KR101677672B1 - Production Method for Mass Manufacturing of High Purity Synthesis Zeolites using Construction Waste - Google Patents

Abstract

The present invention relates to a method for the mass production of high-purity synthetic zeolite using zeolite-type construction waste, which can be used as an agent for purifying soil and water quality using an aged clay brick discarded after construction or a clay brick discarded as a defect in a production process of the clay brick used as a construction material. The manufacturing method of the present invention does not need a CaO elution removing process essentially required for the existing manufacturing method of synthetic zeolite, and has effects in producing the same in large quantities with a high purity.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high purity synthetic zeolite,

The present invention relates to a method for mass production of high purity synthetic zeolite using construction waste, and more particularly, to a method for mass production of high purity synthetic zeolite using building waste by using clay bricks which are discarded as defective in the production process of clay bricks used as building materials or clay bricks The present invention relates to a high-purity synthetic zeolite mass production method using a zeolite-type building waste usable as a water purification agent.

Currently, clay bricks are one of the well-being building materials that have been used for a long time. Unlike cement, it has good ventilation, warmth and strength and is widely used in interior and exterior of buildings and high-grade power houses. In the case of defective products produced during production, old clay bricks broken during construction and clay bricks cut during construction, It is discarded. Especially, in the case of stock bricks loaded in clay brick factory for a long period of time after production, it is almost impossible to sell and it is loaded on the production factory. Discarded bricks are also disposed of at the level of loading / unloading at the site or at the site of construction waste.

The method of recycling these clay bricks is to recycle some of the inventories and poor bricks during the production of clay bricks. The clay brick thus produced has a remarkably poor mechanical strength and other physical properties as compared with the brick made of the new raw material, which makes it difficult to produce excellent bricks. This is because the brick components oxidized at high temperatures are put back into the bricks, which is considered to be due to the fact that they are not properly combined with the existing soil components. Therefore, some brick factories try not to use these methods largely but they are inevitably used only for some low-grade bricks because they are produced in stock and bad in the production process. Therefore, it is necessary to recycle these defects, stocks, and discarded bricks as useful resources.

Particularly, clay bricks are not waste materials, but they are artificially produced by applying high temperature in general soil (clay, loess, kaolin, etc.), so that the ingredients are very useful resources and can be recycled. Among them, silica (SiO ₂ ) and alumina (Al ₂ O ₃ ) components contained in clay bricks are useful components for producing zeolite. Zeolite is a useful resource for various industries and is applied to various fields such as synthetic detergent raw materials, animal feed additive, soil / water quality / air purification agent, algaecolorant, soil soil and fertilizer, chemical catalyst, environment-friendly brick, And the required amount is more than tens of millions of tons per year, and the application market is also increasing every year.

The zeolite produced using the discarded clay bricks can be used as a raw material for bricks. The clay bricks thus produced can be recreated with zeolite bricks, which can be used as high value bricks and building materials as functional bricks. The zeolite can be used as a soil / water quality / atmospheric cleaner, and it can be used as an adsorbent for purifying heavy metals in land, petroleum pollutants, ammonia superfamily substances, heavy metals in water, pollutants in nitrogen, It can be used for adsorbent materials for purification of wastewater for industrial use / life use / livestock including livestock manure, filter for deodorization of refrigerator, air purifier filter, industrial VOCs / sulfuric acid removal process. In addition, it can be used in various industrial fields such as chemical catalysts, fertilizers, and algae removing agents.

At present, there is no technology to synthesize zeolite in large quantities by using waste resources. Most of them are produced by using fly ash of thermal power plant, and most of them use extraction process or hydrothermal synthesis method. There are many difficulties and purity is also low purity, so application field is limited.

