KR100392701B1 - A mesoporus zeolite honeycomb and a method for producing thereof - Google Patents

Abstract

The present invention relates to a mesoporous zeolite honeycomb structure and a method for manufacturing the same, and more particularly, to a mesoporous zeolite honeycomb structure for use in the field of adsorption or catalytic reaction of large organic molecules such as dioxins and the like and a method of manufacturing the same.

The present invention uniformly dry mixes 60 to 90% by weight of mesoporous zeolite as a raw material and 9 to 35% by weight of an inorganic binder in a solid state to form a mixture, and forms a mixture of alumina sol or silica as a liquid inorganic binder as a component in the mixture. 1 to 5% by weight of the sol, 2 to 10 parts by weight of the organic binder, 1 to 8 parts by weight of the plasticizer, 0.3 to 5 parts by weight of the lubricant, and 50 to 200 parts by weight of the distilled water, based on the total weight of the raw materials and the subsidiary materials, are uniformly added. Mesoporous zeolite honeycomb is prepared by wet kneading to prepare an initial clay, and aged the initial clay for about one day at room temperature, forming the dried clay, drying and firing at 650 to 800 ° C. for 4 to 6 hours. Provide a structure.

When the mesoporous zeolite honeycomb molded body according to the present invention is used in various industrial processes, the mesoporous zeolite honeycomb molded body can be effectively used for the adsorption, separation process and catalytic reaction of large organic molecules that could not be utilized as a conventional zeolite material.

Description

Mesoporus zeolite honeycomb structure and method for producing the same

The present invention relates to a mesoporous zeolite honeycomb structure and a method for manufacturing the same, and more particularly, to a mesoporous zeolite honeycomb structure and a method for producing the same for use in fields such as adsorption, separation and catalysis of large organic molecules such as dioxins.

Flue gases generated in industrial processes typically include large organic molecules such as particulate matter, gaseous pollutants or dioxins. However, in order to adsorb and remove giant organic molecules such as dioxins, conventional zeolites could not be directly applied as they are. This is because micropores of conventional adsorbents are so small that giant organic molecules such as dioxins can be adsorbed onto the micropores. Because it was not. In order to overcome this phenomenon, inevitably, the raw material (mesoporous zeolite) with larger micropores must be used, but in this case, the hydrothermal stability and mechanical strength of the raw material (mesoporous zeolite) itself are insufficient during the molding process. Not only the pore structure of the material is destroyed by the high heat treatment at the time of pressure or firing, but also the internal surface area is drastically reduced to lose the adsorption characteristics of the material, and there is also a problem that the metal catalyst component is released. In addition, since the specific surface area of the mesoporous zeolite material itself is very large and there is almost no caking, it was not easy to form a honeycomb structure because the moldability is poor even if the inorganic binder and the organic binder are simply added. Therefore, despite the need to develop an adsorbent using mesoporous zeolites, honeycomb molding techniques using mesoporous zeolite materials and specific applications using the same have not been published.

The present inventors earnestly analyze the above-described problems and undergo several repeated experiments, and based on mesoporous zeolite material as a basic composition, dry mixing them with a specific inorganic binder in a proportion, and then again with a specific organic additive. Liquid alumina sol and silica sol, which are inorganic binders, are added alone or in a mixed composition in a proportion with mixed water and uniformly wet mixed to prepare initial clay, and the above initial clay is aged for about one day. The present invention is made by manufacturing a honeycomb molded body by extruding aged clay, and confirming that when the molded body is dried and calcined at a high temperature, a mesoporous zeolite honeycomb structure having excellent properties such as specific surface area and strength is produced. It was completed.

Accordingly, an object of the present invention is to provide a honeycomb structure made of mesoporous zeolite which can be effectively used for adsorption removal of large organic molecules such as dioxins and the like and a manufacturing method thereof.

1 is a schematic manufacturing process diagram of mesoporous zeolite honeycomb

2 is an XRD measurement result of mesoporous zeolite powder according to each firing temperature in the firing step of the manufacturing process of the present invention.

