very difficult, but the present invention is characterized by providing physical plasticity by applying external force.

Hereinafter, the present invention will be described in detail.

That is, in the present invention, the raw materials are dry mixed by using a vibration mill and a KO-NEADER MIXER, and a pug mill and a roll mill (ROLL) as a treatment process for imparting plasticity required for extrusion molding. -MILL) was applied.

The vibratory grinder is a ball filled in a cylindrical container. Vibration is applied and vibration is applied for 5 to 10 minutes, and raw material mixing and grinding operations are preferably performed for about 7 minutes.

In the kneader mixer, the mixed raw materials are mixed between one stirring shaft and the wall, and the mixed raw materials are continuously discharged by the spiral motion of the stirring blades.

The roll mill passes the mixed raw materials between the two rotating rolls, and the raw materials passed through are subjected to shear compressive stress, which causes plasticity of the raw materials and induces interlayer dehydration in addition to the added moisture to have a predetermined viscosity. Repeated roll milling is suitable for 2-3 times, and the high number of repeats does not improve plasticity.

The raw material passed through the roll mill can be molded by itself due to very high pressure, but there is a high possibility of causing cracks during lamination and drying. Therefore, in the present invention, through the pug mill is attached to the spiral blades of the two axes to solve the residual stress generated during the roll mill operation, while mixing the raw materials sufficiently to facilitate the extrusion.

The mixed raw materials as described above have suitable properties for the extrusion molding of the carrier for fixing the microorganism. Preferably, the raw materials are primarily mixed in the input part of the two mills, and the mixed raw materials are molded into Φ7 mm and sent to the degassing chamber. Degassing is carried out at ­3-5 Kg / ㎠ in the degassing chamber and is extruded in the shape of pipe, rod, etc. at the same time as degassing in the extrusion mold with inclination of 40-60˚.

Moreover, the shaping | molding method with respect to the support | carrier which has deodorization characteristic is as follows. The mixture discharged from the pug mill is passed between two constant grooved ROLLs to form a product having the same size and shape, and the composition and other processes of the starting raw materials are the same, and only the molding process is different.

The molded product as described above is subjected to a drying process in a drying furnace of 40-60 ℃ and thus the molded product has a high strength. Regardless of the composition ratio of the added raw materials, the firing process is maintained at a temperature of 700 ° C. at a temperature increase rate of 3-6 ° C. per minute and maintained for 60 minutes. This is a measure to ensure that the organic matter of the composition is completely burned and the resulting volume change does not affect the physical properties. That is, since the combustion of the added organic binder and the additive is almost performed, and the interlayer dehydration of the added raw material proceeds actively. The temperature is then raised to 900 ° C at the same rate, followed by a 60-minute holding time, allowing the reactions to continue to 750-900 ° C to occur smoothly. In the present invention, the maximum firing temperature is determined by the amount of Al ₂ O ₃ added, and then the furnace is cooled in a suitable firing temperature range, for example, 1300-1350 ° C. for 2-6 hours. The firing atmosphere is preferably an acidic atmosphere and requires ambient in the 450-650 ° C section upon cooling. This section is a temperature section in which the kiln refractory and products are protected from thermal shock, and the other temperature gradient section is not sensitive to the cooling rate.

The ceramic carrier according to the present invention is chemically stable and has excellent physical properties, has excellent microbial adhesion ability, has a low wear rate in the aeration tank, and biofilms are formed evenly from inside to outside to form wastewater treatment and deodorization efficiency. .

Hereinafter, the porous ceramic carrier according to the present invention and a manufacturing method thereof will be described in detail with reference to Examples, but the following Examples do not limit or limit the present invention.

Example 1

40 parts by weight of aluminum hydroxide having a particle size of 60 μm, 6 parts by weight of bentonite having a particle size distribution of 325 μm, 20 parts by weight of water (H ₂ O), 14 parts by weight of talc having a particle size of 325 μm, and a particle size distribution of 325 μm. 10 parts by weight of pottery stone and 100 parts by weight of pore former carbon of 100MESH are mixed at a speed of 30-50 RPM in a vibratory grinder and a conical mixer, and then passed through a roll mill at 20 RPM, and a pipe (PIPE) in an extruder through a pug mill. A molded article of was prepared. The produced molded product was dried at a temperature of 50 ° C for 12 hours.

The product was heated to 700 ° C. per minute in a gas or electric furnace using gas as a heat source, and heated to 700 ° C. for 1 hour. It heated up again at 900 degreeC at the same speed. Then, the temperature was raised to 1300 ° C. and maintained for 4 hours. After the power was cut off by natural cooling to finish the firing process to prepare a porous ceramic carrier.

The physical properties of the SAMPLA thus obtained are shown in Table 5 and the porosity and strength of the ceramic carrier are shown in Table 6.

Table 5.

