KR20120040388A - Method for preparing catalyst carrier using an extrusion-molding - Google Patents

Abstract

PURPOSE: A method for manufacturing a catalyst carrier based on extraction molding is provided to prevent the generation of high voltages by setting additives and composition ratios for the extraction molding of synthetic zeolite. CONSTITUTION: A solid mixture is prepared by mixing iron and potassium carried synthetic zeolite catalytic materials and solid raw material components. The solid raw material components include solid phased inorganic or organic binders. The average particle size of the solid raw material components is in a range between 5 and 100um. A liquid mixture is prepared by mixing liquid raw material components. The liquid raw material components include solvent, liquid phased inorganic or organic binders, and liquid additives. The solid mixture mixes with the liquid mixture to obtain a catalyst carrying composition. The catalyst carrying composition is extraction molded, dried, and thermal treated.

Description

Method for producing catalyst carrier by extrusion molding {METHOD FOR PREPARING CATALYST CARRIER USING AN EXTRUSION-MOLDING}

The present invention relates to a method for producing a catalyst carrier by extrusion molding, and more particularly, since the additive and the composition ratio are selected to be suitable for the extrusion molding of the synthetic zeolite loaded with iron (Fe) and potassium (K), the catalytic reaction By preventing the occurrence of high pressure by using, it is possible to maintain the honeycomb form and to extend the life and protection of the extruder and to produce a uniform honeycomb catalyst carrier or support, and to reduce the climate change N ₂ O and NOx at the same time It relates to a method for producing a catalyst carrier by extrusion molding that can be used as a catalyst.

As is well known, extrudates of catalyst carriers, such as zeolite honeycomb structures and the like, are typically prepared through the steps of mixing, kneading, extruding, drying and heat treating catalysts, inorganic or organic binders and other additives. It is one of the techniques to control the physical properties of the final product by improving the mixing process.

There are natural mixing methods and compulsory mixing methods as raw materials for producing an extruded article. In the former case, there is a problem of prolonged mixing time and insufficient mixing properties. Is used.

For example, Korean Patent Application Publication No. 1993-6206 discloses a method of manufacturing a ceramic molded article by supplying and mixing used materials to an extruder and then extruding through a die after degassing.

However, in this patent, when the raw materials are fed to the extruder at the same time and mixed, the unmixed raw material remains inside the molding machine and is transferred to the die, thereby inducing a flow of unsoiled raw material (raw composition). There is a drawback that is easy to cause the appearance defect of the final molding.

In addition, in the case of using the material mixing method disclosed in Korean Patent Application Publication Nos. 1995-1384 and 1995-4143, the separation phenomenon occurred due to the particle size and specific gravity difference of the raw material components, and the centrifugal force, The final physical properties are impaired by the mechanical external force applied to the mixture, such as shearing force, not only to obtain a molding of satisfactory quality, but also have a long mixing time.

Accordingly, the present inventors earnestly studied a method of improving the mixing degree of raw materials by overcoming the particle size and specific gravity difference of raw material components. In Korean Patent No. 10-0661638,

(1) Rotors having a rotational speed of 100 to 500 rpm and a solid material component having a catalyst material having an average particle size in the range of 0.1 to 10 μm and a solid inorganic or organic binder having an average particle size in the range of 10 to 100 μm. A mixture of 50 to 200 rpm for 1 to 5 minutes in a mixer in the opposite rotation to prepare a solid mixture,

(2) preparing a liquid mixture by mixing the liquid raw material components including the solvent, the liquid inorganic or organic binder and the remaining liquid additive at a speed of 30 to 150 rpm in a mixer equipped with a rotary motor and an impeller; ,

(3) 0.5 to 5 l / minute of the liquid mixture to the solid mixture, a rotor having a rotational speed of 100 to 500 rpm and a fan having a rotational speed of 50 to 200 rpm for 1 to 5 minutes in a rotating mixer After the catalyst carrier composition is mixed to obtain a catalyst carrier composition, the method for producing a catalyst carrier including extrusion molding, drying and heat treatment is disclosed, thereby improving the quality of the final product.

However, since such a conventional manufacturing method is usually formed under high pressure, it may lead to mechanical defects in the extruder and kneader and to the roughness of the honeycomb's appearance. Selection and composition costs are required.