Korean Patent No. 10-1138854 (registered May 16, 2012) discloses synthetic zeolite synthesized from wastes containing silica and alumina. The fly ash is mixed with an alkaline substance to be fused, the water, the aluminum-containing substance and the zeolite seed are mixed, followed by aging and crystallization to produce a synthetic zeolite. However, this patent disadvantageously has a low crystallinity and low purity of zeolite having large pores such as zeolite X type and Y type, in addition to zeolite A type, since a large amount of CaO component as a crystallization inhibitor is mixed.

Korean Patent No. 10-1602926 and No. 10-1602933 (registered on Mar. 23, 2016) have proposed a method for efficiently synthesizing zeolite in large quantities by using bottom as a waste of coal mine power plant and coal-fired power plant. The zeolite was prepared by pulverizing the calcined stone and the bottom material and reducing the CaO content, which is interfered with the formation of zeolite crystals, to 1 to 3% by weight in a general synthesis reactor other than the hydrothermal synthesis reactor. This method has the advantage of being able to produce zeolite of various types (A type, X type, NaP1 type, etc.) with high crystallinity and relatively high purity (about 90%), There is a drawback in that it may lead to a rise in process time and a process cost.

However, there has been proposed a mass production method of a high-purity synthetic zeolite using a construction waste capable of reducing the process time for mass production by lowering and removing the CaO component, thereby lowering the process cost and synthesizing a high-purity zeolite in a large amount none.

Korean Patent No. 10-1138854 (2012.05.16) Korean Patent No. 10-1602926 and No. 10-1602933 (Jul.

The main object of the present invention to solve the above-mentioned problems of the related art is to provide a method for producing a fused clay brick by pulverizing a clay brick to be discarded, mixing the clay brick and the alkali material in powder form, Are mixed with water together with the aluminum-containing material and the zeolite seed, and the zeolite is produced through aging, crystallization and drying, and the process is to produce a large quantity of the fused product at a constant quality.

In addition, a high-purity (over 90%) and high-volume synthetic zeolite with high added value is produced by using recycled clay bricks with low recyclability, and SiO ₂ and Al ₂ O ₃ , Type zeolite, and which can mass-produce various types of high-purity zeolite in a batch-type reactor at atmospheric pressure as well as a hydrothermal synthesis reactor.

Also, it is an object of the present invention to provide a manufacturing method capable of improving productivity by allowing a high purity, crystallization, and mass production easiness to be achieved even when various types of zeolite are produced using clay soil bricks classified as waste building materials .

According to an aspect of the present invention, there is provided a method for mass production of high purity synthetic zeolite using waste building material, the method comprising: a first step of pulverizing a waste building material into a powder having a size of 30mesh or less using a continuous crusher;

A second step of charging pulverized pulverized construction materials of the first step into a powdery alkaline substance and a stirrer and stirring the charged mixed powder uniformly; A third step in which the mixed powder uniformly stirred through the second step is introduced into a heating tank to be heated and the molten alkali material is fused with pulverized building material pulverized by heat; A fourth step of mixing water, an aluminum source and a zeolite seed with the fusion product obtained in the third step; A fifth step of aging the mixture of the fourth step while heating at low temperature; A sixth step of crystallizing in the fifth step the temperature of the aging of the aged mixture is elevated to synthesize and grow zeolite crystals; And a seventh step of producing the zeolite synthesized in the sixth step by filtration, washing with water, and drying the zeolite, thereby producing a high-purity synthetic zeolite mass production process using the waste building material.

Further, in the present invention, the waste building material may be a clay brick.

Further, the clay brick of the present invention may include a metal oxide.

In addition, the present invention is the metal oxide may include _{SiO 2, Al 2 O 3,} CaO, K 2 O, MgO, Fe 2 O 3, and TiO _2.

Also, the metal oxide may include 50 to 70 parts by weight of SiO ₂ , 15 to 25 parts by weight of Al ₂ O ₃ , 0.1 to 2 parts by weight of CaO, 3 to 7 parts by weight of K ₂ O, 0.1 to 2 parts by weight of MgO, 2 to 10 parts by weight of Fe ₂ O ₃ , 0.5 to 2 parts by weight of TiO ₂ , and 0.1 to 10 parts by weight of other metal oxides.