Classification Test Result

Apparent weight (g / cc) 2.4

Specific surface area (m ² / cg) 1.7 x 10-2

PORE SIZE (h) 5-150

Compression Load (kgf) 500

Example 2

50 parts by weight of aluminum hydroxide having a particle size of 60 μm, 5 parts by weight of bentonite having a particle size distribution of 325 μm, 23 parts by weight of water (H ₂ O), 10 parts by weight of talc having a particle size of 325 μm, and a particle size distribution of 325 μm. The raw material consisting of 5 parts by weight of pottery stone and 30 parts by weight of pore former carbon of 100MESH was mixed at a speed of 30-50 RPM in a vibratory grinder and a conical mixer, and then passed through a roll mill at 20 RPM, and passed through a pug mill to a tubular molded body in an extruder. Was prepared. The produced molded product was dried at a temperature of 50 ° C for 12 hours.

The product was heated to 700 ° C. per minute in a gas or electric furnace using gas as a heat source, and heated to 700 ° C. for 1 hour. It heated up at 900 degreeC at the same speed. Then, the temperature was raised to 1330 ° C. and maintained for 4 hours. After the power was cut off by natural cooling to finish the firing process to prepare a porous ceramic carrier.

Example 3

40 parts by weight of aluminum oxide having a particle size of 60 μm, 6 parts by weight of bentonat having a particle size distribution of 325 μm, 20 parts by weight of water, 24 parts by weight of talc having a particle size of 325 μm, and 10 parts by weight of stone having a particle size distribution of 325 μm. , 100MESH of pore former carbon 30 parts by weight was mixed in a vibratory crusher and a mixer mixer at a speed of 30-50 RPM, then passed through a roll mill at 20 RPM and through a pug mill to produce a tubular shaped body in an extruder. . The produced molded product was dried at a temperature of 50 ° C for 12 hours.

The product was heated to 700 ° C. per minute in a gas or electric furnace using gas as a heat source, and heated to 700 ° C. for 1 hour. It heated up again at 900 degreeC at the same speed. Then, the temperature was raised to 1300 ° C. and maintained for 3 hours. After the power was cut off by natural cooling to finish the firing process to prepare a porous ceramic carrier. The porosity and strength of the ceramic carrier are shown in Table 6.

Example 4

50 parts by weight of aluminum oxide having a particle size of 60 μm, 5 parts by weight of bentonite having a particle size distribution of 325 μm, 23 parts by weight of water, 10 parts by weight of talc having a particle size of 325 μm, 5 parts by weight of pottery having a particle size distribution of 325 μm, A raw material consisting of 30 parts by weight of 100MESH pore-forming agent carbon was mixed at a speed of 30-50 RPM in a vibration mill and a conical mixer, and then passed through a roll mill at 20 RPM and a pug mill to prepare a tubular molded body in an extruder. The produced molded product was dried at a temperature of 50 ° C for 12 hours.

The product was heated to 700 ° C. per minute in a gas or electric furnace using gas as a heat source, and heated to 700 ° C. for 1 hour. It heated up again at the same speed up to 900 degreeC. Then, the temperature was raised to 1340 ° C. and maintained for 3 hours. After the power was cut off by natural cooling to finish the firing process to prepare a porous ceramic carrier.

Example 5

50 parts by weight of aluminum hydroxide or aluminum oxide having a particle size of 60 μm, 5 parts by weight of bentonite having a particle size distribution of 325 μm, 23 parts by weight of water, 10 parts by weight of talc with a particle size of 325 μm, and 10 By weight, a raw material consisting of 25 parts by weight of 100MESH pore-forming carbon is mixed in a vibration mill and a kneader mixer at a speed of 30-50 RPM, then passed through a roll mill at 20 RPM and then through a pug mill to form a tubular molded body in an extruder. Was prepared. The produced molded product was dried at a temperature of 50 ° C for 12 hours.

The product was heated at 700 ° C. per minute at a heating rate of 3-6 ° C. per minute in a gas furnace or an electric furnace using gas as a heat source, and then heated to 700 ° C. for 1 hour. It heated up again at the same speed up to 900 degreeC. Then, the temperature was raised to 1330 ° C. and maintained for 4 hours. After the power was cut off by natural cooling to finish the firing process to prepare a porous ceramic carrier. The porosity and strength of the ceramic carrier are shown in Table 6.

Table 6

Item Example 1 Example 2 Example 3 Example 5

Porosity (%) 57 63 58 55

Average pore diameter (㎛) 70 60 70 50

Compression Load (kgf) 500 450 450 550

Component Al ₂ O ₃ 41.1 51 41.1 50

SiO2 13.2 9.9 13.2 10

MgO 4.6 3.3 4.6 3.5

CaO 6.6 3.4 6.6 3.6

K2O 0.1 0.1 0.1 0.1

The sample was randomly collected, and there was no significant change in the physical properties of aluminum hydroxide and alumina. The relationship between the amount of the pore-forming agent added and the physical property was improved when the pore-forming agent was incorporated in small amounts, but other physical properties were good. Did. Aluminum oxide showed good characteristics in water treatment efficiency.

The microorganisms were attached to the porous ceramic carrier according to the embodiment to test the performance by treating the waste water.

