JP2006021981A - Method for producing artificial zeolite using frp waste material and artificial zeolite produced by the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reutilize an FRP waste material by synthesizing P-type zeolite or X-type zeolite by reacting the FRP waste material as a main raw material. <P>SOLUTION: The method for producing the artificial zeolite comprises pulverizing the FRP waste material after burning organic substances contained in the FRP waste material or pulverizing the FRP waste material into particles having particle diameters of ≤200 μm without burning the organic substances, then adding a silicon source and sodium hydroxide, and reacting the resulting mixture at a prescribed temperature. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing artificial zeolite, and more particularly to a method for producing artificial zeolite using FRP waste as a raw material and an artificial zeolite produced by the method.

Recently, instead of high-purity synthetic zeolite manufactured for industrial use, considering the reuse of waste, artificial zeolite production methods using coal ash, paper sludge incineration ash, aluminum dross, etc. as raw materials Proposed. For example, a method for producing artificial zeolite using coal ash as a main raw material (for example, see Patent Document 1) and a method for producing artificial zeolite using papermaking sludge (for example, see Patent Document 2) have been proposed.
These proposals, for example, were made as a means for reusing (recycling) waste such as coal ash as simple waste, not as simple waste. It also plays a role as waste recycling.
JP-A-11-199225 JP 2002-34814 A

By the way, as in the case of the coal ash and paper sludge incineration ash described above, the post-treatment of the FRP waste material has become a problem. FRP molded products are highly durable and widely used as various products. Housing equipment such as bathroom units, system kitchens, purification layers, industrial equipment such as pipes and housings, tanks, containers, boats, ships, automobiles, vehicles Various molded products such as helmets have been developed.
However, when such FRP molded products are no longer needed, the excellent properties cannot be damaged and decomposed or rotted. FRP industry groups can recycle as a fuel for cement production. However, the actual situation is still discarded by incineration or landfill disposal.

The present invention focuses on such abandoned FRP waste material, and synthesizes A-type, P-type zeolite or X-type zeolite using this as a raw material , and provides a method for producing an artificial zeolite that can be stably and smoothly reacted. The purpose is to provide.

The present inventor paid attention to the fact that the FRP constituent component contains a large amount of an aluminum component in silica / alumina necessary for the synthesis of zeolite when processing such FRP waste material. Therefore, it was speculated that the synthesis of zeolite would be possible if a silicon source such as water glass was added.

That is, the present invention relates to the production of artificial zeolite using FRP waste material, in which FRP waste material containing an aluminum component is combusted and then pulverized, and a silicon source and sodium hydroxide or an aqueous solution thereof are added to the pulverized product and heated. A method (first invention) is provided.
In the present invention, the FRP waste material containing an aluminum component is pulverized to 200 microns or less, sodium hydroxide or an aqueous solution thereof is added to the pulverized product and heated, then a silicon source is added, and further heated. A method for producing the artificial zeolite used (second invention) is provided.
Furthermore, this invention provides the artificial zeolite manufactured by the said manufacturing method using the FRP waste material containing an aluminum component as a raw material.

  According to the present invention, the FRP waste material containing an aluminum component is burned or finely pulverized, so that the subsequent zeolite synthesis reaction performed by adding a silicon source and an aqueous sodium hydroxide solution is performed smoothly and stably. Artificial zeolite can be produced efficiently and resources can be reused.

The present invention is described in further detail below.
First, the first invention will be described.
FRP of FRP waste material containing an aluminum component used in the present invention is an abbreviation for fiber-reinforced plastics, and its constituent components are generally unsaturated polyester resins, vinyl ester resins, acrylic resins, It mainly consists of thermosetting resins such as epoxy resins and phenolic resins, and reinforcing materials that represent glass fibers.
FRP used in the present invention contains unsaturated polyester resin, vinyl ester resin, acrylic resin alone or mixture of thermosetting resin and reinforcing glass fiber, and inorganic filler, which are classified according to the molding method. Sheet molding compound (SMC) method and bulk molding compound (BMC) method can be used.

_Reference material: According to the actual state of FRP molding [Polymer Publishing Co., Ltd., issued October 30, 1984], the SMC method contains 15-50% by weight glass fiber for reinforcement, 40-50% resin, and filling The material is 45 to 0%, the BMC method is 10 to 30% by weight of glass fiber, the resin is 20 to 30%, the filler is 70 to 40%, and the content of the filler is much higher in BMC than in SMC.
According to the above-mentioned reference materials, calcium carbonate is used as a filler for general molded products, but for molded products that require high quality performance such as flame retardancy, electrical properties, and corrosion resistance, alumina is used instead of calcium carbonate. Aluminum-based fillers such as aluminum hydroxide are used.
The FRP used as the raw material of the zeolite of the present invention is preferably a BMC waste material formed as a flooring, a table, a kitchen top plate, a vanity, a bathtub and a bathtub unit as an artificial marble containing a large amount of aluminum components.

Examples of the method for burning FRP waste include a method using a gas burner, an electric furnace, a gas furnace, or the like.
By burning FRP waste material, for example, in BMC waste material, a combustion product (about 10% by weight of S _i O ₂ , about 77% by weight of Al ₂ O ₃ , about 8% by weight of CaO and about 2% by weight of ZnO ( Ash) is obtained.
Examples of the method for pulverizing the burned material include a grinding mill.
The pulverized product is a powder having an average particle size of 200 microns or less.

In the present invention, a silicon source and sodium hydroxide or an aqueous solution thereof are then added to such a pulverized product and heated.
Examples of the silicon source include sodium silicate, and filtrate after alkaline hydrothermal reaction of coal ash, gray clay, and ash diatomaceous earth. Of these, sodium silicate or an aqueous solution thereof is preferred. If the filtrate after alkaline hydrothermal reaction of waste containing a large amount of silicon is used as the silicon source, the cost is low and there is an economic advantage, and the amount of P-type zeolite is increased by increasing the amount for a while. Is synthesized stably.
Examples of the waste containing a large amount of silicon include paper sludge incineration ash, foundry waste sand, and nacre.