In the present invention, it is preferable that the metal oxide is at least one selected from the group consisting of 64 ± 0.25 wt% of SiO ₂ , 19 ± 0.25 wt% of Al ₂ O ₃ , 1 ± 0.25 wt% of CaO, 5 ± 0.25 wt% of K ₂ O, MgO 1 ± 0.1 wt%, Fe ₂ O ₃ 7 ± 0.25 wt%, TiO ₂ 1 ± 0.25 wt%, and the wt% of the other metal oxides may correspond to the wt% sum of the metal oxides by 100 wt%.

In the third step, the alkaline substance selected from sodium hydroxide (NaOH) and sodium carbonate (Na2CO3) is selected and used, and the powdery alkaline substance selected for 100 parts by weight of the pulverized powdery clay brick pulverized product is mixed with 50 to 200 By weight, and heat-treated at 500 to 900 ° C for 0.5 to 3 hours to obtain an aggregate of clay bricks and an alkali material.

In the fourth step, 200 to 1000 parts by weight of water, 5 to 25 parts by weight of an aluminum source and 0.5 to 5 parts by weight of a zeolite seed may be mixed with 100 parts by weight of the floor material fused product produced in the third step.

Also, the aluminum source may be NaAlO ₂ .

The fifth step may be carried out at a temperature of 20 to 60 ° C. for 3 to 12 hours.

In the sixth step, crystallization may be performed for 2 to 72 hours in a batch reactor at 80 to 100 ° C and normal pressure.

The present invention has the effect of producing zeolite by using waste clay brick which is a waste building material which is low in recycling rate and is generated in construction, production process and daily life.

In addition, there is an advantage that a CaO elution removing step, which is indispensably required in a conventional method for producing synthetic zeolite by using calcined stone or Bottom ash, is not required.

In addition, the clay brick pulverized material and the alkali material are mixed and stirred at a high temperature and mixed with each other as much as possible, and then mixed with the aluminum-containing material in a crystallized state to produce various types of zeolite with high purity.

In addition, since hydrothermal reaction is not performed, it can be produced in a batch reactor under atmospheric pressure, so mass production can be achieved by a continuous process using a batch reactor, thereby reducing production costs.

In addition, since the conventional synthetic zeolite synthesis process is simply constituted, manufacturing time and cost can be reduced.

1 is a flowchart of a manufacturing process according to an embodiment of the present invention.
2 shows the results of analysis of zeolite 4A prepared according to one embodiment of the present invention.
3 is a SEM photograph (5,000 magnification) of zeolite 4A prepared according to one embodiment of the present invention.
4 shows the results of analysis of zeolite NaP1 prepared according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to the accompanying drawings. It should be understood, however, that the appended drawings illustrate only the contents and scope of technology of the present invention, and the technical scope of the present invention is not limited thereto. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea of the present invention based on these examples.

In addition, terms and words used in the present specification and claims should not be construed to be limited to ordinary or dictionary meanings, and the inventor should appropriately define the concept of the term to describe its invention in the best way. It should be construed as meaning and concept consistent with the technical idea of the present invention. Therefore, the embodiments described herein are merely the most preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention, so that there are various equivalents and modifications that can be substituted at the time of the present application It should be understood.

1 is a flowchart of a manufacturing process according to a preferred embodiment of the present invention.

The method for producing various types of high purity zeolite by using the waste clay brick according to the present invention is characterized in that the first step which is a pulverizing step, the second step which is a mixed powder stirring step, the third step which is a fusing step, A fourth step, a fifth step as an aging step, a sixth step as a crystallization step, and a seventh step as a commercialization step.

The waste building material may be a clay soil brick, a waste yellow brick, a waste clay brick, a waste kaolin brick, a waste cement brick, and a waste concrete brick.