The present invention has been devised according to the object of the present invention is to select a suitable additive for the extrusion molding of iron (Fe) and potassium (K) and to select a composition ratio to prevent the occurrence of high pressure to support a uniform honeycomb catalyst carrier Another object of the present invention is to provide a method for preparing a catalyst carrier by extrusion molding which can maintain a honeycomb form and extend the life and protection of the support and the extrusion machine.

The present invention to achieve the above object

(1) solid with inorganic or organic binder having a catalyst material of synthetic zeolite loaded with iron (Fe) and potassium (K) having an average particle diameter in the range of 0.1 to 20 µm and an average particle diameter in the range of 5 to 100 µm Raw materials are mixed for 1 to 5 minutes in a mixer in which a rotor having a rotational speed of 100 to 500 rpm and a fan having a rotational speed of 50 to 200 rpm are reversely rotated to prepare a solid mixture,

(2) preparing a liquid mixture by mixing the liquid raw material components including the solvent, the liquid inorganic or organic binder and the remaining liquid additive at a speed of 30 to 150 rpm in a mixer equipped with a rotary motor and an impeller; ,

(3) 0.5 to 5 l / minute of the liquid mixture to the solid mixture, a rotor having a rotational speed of 100 to 500 rpm and a fan having a rotational speed of 50 to 200 rpm for 1 to 5 minutes in a rotating mixer After mixing to obtain a catalyst carrier composition, it comprises extrusion molding, drying and heat treatment.

In the present invention, the solid inorganic binder may be used in an amount of 10 to 30% by weight of clay and bentonite based on 100% by weight of the catalytic material.

In addition, the solid organic binder may be used in an amount of 2 to 3% by weight based on 100% by weight of the catalyst material, a cellulose-based compound such as methylcellulose, polyvinyl alcohol, and starch.

For uniform kneading of the other components, distilled water as a solvent may be used in an amount of 10 to 25% by weight based on 100% by weight of the catalyst material.

Glycerin and ethylene glycol may be used as the plasticizer (PEG), and stearic acid, wax emulsion, or polyethylene glycol may be used as the lubricant.

N ₂ O and NO x may be simultaneously reduced at 450 ° C. by the catalyst carrier of the synthetic zeolite loaded with iron (Fe) and potassium (K) of the present invention.

According to the present invention, since the additive and the composition ratio are selected to be suitable for the extrusion molding of the synthetic zeolite carrying iron (Fe) and potassium (K) as the catalyst support, the catalyst carrier or support in the form of a uniform honeycomb to prevent high pressure generation can be maintained for longer life and protect the honeycomb form produced in the extrusion molding machine, it has the effect that can be used as a catalyst capable of reducing climate change materials of N ₂ O and NOx at the same time.

Figure 1 shows an example of the mixing process of the raw material composition in the method for producing a catalyst carrier according to the present invention,
2 shows an example of mixers used in the process of the invention,
Figure 3 shows an external photograph of the catalyst carrier prepared according to Example 1 and Comparative Example 1 of the present invention, respectively,
FIG. 4 is a graph showing the results of an active experiment which can confirm that N ₂ O and NO x are simultaneously reduced by the catalyst carrier of the present invention in which iron (Fe) and potassium (K) are supported.

Hereinafter, with reference to the accompanying drawings will be described in detail the present invention.

In the present invention, the catalyst carrier composition is usually composed of a catalyst component as a main ingredient and an inorganic binder as a sub ingredient, and an organic binder for improving binding force as another additive, a plasticizer for imparting lubricity and moldability, a lubricant, and distilled water as a solvent. And the like can be prepared.

In the present invention, in the preparation of such a catalyst carrier composition, as shown schematically in FIG. 1, raw materials are separated into solid components and liquid components, previously mixed separately, and then combined and mixed again to obtain clay, which is a raw material composition. As a solid component controlled to a powder of a predetermined size, that is, a catalyst material having an average particle diameter in the range of 0.5 to 10 μm and a solid inorganic or organic binder having an average particle diameter in the range of 10 to 100 μm, is shown in FIG. 2A. The mixture is placed in a mixer equipped with a rotor and a pan as shown. At this time, the rotation speed of the rotor is set to 100 to 500 rpm, preferably 150 to 400 rpm, and the rotation speed of the fan is set to 50 to 200 rpm, preferably 100 to 150 rpm, but the rotation direction is reversed for 1 to 5 minutes. Preferably, mixing can be carried out for 2 to 3 minutes. The reason for using the solid component controlled in such a size is to improve the formability and strength by forming a particle size distribution in the state of closest filling to increase the specific surface area.