The existing merger septic tank has an anaerobic reactor, aerobic reactor, flow control tank, and biofiltration tank. The ceramic carrier of the present invention is filled with 10% of anaerobic reactors and 25% of aerobic reactors, and the initial seeding is sludge of the existing septic tank. It was planted using. The combined septic tank capacity is 3 rubes, and the application of the same system to the acrylic box containing 0.1 samples (0.1 rube scale) stabilizes the microorganisms attached to the surface of the ceramic carrier from about 15 days after the ceramic carrier is injected. The result was very good. The same sample was planted under the same conditions, and the results are shown in Table 7.

TABLE 7

Classification Example 1 Example 2 Example 3 Example 5

Influent Water Treatment Water Quality Influent Water Treatment Water Quality Influent Water Treatment Water Quality Influent Water Treatment Water Quality

TCOD 140 36 140 30 140 28 140 35

SCOD 90 20 90 20 90 18 90 20

TSS 93 7.6 93 6.8 93 7.0 93 8.3

NH4 + -N 26 2.0 26 2.0 26 2.0 26 2.1

Example 6

Except for obtaining the molded body by passing through the symmetrical grooves in the grooves of 30mm width 5mm depth 5mm depth except for the extrusion process, the water content is 17 parts by weight in Examples 1, 2, 3, 4 Ceramic carriers having deodorizing characteristics were prepared in the same manner as in 2, 3, and 4.

Deodorization performance test for the deodorizing ceramic carrier according to Example 6 was carried out for a relatively high concentration of odor generated in the wastewater treatment plant concentration tank. An acrylic device with a diameter of 50 cm and a height of 1.5 m is filled with 50% of the carrier of Example 6 by using a device consisting of an odor supply device, an injection device, and a reaction device. Application test was performed and the results as shown in Table 8 below were obtained.

Table 8

Classification Inflow Concentration (ppmv) Emission Concentration (ppmv) Removal Rate (%)

H ₂ S 30 0.11 97

CH ₃ SH 2.3 0.6 87

(CH ₃ ) ₂ S ₂ 0.4 12 80

Example 7

Carbonylmethylcellulose as an organic binder in a ceramic carrier composition comprising 45-60 parts by weight of talc, 40-55 parts by weight of aluminum oxide, 5-15 parts by weight of Pottery Stone and 20-35 parts by weight of pore forming agent carbon. (CMC) 10-20 parts by weight of 3-5% aqueous solution, 5-10 parts by weight of Vegamol and 10 parts by weight of water were added, mixed at a speed of 30-50 RPM in a vibration mill and a kneader mixer, and then passed through 20 RPM in a roll mill. Tubular shaped bodies were produced in an extruder via a pug mill. The produced molded product was dried at a temperature of 50 ° C for 12 hours.

The product was heated to 700 ° C. per minute in a gas or electric furnace using gas as a heat source, and heated to 700 ° C. for 1 hour. The temperature is raised to the same speed again to 900 ℃. Then, the temperature was raised to 1335 ° C. and maintained for 4 hours. After the power was cut off by natural cooling to finish the firing process to prepare a porous ceramic carrier.

In the present invention, the carrier was prepared using the conventional wet mixing method used in the manufacturing process of the ceramic carrier, keeping the characteristics of the initial raw material as it is, and a carrier having excellent physical properties and good chemical resistance was prepared.

Excellent physicochemical properties ensure excellent durability even in wastewater containing various chemical properties to form microbial membranes as well as being porous, allowing evenly distributed microorganisms to maintain good and stable effluent quality, especially deodorization When used for the purpose of showing excellent properties.

Claims (6)

30-50 parts by weight of aluminum oxide (Al ₂ O ₃ ) or aluminum hydroxide, 5-10 parts by weight of bentonite, 5-15 parts by weight of pottery stone, 5-15 parts by weight of talc (TALC), water 10 Ceramic carrier, characterized in that consisting of -40 parts by weight and 20-35 parts by weight of pore-forming agent carbon. A ceramic carrier comprising 45-60 parts by weight of talc, 40-55 parts by weight of aluminum oxide, 5-15 parts by weight of pottery stone, 20-40 parts by weight of water, and 20-35 parts by weight of pore-forming carbohydrate. The ceramic carrier according to claim 1, further comprising 10-20 parts by weight of 3-5% aqueous carbonylmethylcellulose (CMC) solution and 5-10 parts by weight of VEGAmol. 30-50 parts by weight of aluminum oxide (Al ₂ O ₃ ), 5-10 parts by weight of bentonite, 5-15 parts by weight of pottery stone, 5-15 parts by weight of talc, 20-30 parts by weight of water Mixing and pulverizing a raw material consisting of 20 to 35 parts by weight of parts and pore-forming carbohydrates; Applying physical external force to impart plasticity to the raw material and relieve residual stress; Molding the raw material; And firing the molded body. 5. The method of claim 4, wherein said mixing and pulverizing is performed by using a vibratory grinder and a conical mixer; The provision of plasticity is carried out using a roll mill, and the release of residual stress is carried out using a pug mill; The molding is a method for producing a ceramic carrier, characterized in that the extrusion molding using an extruder or compression molding between the grooved roll symmetrically on both sides. The method of claim 4, wherein the firing is carried out at 1300-1350 ℃.