These bricks may comprise a metal oxide, the metal oxide may include _{SiO 2, Al 2 O 3,} CaO, K 2 O, MgO, Fe 2 O 3, and TiO _2.

The metal oxide is SiO _2, 50 to 70 parts by weight, Al ₂ O ₃ 15 to 25 parts by weight, CaO 0.1 to 2 parts by weight, K ₂ O 3 to 7 parts by weight, MgO 0.1 to 2 parts by weight, Fe ₂ O ₃ 2 To 10 parts by weight of TiO _2, 0.5 to 2 parts by weight of TiO ₂ , and 0.1 to 7 parts by weight of other metal oxide.

In addition, the metal oxide is SiO _2, 35 to 45 parts by weight, Al ₂ O ₃ 5 to 15 parts by weight, CaO 0.1 to 5 parts by weight, K ₂ O 5 to 15 parts by weight, MgO 0.1 to 2 parts by weight, Fe ₂ O ₃ 23 to 33 parts by weight of TiO _2, 0.1 to 7 parts by weight of TiO _{2, and} 0.1 to 7 parts by weight of other metal oxides.

The other metal oxide may be any one or more of Na ₂ O, P ₂ O ₅ , SO ₃ , Cr ₂ O ₃ , MnO, NiO, ZnO, Rb ₂ O, SrO, Y ₂ O ₃ , ZrO ₂ , have.

The metal oxide of the present invention is composed of 64 ± 0.25 wt% of SiO2, 19 ± 0.25 wt% of Al2O3, 1 ± 0.25 wt% of CaO, 5 ± 0.25 wt% of K2O, 1 ± 0.1 wt% of MgO, 7 ± 0.25 wt% of Fe2O3, 1 ± 0.25 wt% of TiO2, and the wt% of other metal oxides may be equal to the wt% sum of the metal oxides by 100 wt%.

Also, the metal oxide of the present invention has a composition of 40 ± 0.25 wt% of SiO _2, 12 ± 0.25 wt% of Al ₂ O ₃ , 0.25 wt% of CaO, 11 ± 0.25 wt% of K ₂ O, MgO 1 ± 0.1 wt%, Fe ₂ O ₃ 28 ± 0.25 wt%, TiO ₂ 3 ± 0.25 wt%, and the wt% of other metal oxides may correspond to the wt% sum of the metal oxides by 100 wt%.

The first step is a step of crushing the clay bricks from the clay soil, and is a step of crushing the poor clay bricks generated in the construction site, the clay brick production site, and municipal wastes. In this first step, it is preferable to crush the clay bricks in the form of powder to the maximum for uniform mixing. The crushing can be performed using a continuous crusher (hammer crusher or scutter crusher) which can be continuously supplied by a conveyor belt. At this time, the degree of pulverization is reduced to 30 mesh or less, preferably 30 to 60 mesh. If the mesh size is larger than the above-mentioned mesh range, energy, processing time, and manufacturing cost for grinding can be excessively increased.

A conventional synthetic zeolite process essentially involves a step of removing the CaO component contained in the raw material component. This excess of CaO constitutes a factor that interferes with the zeolite crystals during the crystallization step of the zeolite, and also causes the disadvantage of lowering the crystallinity and purity of the zeolite. Further, in order to lower the content of CaO substantially, the content of CaO component is adjusted by stirring in hot water at a predetermined temperature in a batch water tank.

In addition, the raw material component treated through such a process is accompanied by a pressing process for removing moisture due to a required water treatment process, thereby increasing the process time and cost. Therefore, it is possible to mass-produce high purity zeolite by using waste building material without CaO elution removal process.

These technical characteristics are considered to be important in the synthetic zeolite process of waste recycling such as bottom ash, bottom ash and fly ash. Only CaO content of 20% or more is considered only, and CaO elution is improved in nodular nodularity It is a process that is absolutely required for improving the purity. Particularly, it is very important to improve crystallinity.