On the other hand, liquid inorganic or organic binders, such as solvents of distilled water, plasticizers, lubricants, and any other liquid additives, which are liquid components constituting the composition, are provided with a rotary motor and an impeller as shown in FIG. The liquid mixture may be mixed by mixing for 1 to 5 minutes, preferably 2 to 3 minutes at a speed of 30 to 150 rpm, preferably 50 to 100 rpm in a mixer that transmits rotational force to induce uniform mixing.

Next, a separately prepared liquid mixture is added to a powdery solid mixture at a flow rate of 0.5 to 3 l / min to perform wet mixing to obtain a catalyst carrier composition. At this time, the rotation speed of the rotor of the mixer is 200 to 500 rpm, preferably 200 to 400 rpm, the rotation speed of the fan is set to 50 to 200 rpm, preferably 100 to 150 rpm, opposite to the rotation direction of the rotor, 1 to Mixing can be carried out for 5 minutes, preferably 3 to 5 minutes.

On the other hand, when the flow rate of the liquid mixture is less than 0.5 l / min, the mixing time is prolonged, re-separation of the components may occur, if the liquid mixture exceeds 3 l / min due to the over-injection of the liquid mixture and the solid mixture and liquid mixture Local agglomeration occurs before this mixture, which adversely affects the degree of mixing.

Subsequently, the catalyst carrier is prepared by extrusion molding, drying and heat treating the obtained carrier composition using a conventional extruder. In this case, the drying may be performed at 25 to 100 ° C. for 100 hours, and the heat treatment may be performed at 400 to 700 ° C. for 5 hours.

As such, in the case of preparing the catalyst carrier composition by separately performing the solid phase mixing and the liquid phase mixing of the raw materials, the mixing degree of the solid component and the liquid component is first increased, so that even if the respective mixtures are added later, the particle size and specific gravity difference of the components are combined. As the separation phenomenon is reduced, the composition can be prepared in a homogeneous state despite a short raw material mixing time of about 10 minutes, and when the homogeneous composition is extruded, it is realized by a mixing method using a conventional extruder. It is possible to solve the cause of the defect of the final molding caused by the unmixed raw material remaining in the extrusion machine.

In the present invention, as the catalyst material, various ceramic materials used as catalyst carriers in various fields may be used. Among them, synthetic zeolite and titanium dioxide supported with iron (Fe) and potassium (K) are suitable for the method of the present invention. Do.

As the solid inorganic binder, clay, bentonite, and the like, which are commonly used in ceramic catalyst carrier compositions, may be used in an amount of 10 to 30 wt% based on 100 wt% of the catalyst material, and as the solid organic binder, such as methyl cellulose Cellulose compounds, polyvinyl alcohol, starch and the like can be used in an amount of 2 to 3% by weight based on 100% by weight of the catalyst material.

Distilled water as a solvent is for uniform kneading of the other components, it may be used in an amount of 10 to 25% by weight based on 100% by weight of the catalyst material.

In the present invention, a plasticizer (PEG) may be glycerin, ethylene glycol, or the like, and stearic acid, wax emulsion, polyethylene glycol, etc. may be used as a lubricant, and other additives commonly added to the composition for extrusion molding may be used.

Hereinafter, the present invention will be described in more detail through embodiments of the present invention, but the present invention is not limited thereto.

Preparation of Extrusion Molding Catalyst Carrier Composition

Example 1

As shown in FIG. 2, in a mixer in which the rotor and the fan rotate in opposite directions, a synthetic zeolite loaded with iron (Fe) and potassium (K) having an average particle diameter of about 5 μm, clay having an average particle diameter of 50 μm, and an average particle diameter of about 50 Methyl cellulose was added in a weight ratio of 100: 32: 3, and then the mixer was operated for about 2 minutes by setting the rotor rotation speed to 300 rpm and the fan rotation speed to 120 rpm to obtain a solid mixture. It was.