The present invention comprises 60 to 90% by weight of mesoporous zeolite as a raw material, 9 to 35% by weight of a solid inorganic binder as a raw material, and 1 to 5% by weight of a liquid inorganic binder as a raw material so that the total weight of the raw materials and the raw materials is 100% by weight. After each weighing, first, 60 to 90% by weight of the mesoporous zeolite and 9 to 35% by weight of the inorganic binder in the solid state are uniformly dry mixed to form a mixture, and then the liquid inorganic inorganic material is added to the mixture. 1 to 5% by weight of the binder, alumina sol or silica sol, and 2 to 10 parts by weight of organic binder, 1 to 8 parts by weight of plasticizer, 0.3 to 5 parts by weight of lubricant, and 50 to 200 of distilled water, based on the total weight of the raw materials and subsidiary materials. Wet kneading by adding the parts by weight uniformly to prepare the initial clay, the initial clay was aged for about one day at room temperature, the aged clay was molded and dried, It provides a mesoporous zeolite honeycomb structure, which is completed by firing at 650 to 800 ° C. for 4 to 6 hours.

In addition, the present invention a). Mixing step of forming the initial clay by mixing the mesoporous zeolite as a raw material, an inorganic binder as a subsidiary material and an organic binder, a plasticizer, a lubricant and distilled water as an additive material; b). Aging step of aging the initial vomiting at room temperature for about one day; c). a molding step of forming the molded body by molding the aged clay in an extrusion molding machine; d). A method of manufacturing a zeolite honeycomb structure comprising a firing step of drying the molded body and baking at a high temperature, wherein the mixing step is a mesoporous zeolite as raw material such that the total weight of the raw material and the subsidiary material is 100% by weight. After weighing ˜90% by weight, 9-35% by weight of the inorganic binder in the solid state and 1-5% by weight of the inorganic binder in the submaterial, respectively, 60-90% by weight of the mesoporous zeolite and the solid state Dry mixing step of uniformly dry mixing 9 to 35% by weight of the inorganic binder to form a mixture; 1 to 5% by weight of the above-mentioned liquid inorganic binder, alumina sol or silica sol, and 2 to 10 parts by weight of organic binder, 1 to 8 parts by weight of plasticizer, and 0.3 to 5, based on the total weight of the raw materials and subsidiary materials. It is made of a wet kneading step of producing the initial clay by uniformly wet kneading by adding parts by weight, and 50 to 200 parts by weight of distilled water, respectively; The d). Firing step adopts an internal drying method that is dried from the inside of the molded body, mesoporous zeolite honeycomb characterized in that the dried molded body is fired for 4 to 6 hours in the temperature range of 650 ~ 800 ℃ It provides a method for producing a structure.

Hereinafter, the present invention will be described in more detail. 1 is a conceptual diagram schematically showing a method for manufacturing a mesoporous zeolite honeycomb structure according to the present invention.

In the present invention, the main raw material is 60 to 90% by weight of mesoporous zeolite having a pore size of about 20 to 100 mm 3 and a specific surface area of about 1000 m 2 / g or more than conventional zeolite materials. At this time, when the mesoporous zeolite is used in an amount of 60% by weight or less, the adsorption performance of macroorganic molecules is extremely low, and when the mesoporous zeolite is used in an amount of 90% by weight or more, the formability is extremely poor and the strength of the final product is not preferable. .