Because of the uniformity of the metal oxide composition of the waste brick, which is a technical feature of the present invention, the CaO content can be excluded to 1% without the elution process of CaO, thereby drastically reducing the process cost and time, thereby achieving mass production and high purity zeolite Can be synthesized. The second step is a step of mixing the clay brick pulverized material with a powdery alkali material and stirring the same.

The mixed alkali material may be selected from sodium hydroxide (NaOH) and sodium carbonate (Na ₂ CO ₃ ). An alkali substance containing a sodium component; An alkali substance including potassium and calcium or barium such as potassium hydroxide, potassium carbonate, calcium hydroxide and barium hydroxide can be selected and used.

It is also preferable that such alkali materials are pulverized to 30 to 60 mesh as in the case of the clay brick pulverized material so as to be mixed in a powder state in a powder state so that uniform mixing is possible.

As the mixing ratio, it is preferable to mix 50 to 200 parts by weight of the powdery alkali material selected with respect to 100 parts by weight of pulverized powdery clay brick pulverized product. When the alkali material is mixed in an amount of 50 parts by weight or less, the formation of an aluminate ion source and a silicate ion source is insufficient and the crystallization is low. When the alkali material is mixed in an amount of 200 parts by weight or more, It is preferable to mix them within the above range because the degree of formation enhancement is insufficient.

As a mixer used for the mixing, it is preferable to uniformly mix the mixture using a ribbon mixer. For the continuous process, a CSTR method can be applied. For example, a plurality of ribbon mixers are installed in series, So that continuous mixing can be performed. The agitation time of the mixed powder agitation step is 5 minutes to 60 minutes, preferably 10 to 20 minutes, in which the clay brick pulverized material and the alkaline material can be mixed well and uniformly.

In the fusing step of the third step, the uniformly stirred mixed powder is charged into a heating tank and heated to fuse the alkali material and the clay brick pulverized material. In the third step, the alkaline material in the mixed powder is melted and fused with the clay brick by the supplied heat. Therefore, when the alkali material and the clay brick are uniformly mixed in powder form, the molten alkali material and the clay brick are fused at a ratio of 1: 1, thereby forming a structure favorable for zeolite synthesis.

That is, by heating, SiO ₂ in the main component of the bricks of the closure site is converted into Na ₂ SiO ₃ soluble in water or NaAlSiO ₄ dissolved in an alkaline aqueous solution, and is converted into NaAlSiO ₄ , which is an aluminate ion source And a silicate ion source.

The heat treatment temperature in such a fusion process is preferably 500 to 900 DEG C and preferably 30 to 180 minutes. That is, when the temperature is lower than 500 ° C, the alkali material is not well melted and fusion with the clay brick is not well performed. When the temperature is higher than 900 ° C, the alkali material is melted excessively and aggregated with the adjacent alkali materials, It is preferable to apply heat in the inside.

In this case, when sodium hydroxide (NaOH) is used as the alkali substance, it is preferable to mix 100 to 120 parts by weight of 100 parts by weight of the clay brick pulverized product, and to effect fusion at 500 to 550 ° C in the fusion step .

When sodium carbonate (Na ₂ CO ₃ ) is used as the alkali substance, it is preferable to mix 50 to 200 parts by weight with respect to 100 parts by weight of the clay brick pulverized product, and to effect fusion at a temperature of 800 to 900 ° C in the fusion step desirable. When sodium carbonate is used and heat is applied at a temperature of 600 ° C or below to allow the fusion to be performed, 50% or more of quartz or aluminum silicate contained in the clay brick pulverized product will not participate in the crystallization to the zeolite. Therefore, it is preferable to control the heat treatment temperature according to the alkali material to be changed into an amorphous or water-soluble form which is easy to use as a zeolite raw material.