Separately, in a mixer equipped with a rotary motor and an impeller, distilled water and glycerin were added, and a rotation speed of 70 rpm was set to operate the mixer for about 2 minutes to obtain a liquid mixture.

Then, the separately obtained liquid mixture was added to the solid mixture obtained at a flow rate of 3 l / min, and then the mixer was set at a rotational speed of 350 rpm and a fan at 120 rpm for about 4 minutes. The catalyst carrier composition was obtained by operating to perform wet mixing.

Subsequently, the obtained composition was extruded using an extruder having a single screw and a molding die having a density of 200 cells per square inch (CPSI) or less, and then subjected to a conventional drying and heat treatment process to carry out a catalyst. The carrier was prepared.

Comparative Example 1

In the mixer in which the rotor and the fan rotate in the opposite direction as shown in FIG. 2, all the components used in Example 1 are added at the same time, and then the rotation speed of the rotor of the mixer is set to 350 rpm and the rotation speed of the fan is set to 120 rpm. The mixer was operated for about 10 minutes to obtain a catalyst carrier composition, and the extrusion, drying and heat treatment processes of the obtained composition were carried out in the same manner as in Example 1 to prepare a catalyst carrier.

3A and 3B show photographs of the extruded catalyst carrier prepared from Example 1 and Comparative Example 1, respectively, from which the catalyst carrier prepared according to the first embodiment of the present invention is the catalyst of Comparative Example 1. It can be seen that it has a uniform appearance than the carrier.

In the present invention, the fan of the mixer is a centrifugal force is generated when rotating to the rotating body, when the centrifugal force is greater than the weight of the mixture, the mixture is attached to the inner wall to rotate. This is because there is a difference in specific gravity of each mixture, the higher the specific gravity, the greater the centrifugal force, which can cause a great disruption to the homogeneous mixing. In order to prevent this phenomenon, by installing a scraper inside the fan to separate the mixture attached to the inner wall has the effect of increasing the mixing degree, as can be seen from Figure 4, iron (Fe) and potassium (K) is It can be confirmed that N ₂ O and NO x were simultaneously reduced at 450 ° C. by the supported catalyst carrier of the present invention.

The difference from the existing Korean Patent Registration No. 10-0661638 is shown in the table below.

What has been described above is only one preferred embodiment of the catalyst carrier production method by extrusion molding according to the present invention, the present invention is not limited to the above-described embodiment, as claimed in the following claims Without departing from the gist of the invention, anyone of ordinary skill in the art to which the present invention will have the technical spirit of the present invention to the extent that various modifications can be made.

Claims (6)

(1) solid with inorganic or organic binder having a catalyst material of synthetic zeolite loaded with iron (Fe) and potassium (K) having an average particle diameter in the range of 0.1 to 20 µm and an average particle diameter in the range of 5 to 100 µm Mixing the raw ingredients to produce a solid mixture,
(2) preparing a liquid mixture by mixing a liquid raw material component comprising a solvent, a liquid inorganic or organic binder, and the remaining liquid additive,
(3) mixing the liquid mixture with the solid mixture to obtain a catalyst carrier composition, and then extruding, drying, and heat treating the same.
Method for producing a catalyst carrier by extrusion molding.
The method of claim 1,
The solid inorganic binder is based on 100% by weight of the catalyst material, the clay, bentonite is used in an amount of 10 to 30% by weight
Method for producing a catalyst carrier by extrusion molding.
The method of claim 1,
As the solid organic binder, a cellulose-based compound such as methyl cellulose, polyvinyl alcohol, and starch are used in an amount of 2 to 3% by weight based on 100% by weight of a catalyst material.
Method for producing a catalyst carrier by extrusion molding.
The method of claim 1,
For uniform kneading of the other components, distilled water as a solvent is used in an amount of 10 to 25% by weight based on 100% by weight of catalyst material.
Method for producing a catalyst carrier by extrusion molding.
The method of claim 1,
As the plasticizer (PEG), glycerin and ethylene glycol are used,
Stearic acid, wax emulsion and polyethylene glycol are used as lubricants.
Method for producing a catalyst carrier by extrusion molding.
The method of claim 1,
N ₂ O and NO x are simultaneously reduced at 450 ° C. by the catalyst carrier of the synthetic zeolite loaded with iron (Fe) and potassium (K).
Method for producing a catalyst carrier by extrusion molding.

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