In the present invention, an inorganic binder in a solid state and a liquid state is used as the submaterial, and an organic binder, a plasticizer, a lubricant, and distilled water are used as the additive material, and these are divided into dry mixing and wet kneading. In the present invention, the weights of the raw materials and the subsidiary materials are respectively calculated such that the total weight of the raw materials and the subsidiary materials is 100% by weight, and each weight of the additive materials is calculated by the weight parts added based on the total weight of the raw materials and the subsidiary materials. It is. First, 60 to 90% by weight of mesoporous zeolite, 9 to 35% by weight of inorganic binder in solid state, and 1 to 5% by weight of inorganic binder in liquid phase (based on solids content) are weighed respectively. Then, 60 to 90% by weight of the mesoporous zeolite and 9 to 35% by weight of the inorganic binder are uniformly dry mixed to form a mixture. As the inorganic binder in the solid state, clay or bentonite may be used alone or in combination. At this time, when the amount of the inorganic binder in the solid state is increased, the strength after firing is increased, but the specific surface area is decreased. On the contrary, when the amount of the inorganic binder is too small, the amount of the inorganic binder in the solid state does not serve as an inorganic binder. Once dry mixing is completed, 1 to 5% by weight of the liquid inorganic binder, alumina sol or silica sol, and 2 to 10 parts by weight of organic binder and plasticizer 1 are added to the mixture based on the total weight of the raw materials and the subsidiary materials. 8 weight part, 0.3-5 weight part of lubricants, and 50-200 weight part of distilled water are added, respectively. Then, the wet kneading process is continued so that all the above components are uniformly mixed to prepare initial clay. In this case, as the organic binder, polyvinyl alcohol and carboxymethyl cellulose are preferable. If the amount is less than 2 parts by weight, the performance as a binder is weak and brittle in the molding step. If the amount is more than 10 parts by weight, the amount of volatilized in the sintering step becomes large, which is not preferable. Glycerin and ethylene glycol are used as a plasticizer, and stearic acid, a wax emulsion zone, polyethyleneglycol, etc. are used as a lubricant. If these are used less than the minimum amount, the expected performance may not be exhibited. On the other hand, if the amount is used more than the maximum amount, the shape of the molded body may be distorted in the forming step, which is not preferable. In addition, the liquid alumina sol and silica sol may be used alone or in combination. In mixed use, the two materials react in the firing step to form alumina silicate components similar to the zeolite materials in the matrix.

In the present invention, the aging step and the forming step are carried out according to a conventional procedure. Therefore, in the above aging step, the initial clay after the mixing step is left to stand at room temperature for about a day to fully mature, and the above-mentioned aging clay is kneaded two or three times in a conventional extrusion molding machine and then extruded into a predetermined shape. .

In the present invention, the molded article is sufficiently dried by adopting an internal drying method which is dried from the inside thereof. When the internal drying method is dried from the outside of the molded body, the internal stress is generated due to the difference in the drying speed between the surface and the inside, thereby causing cracks or cracks in the molded body, thereby preventing this phenomenon. In order to dry slowly from the inside of the molded body. The sufficiently dried molded product is fired for 4 to 6 hours at a temperature range of 650 to 800 ° C. If the firing temperature is not higher than 650 ° C, it is not sufficiently fired, whereas if the firing temperature is higher than 800 ° C, the strength is remarkably increased, but the crystal structure of the mesoporous zeolite material after the firing process is collapsed, which is not preferable. . In fact, after firing the molded body at a temperature range of 650 ° C. to 1050 ° C., the mesoporous zeolite powder was measured by XRD, and the result was as shown in FIG. 2. According to FIG. 2, the zeolite crystal structure was completely collapsed at the firing temperature of 950 ° C. or higher, and the firing temperature of the mesoporous zeolite molded body was set at a temperature range of 650 to 800 ° C. in the firing step.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are only presented on the basis of the most preferred embodiments so that the technical idea of the present invention can be easily carried out by those skilled in the art, the scope of the present invention is limited to the following examples It is self-evident.

<Example 1>

170 g of synthetic mesoporous zeolite powder having a specific surface area of at least 1000 m 2 / g and an average particle diameter of 1.0 m and 26 g of bentonite as an inorganic binder were weighed, and then thoroughly mixed in a high-speed kneader, followed by carboxymethyl as an organic binder. 6 g of cellulose, 4 g of glycerin as a plasticizer, 7 g of wax emulsion as a lubricant, and 120 g of distilled water, and 124 g of mixed water in which 4 g of silica sol was applied as a solid content based on silica sol as an inorganic binder were added, followed by wet kneading. Prepared. Thereafter, the initial clay was left to stand at room temperature for one day to ripen to uniformly disperse moisture and organic additives. The aged clay was put into a vacuum extrusion molding machine and kneaded two or three times. Then, a honeycomb mold having a cell size of 200 cells / in ² was attached and extruded to form a mesoporous zeolite honeycomb structure. The mesoporous zeolite honeycomb molded body was sufficiently dried through a working process, and then calcined in an electric furnace at a baking temperature of 650 ° C. 700 ° C. 750 ° C. 800 ° C. for 5 hours, respectively, to prepare a mesoporous zeolite honeycomb structure. For each honeycomb structure completed through the above process, the specific surface area and the compressive strength, which are physical properties thereof, were measured, and the measurement results are shown in Table 1 below.