Next, the mixing step of the fourth step is performed. The fourth step is a step of mixing the flooring fusion material, the water, the aluminum source and the zeolite seed, which have been subjected to the fusion process in the previous third step.

As the mixing ratio, 200 to 1000 parts by weight of water, 5 to 25 parts by weight of an aluminum source and 0.5 to 5 parts by weight of a zeolite seed are mixed with 100 parts by weight of the clay brick fused product produced in the fusing step.

When the water is mixed in an amount of 200 parts by weight or less, the amount of the zeolite to be added is lowered. When the water is mixed in an amount of 1000 parts by weight or more, the crystallization rate is slowed, , And more preferably 400 to 500 parts by weight.

In addition, the aluminum source is added to control SiO ₂ / Al ₂ O _3, which is the composition ratio of the finally required synthetic zeolite. As the aluminum source, an aluminum-based waste coagulant (Al content: 5 to 40 wt%) is used, and NaAlO ₂ is typically used.

In addition, the zeolite seed serves to determine the shape of the finally produced synthetic zeolite. In particular, since the purity is high in the present invention, a circulation process may be further included in the process so that some of the produced zeolite can be reused as a seed.

In order to carry out the mixing process of the fourth step, a plurality of synthesis reactors for containing the respective mixtures are formed, and they are installed in series to allow the synthesis reactors to be sequentially passed through the mixer, , And each of them reacts independently, and then sequential discharge is performed.

In the fifth step, the mixture in the fourth step is aged while being heated at a low temperature of 20 to 60 캜 to be aged.

This step is a step of stirring the mixture of clay bricks and water so that they can be sufficiently melted, and it is preferable to stir the mixture for 3 to 12 hours. When the aging time is less than 3 hours, the amount of the clay brick fused is not sufficiently dissolved in water, so that the amount synthesized in the crystallization step is lowered. When the aging time exceeds 12 hours, the degree of crystallization is insufficient. .

The sixth step is a step of raising the temperature of the aged mixture to 80 to 100 캜 through the fifth step to synthesize and grow zeolite crystals.

The sixth step in which the present crystallization is carried out can be carried out in a hydrothermal reactor, but also in a general batch reactor. Therefore, it is possible to produce a zeolite crystallized in a similar manner to the continuous process by installing a plurality of batch reactors in parallel and successively performing a crystallization reaction by a time difference to perform sequential discharge.

The sixth step is performed for 2 to 72 hours to allow crystallization to proceed. Preferably, the crystallization proceeds in the reaction vessel for 3 hours or more. The duration of performing the crystallization according to the type of zeolite can be controlled within the above range have.

In the seventh step, the zeolite-type cleaning agent synthesized through crystallization in the sixth step is filtered, washed, and dried to produce a commercial product.

That is, in the zeolite-type cleaning agent crystallized in the seventh step, the mother liquor and the metal ion adhered to the cleaning agent are removed through filtration and washing with distilled water, and dehydration is performed through a continuous filter press. In addition, the wastewater generated in the dehydration process can be used in place of water to be mixed with the flooring fusing in the mixing step.

The drying is performed at a temperature in the range of 90 to 100 ° C, and continuous drying can be performed through continuous tunnel drying.

In addition, the zeolite that has been dried is commercialized in powder form.

In addition, the zeolite in the powder state forms a granule by adding moisture or a binder to the raw material in a powder product requiring granulation. Specifically, zeolite is excellent in the ability to adsorb odor in the air, but when it is used as a raw material for the powder, the gap between the particles and the particles is very small and scattered. Although zeolite can be used to remove particles and select particles larger than the appropriate size, granulation is still necessary because the powder generated in the pulverization process must be discarded.

As a technique for granulating a raw material present in a powder form, a disk type granulator or a drum type granulator may be used. In the case of a disk-type granule forming apparatus, when the particles move beyond the angle of repose by the rotation of the disk, a rolling phenomenon occurs in which the inclined bottom surface of the molding apparatus is rubbed with a taro. When a binder or moisture is further injected into the powder, And the rounded spherical granules are formed through this repetition process.