  Heating is preferably performed at a temperature of 40 to 150 ° C. for 0.5 to 60 hours. Examples of the heating method include steam heating, electric heater, microwave, solar heat and the like. By such heating, the aluminum in the pulverized product, the silicon source, and sodium hydroxide react with each other, and it becomes possible to produce zeolite.

Next, the second invention will be described.
As a method of pulverizing the FRP waste material containing an aluminum component into a powder of 200 microns or less, a method of pulverizing the FRP waste material stepwise is preferable. For example, a large shaped body such as a bathtub is roughly crushed to about 300 mm square or less with a cutting machine or a crusher, then crushed to a diameter of about 20 mm or less with a general crusher equipped with a sieve, and then finely pulverized with a grinding mill. There is a method of obtaining a fine powder having a diameter of 200 microns or less by a series of steps.

Sodium hydroxide or an aqueous solution thereof is added to the resulting fine powder and heated. The heating at this time is performed at a temperature of 40 to 150 ° C.
Next, a silicon source is added and further heated in the above temperature range.

  The artificial zeolite produced by the above production method using FRP waste material containing an aluminum component as a raw material has excellent adsorption ability, ion exchange ability and the like, and is useful in various industrial fields.

Example 1
First, using a gas burner, the FRP waste material of the kitchen counter containing 65% by weight of aluminum hydroxide was burned, and the contained organic substances were removed by incineration to obtain 2 sets (A, B) of 5 g of samples.
Each sample was then pulverized. Here, the particle size was 200 microns or more. However, it has been found that using 200 microns or less is excellent in later synthesis reaction.

Next, 6 g of sodium silicate as a silicon source was added to 5 g of one sample A, and 8 g of sodium silicate was added to 5 g of the other sample B. Each was added with a 2.0 mol / L sodium hydroxide aqueous solution. 40 ml was added and reacted at 100 ° C. for 3 hours.
As a result, as shown in the graphs of FIGS. 1 and 2, the peak of P-type zeolite could be confirmed in Sample A and Sample B, and P-type zeolite could be synthesized in any case.

Comparative Examples 1 and 2
Here, similarly, using the gas burner, the FRP waste material used in Example 1 was combusted, and the contained organic substances were removed by incineration to obtain 2 sets (C, D) of 5 g of samples.
Each sample was then pulverized. Here, the particle size was 200 microns or more.

Next, 2 g of sodium silicate as a silicon source was added to 5 g of one sample C (Comparative Example 1), and 4 g of sodium silicate was added to 5 g of the other sample D (Comparative Example 2). 40 ml of 0 mol / L sodium hydroxide was added and reacted at 100 ° C. for 3 hours.
As a result, as shown in the graphs of FIG. 3 (Comparative Example 1) and FIG. 4 (Comparative Example 2), generation of sodalite was confirmed in Sample C and Sample D. And it turned out that the peak of sodalite becomes high, so that the quantity of sodium silicate increases.
Example 2

Here, first, the organic matter contained in the FRP waste material used in Example 1 was pulverized and sieved to obtain 10 g of a sample of 200 microns or less.
Next, 80 ml of a 2.0 mol / L aqueous sodium hydroxide solution was added to 10 g of the sample and heated on a hot plate for 1 hour. The heating temperature was about 95 ° C.
Next, 100 mL (sample A) and 200 mL (sample B) of filtrate (Si concentration: 32 g / L) obtained by subjecting the waste clay incineration ash to alkaline hydrothermal treatment were added as a silicon source, and the mixture was further heated for 3 hours to be reacted. The heating temperature was about 95 ° C.
As a result, as shown in FIGS. 5 and 6, the peak of the original aluminum hydroxide could not be confirmed in the X-ray diffraction diagram after the conversion. The aluminum hydroxide in the sample was completely dissolved in the alkaline solution.

  As described above, it can be seen that even if the FRP waste material is not combusted, the reaction can be performed smoothly and stably with a sufficient aluminum source contained in the FRP waste material if it is pulverized to 200 microns or less. Different types of zeolite such as X-type zeolite can be synthesized.

Industrial application fields

  As an application example of the present invention, FRP waste material is generated in residential buildings, transportation equipment, leisure fields, etc., and at the same time, it can synthesize artificial zeolite with excellent ion exchange capacity etc. It can be used in various industrial fields.

Example 1 is an X-ray diffraction diagram after reaction of Sample A. FIG. FIG. 1 is an X-ray diffraction diagram after reaction of Example 1 sample B. 2 is an X-ray diffraction diagram after reaction of Comparative Example 1-Sample C. FIG. 2 is an X-ray diffraction diagram after reaction of Comparative Example 2 sample D. FIG. Example 2-X-ray diffraction diagram after reaction of sample A. FIG.

Claims (4)

  A method for producing an artificial zeolite using FRP waste material, wherein the FRP waste material containing an aluminum component is combusted and then pulverized, and a silicon source and sodium hydroxide or an aqueous solution thereof are added to the pulverized product and heated.   An FRP waste material containing an aluminum component is pulverized to 200 microns or less, sodium hydroxide or an aqueous solution thereof is added to the pulverized product and heated, then a silicon source is added, and further heated. Production method.   The method for producing artificial zeolite using the FRP waste material according to claim 1 or 2, wherein the silicon source is sodium silicate or an aqueous solution thereof.   The artificial zeolite manufactured by the manufacturing method of Claim 1 thru | or 4 using the FRP waste material containing an aluminum component as a raw material.

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