<Example 2>

Except for using 160g of the synthetic mesoporous zeolite powder and 46g of the bentonite as the inorganic binder, it proceeded in the same manner as in Example 1, and the results are shown in Table 1 below.

<Example 3>

The procedure was the same as in Example 1, except that 150 g of the synthetic mesoporous zeolite powder was used and 56 g of bentonite, the inorganic binder, was used. The results were as shown in Table 1 below.

<Example 4>

The procedure was the same as in Example 1, except that 140 g of the synthetic mesoporous zeolite powder was used and 66 g of bentonite, the inorganic binder, was used. The results are shown in Table 1 below.

Water composition Specific surface area (㎡ / g) Compressive strength (kg / ㎠) 650 ℃ 700 ℃ 750 ℃ 800 ℃ 650 ℃ 700 ℃ 750 ℃ 800 ℃ Example 1 736.3 635.6 588.1 403.3 13.5 14.3 20.4 33.9 Example 2 776.2 665.7 612.3 358.0 15.2 16.1 22.5 35.7 Example 3 712.2 614.5 580.5 352.1 16.4 17.7 24.6 38.2 Example 4 534.2 427.2 349.9 302.7 19.6 19.9 29.8 45.6

Example 5

In Example 1 above, except that 120 g of distilled water was used as an inorganic binder and 2 g each of a liquid silica sol and an alumina sol were used as a solid content basis, thereby making 124 g of mixed water and kneading by adding the mixed water. It proceeded in the same manner as in Example 1. For each honeycomb structure completed through the above process, the specific surface area and the compressive strength, which are physical properties thereof, were measured, and the measurement results are shown in Table 2 below.

<Example 6>

In Example 2 described above, except that 120 g of distilled water was used as an inorganic binder and 2 g each of a liquid silica sol and an alumina sol were used as solid standards, and thus 124 g of mixed water was added and kneaded by addition of the mixed water. It proceeded in the same manner as in Example 2, the results were as shown in Table 2 below.

<Example 7>

In Example 3 above, except that 120 g of distilled water was used as an inorganic binder and 2 g each of liquid silica sol and alumina sol were used as solid content standards, thereby making 124 g of mixed water and kneading by adding the mixed water. It proceeded in the same manner as in Example 3, the results were as shown in Table 2 below.

<Example 8>

In Example 4 above, except that 120 g of distilled water was used as an inorganic binder and 2 g of silica sol and alumina sol, respectively, as a solid content standard, 124 g of mixed water was added, and the mixed water was added and kneaded. It proceeded in the same manner as in Example 4, the results were as shown in Table 2 below.

Water composition Surface Area (㎡ / g) Compressive strength (kg / ㎠) 650 ℃ 700 ℃ 750 ℃ 800 ℃ 650 ℃ 700 ℃ 750 ℃ 800 ℃ Example 5 737.9 636.9 589.2 405.8 12.7 13.9 19.6 32.8 Example 6 778.8 669.8 615.6 360.1 14.5 15.7 21.1 33.4 Example 7 715.1 615.7 582.9 354.2 15.3 16.8 23.9 37.5 Example 8 537.4 430.3 353.1 305.9 19.1 20.1 29.6 43.3

In analyzing the above examples, it can be seen that under the same firing temperature conditions, as the composition ratio of the inorganic binder gradually increases, the surface area of the honeycomb structural body, which is the final product, decreases, while its compressive strength increases. In addition, under the same ratio of raw material conditions, as the firing temperature increases, the specific surface area of the honeycomb structure decreases, whereas the compressive strength of the honeycomb structure increases significantly. On the other hand, if the addition of alumina sol and silica sol in addition to the bentonite as an inorganic binder, the specific surface area is slightly increased than when only silica sol alone is added, it can be seen that there is no significant difference in the compressive strength.

In the case of the conventional honeycomb structured manufacturing method as described above, the hydrothermal stability and mechanical stability of the mesoporous zeolite material itself is insufficient, the molded body is broken by the molding pressure during the molding process, or high heat treatment in the firing process Although the pore structure of the final product was destroyed by the present invention, the present invention simplified the manufacturing process of mesoporous zeolite honeycomb structure by directly adding the inorganic binder without colliding in the initial mixing step, and also bentonite as the inorganic binder. In addition, by adding silica sol or the like, the specific surface area of the mesoporous zeolite honeycomb structure after firing was greatly improved, and the compressive strength was also significantly improved.