Hereinafter, the present invention will be described in more detail with reference to examples.

(Example 1)

The production of the zeolite A type of the present invention was carried out in the process of receiving and crushing the bricks of the landfill site (first step). I received clay bricks (red bricks) that were abandoned at the general construction site. The received clay bricks were pulverized to 30 mesh (about 600 μm) or less through a crusher.

Powdered clay bricks were analyzed for their composition using XRF and are shown in Table 1 below.

[Table 1]

- Mixed powder agitation process and fusion process (second process and third process)

100 g of the pulverized clay brick was pulverized and put into a mixer. 120 g of powdery sodium hydroxide was selected as an alkali substance, and 120 g of the powder was added to a mixer and stirred for 10 minutes to prepare a mixed powder.

The mixed powder of the clay brick pulverized product and sodium hydroxide was put into a heating tank and heated at 500 캜 for about 1 hour to be fused.

- mixing process, aging process and crystallization process (fourth process, fifth process and sixth process)

100 g of fused clay brick fused, 500 mL of water, and 1 g of zeolite 4A seed were added to the synthesis reaction tank.

In addition, the NaAlO ₂ is selected as it is the molar ratio of SiO ₂ / Al ₂ O ₃ of 5.8 flooring aluminum source In a further 53g was adjusted to a molar ratio of SiO ₂ / Al ₂ O ₃ to 2.0.

The mixture was aged at a low temperature of 30 캜 for 5 hours with heating, and the fused clay bricks were sufficiently dissolved in water.

The heating temperature of the aged mixture was raised to 90 캜 and stirred for 5 hours to proceed crystallization.

- Zeolite commercialization process (Seventh process)

The crystallized zeolite was filtered and washed with distilled water, dehydrated and dried at 100 ° C. in a drying oven to produce powdered zeolite 4A.

[Table 2]

The components of the produced zeolite 4A were analyzed by XRF and are shown in Table 2.

As a result, it was found that high purity zeolite can be produced with a purity of about 95% or more.

In FIG. 2, the crystallization state was confirmed by XRD analysis of the prepared zeolite 4A.

As a result, a crystal peak almost coinciding with that of commercial zeolite was observed, and crystallization was also found to be high.

FIG. 3 shows an SEM photograph of the prepared zeolite 4A, which shows a typical zeolite 4A shape of a cube.

(Example 2) Production of zeolite NaP1 type of the present invention

- Closing land brick receiving and crushing process (first process)

I received clay bricks (red bricks) that were abandoned at the general construction site. The received clay bricks were pulverized to 30 mesh (about 600 μm) or less through a crusher.

- Mixed powder agitation process and fusion process (second process and third process)

100 g of the pulverized clay brick was pulverized and put into a mixer. 120 g of powdery sodium hydroxide was selected as an alkali substance, and 120 g of the powder was added to a mixer and stirred for 10 minutes to prepare a mixed powder.

The mixed powder of the clay brick pulverized product and sodium hydroxide was put into a heating tank and heated at 500 캜 for about 1 hour to be fused.

- mixing process, aging process and crystallization process (fourth process, fifth process and sixth process)

100 g of fused clay brick fused, 500 mL of water and 1 g of zeolite NaP1 seed were added to the synthesis reaction tank.

In addition, since the molar ratio of SiO ₂ / Al ₂ O _{3 in} the bottom layer was 5.8, 10 g of NaAlO ₂ selected as an aluminum source was further added to adjust the molar ratio of SiO ₂ / Al ₂ O ₃ to 4.0.

The mixture was aged at a low temperature of 30 캜 for 5 hours with heating, and the fused clay bricks were sufficiently dissolved in water.

The heating temperature of the aged mixture was raised to 90 캜 and stirred for 20 hours to proceed crystallization.