In addition, the conventional zeolite molded body has a pore size of less than 10 μs, which limits the size of the reactants. Therefore, the zeolite molded body was not applicable to the adsorption or separation of large organic molecules, the reaction of the catalytic reaction, or the reaction having a large effect on the mass transfer rate. The honeycomb structure has a mesoporous zeolite material with a pore size of about 20 to 100 mm 3 and a specific surface area of about 1000 m 2 / g or more than conventional zeolite material, so that it is easy to diffuse materials, so that the adsorption, separation, and catalyst of large organic molecules are easy. In addition to the reaction, effects that can be widely used for reforming petroleum, synthesizing large organic molecules, and removing industrial gas waste are expected.

Although the present invention has been described above by way of example drawings and examples, this is only for describing the most preferred embodiments of the present invention, it is obvious that the present invention is not limited thereto. In addition, anyone of ordinary skill in the art will be able to make various modifications and imitations by the description of the present specification, but it will be apparent that this is also outside the scope of the present invention.

Claims (4)

60 to 90% by weight of mesoporous zeolite as a raw material, 9 to 35% by weight of an inorganic binder in a solid state and 1 to 5% by weight of a liquid inorganic binder as a component were weighed so that the total weight of the raw material and the component was 100% by weight. Thereafter, first, uniformly dry mix 60-90% by weight of the mesoporous zeolite and 9-35% by weight of the inorganic binder in the solid state to form a mixture, and then add the alumina as the liquid inorganic binder to the mixture. 1 to 5% by weight of sol or silica sol, 2 to 10 parts by weight of organic binder, 1 to 8 parts by weight of plasticizer, 0.3 to 5 parts by weight of lubricant, and 50 to 200 parts by weight of distilled water, based on the total weight of the raw materials and subsidiary materials. By adding and uniformly wet kneading to prepare the initial clay, the initial clay was aged at room temperature for about a day, and the above-mentioned mature clay was molded and dried, and then 650 to 800 ° C. Standing mesoporous zeolite honeycomb structure, characterized in that the finished by baking for 4 to 6 hours. The mesoporous zeolite honeycomb structure according to claim 1, wherein the mesoporous zeolite has a pore size of about 20 to 100 GPa and a specific surface area of about 1000 m 2 / g or more. a). a mixing step of forming initial clay by mixing mesoporous zeolite as a raw material, an inorganic binder as an ingredient and an organic binder, a plasticizer, a lubricant, and distilled water as an additive material; b). Aging step of aging the initial vomiting at room temperature for about one day; c). a molding step of forming the molded body by molding the aged clay in an extrusion molding machine; d). A method of manufacturing a zeolite honeycomb structure, comprising a firing step of drying the molded body and baking at a high temperature, In the mixing step a). 60 to 90% by weight of the mesoporous zeolite as the raw material, 9 to 35% by weight of the inorganic binder in the solid state, and the liquid inorganic binder as the component so that the total weight of the raw materials and the component is 100% by weight. A dry mixing step of uniformly dry mixing the mesoporous zeolite with 60 to 90 wt% of the mesoporous zeolite and 9 to 35 wt% of the inorganic binder in the solid state to form a mixture; 1 to 5% by weight of the above-mentioned liquid inorganic binder, alumina sol or silica sol, and 2 to 10 parts by weight of organic binder, 1 to 8 parts by weight of plasticizer, and 0.3 to 5, based on the total weight of the raw materials and subsidiary materials. It is made of a wet kneading step of producing the initial clay by uniformly wet kneading by adding parts by weight, and 50 to 200 parts by weight of distilled water, respectively; The d). Firing step adopts an internal drying method that is dried from the inside of the molded body, mesoporous zeolite honeycomb characterized in that the dried molded body is fired for 4 to 6 hours in the temperature range of 650 ~ 800 ℃ Method for producing a structure. 4. The method according to claim 3, wherein the mesoporous zeolite has a pore size of about 20 to 100 microns and a specific surface area of about 1000 m 2 / g or more.