- Zeolite commercialization process (Seventh process)

The crystallized zeolite was filtered and washed with distilled water, dehydrated and dried at 100 ° C in a drying oven to produce zeolite NaP1 in powder form.

[Table 3]

The components of the produced zeolite NaP1 were analyzed by XRF and shown in Table 3.

As a result, it was found that high purity zeolite can be produced with a purity of about 93% or more.

In FIG. 4, crystallization state was confirmed by XRD analysis of the prepared zeolite NaP1.

As a result, a crystal peak almost coinciding with that of commercial zeolite was observed, and crystallization was also found to be high.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention. I will understand.

Therefore, the scope of the present invention should not be limited to the above-described embodiments, but should be determined by equivalents to the appended claims, as well as the appended claims.

Claims (11)

A method for mass production of high purity synthetic zeolite using waste building materials,
A first step of crushing the waste building material into a powder having a size of 30mesh or less using a continuous crusher;
A second step of charging pulverized waste construction material in the first step into a powdery alkaline substance and a stirrer and uniformly stirring the charged mixed powder;
A third step in which the mixed powder uniformly stirred through the second step is introduced into a heating tank to be heated and the molten alkali material is fused with pulverized building material pulverized by heat;
A fourth step of mixing water, an aluminum source and a zeolite seed with the fusion product in the third step;
A fifth step of aging the mixture of the fourth step while heating at low temperature;
A sixth step of crystallizing the zeolite crystals so that the zeolite crystals are synthesized and grown by raising the heating temperature of the aged mixture in the fifth step;
And a seventh step of filtrating, washing and drying the zeolite synthesized in the sixth step to produce a product
The waste building material is clay brick,
Wherein the clay brick comprises a metal oxide,
The metal oxide includes _{SiO 2, Al 2 O 3,} CaO, K 2 O, MgO, Fe 2 O 3, and TiO _2,
Wherein the metal oxide is selected from the group consisting of SiO ₂ 64 ± 0.25 wt%, Al ₂ O ₃ 19 ± 0.25 wt%, CaO 1 ± 0.25 wt%, K ₂ O 5 ± 0.25 wt%, MgO 1 ± 0.1 wt% %, Fe ₂ O ₃ 7 ± 0.25 wt%, TiO ₂ 1 ± 0.25 wt%, and the wt% of the other metal oxides corresponds to the wt% sum of the metal oxides and 100 wt%
The aluminum source is NaAlO ₂ ,
Wherein the molten ratio of SiO ₂ / Al ₂ O ₃ is adjusted to 2.0 to 4.0 by the introduction of the aluminum source, and the mass production of high purity synthetic zeolite using the waste building material.
delete delete delete delete delete The method according to claim 1,
In the third step, an alkaline substance is selected from sodium hydroxide (NaOH) and sodium carbonate (Na ₂ CO ₃ )
The powdery alkali substance is mixed in an amount of 50 to 200 parts by weight with respect to 100 parts by weight of the pulverized powdery clay brick pulverized product,
Treated at 500 to 900 ° C. for 0.5 to 3 hours to fuse the clay brick and the alkali material. The method for mass production of high-purity synthetic zeolite using the waste building material according to claim 1,
The method according to claim 1,
Wherein the fourth step is performed by mixing 200 to 1000 parts by weight of water, 5 to 25 parts by weight of an aluminum source and 0.5 to 5 parts by weight of a zeolite seed with respect to 100 parts by weight of the fusion product produced in the third step. A method for mass production of high purity synthetic zeolite using.
delete The method according to claim 1,
Wherein the fifth step is carried out at a temperature of 20 to 60 ° C for 3 to 12 hours, thereby producing a high-purity synthetic zeolite.
The method according to claim 1,
Wherein the crystallization is performed for 2 to 72 hours in a batch reactor at 80 to 100 DEG C and atmospheric pressure. The method for mass production of high purity synthetic zeolite using the waste building material according to claim 1,

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