JP2002068731A - Method for manufacturing synthetic zeolite and manufacturing apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a synthetic zeolite, which can supply an inexpensive synthetic zeolite by improving its manufacturing efficiency. SOLUTION: The continuous production method/apparatus 1 for synthetic zeolite have at least synthetic zeolite generating process/device 3 in which a slurry containing a synthetic zeolite raw material whose silicon-aluminum ratio is already adjusted and an alkaline aqueous solution, is continuously passed through a heated reaction tube 16 which is set in a prescribed condition and is heated. Further, the method/apparatus have the synthetic zeolite separation process/device 4, the zeolite type conversion process/device 6 and the zeolite dehydration process/device 8. Since the respective process/device have the pressure difference from each other, the slurry or the zeolite can be transferred forcibly.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an artificial zeolite and an apparatus for producing the same, and more particularly, to promote an artificial zeolite synthesis reaction from a slurry by a stirring action in a reaction tube and heat the slurry. TECHNICAL FIELD The present invention relates to a method for producing an artificial zeolite in which the production efficiency is improved by continuously passing the zeolite through a reaction tube, and an apparatus for producing the same.

[0002]

2. Description of the Related Art Artificial zeolites are crystals formed from coal ash, aluminosilicate, or the like, and are zeolites artificially formed by heat treatment under alkaline conditions.
This artificial zeolite has a cation exchange function, adsorption function,
It has various promising properties such as catalytic function. In addition, it is attracting attention in various fields as a substance with further potential, such as the development of new functionality and the expansion of applications.

As an apparatus for producing such an artificial zeolite, Japanese Patent Application Laid-Open Nos. Hei 6-321525 and Hei 6-321
There is known a batch type or semi-batch type so-called batch type reactor as disclosed in JP-A-526. Also,
As a continuous production method, Japanese Patent Application Laid-Open No. 10-3245
There is known a continuous production apparatus employing a circulating fluidized reaction tank as disclosed in JP-A-18.

[0004]

The artificial zeolite is a substance having extremely excellent properties such as a cation exchange function, an adsorption function, and a catalyst function and a further possibility. It is essential that they be produced at a price appropriate for their use.

However, the conventional production apparatus described above requires a long time to produce an artificial zeolite, and it is still insufficient for producing an artificial zeolite having excellent quality at low cost. That is, artificial zeolite can be produced by stirring under predetermined conditions, but in the above-mentioned batch or semi-batch reactor, heated steam is blown into the reactor or heated from outside the reactor. So that the slurry containing the artificial zeolite raw material and the alkaline aqueous solution that have been adjusted to the silicate ratio, which has been put into the reaction tank,
It takes a long time to reach a predetermined condition, and furthermore, since the stirring is mechanical stirring using a propeller or the like, there is a problem that the stirring cannot be performed sufficiently and the reaction cannot be promoted.
Further, in a continuous production apparatus employing a circulating fluidized reaction tank, although stirring is performed relatively well, heating is performed in the same manner as in the batch type or semi-batch type described above. It takes a long time to reach the above condition, and there is a problem that the reaction cannot be promoted.

The present invention solves the above-mentioned problems, and a method for producing an artificial zeolite, in which a synthetic reaction of an artificial zeolite is promoted by a stirring action generated in a reaction tube to improve the production efficiency, and a production efficiency of the artificial zeolite. To provide an artificial zeolite production apparatus capable of supplying an inexpensive artificial zeolite by improving the above.

[0007]

According to a first aspect of the present invention, there is provided a method for producing an artificial zeolite, wherein a slurry containing an artificial zeolite raw material and an aqueous alkali solution adjusted to a predetermined silicate ratio is set to predetermined conditions and heated. It is characterized by having at least an artificial zeolite production step of continuously passing through the inside of the reaction tube.

According to the present invention, there is provided an artificial zeolite producing step in which a slurry containing an artificial zeolite raw material having an adjusted silicate ratio and an alkaline aqueous solution continuously passes through a heated reaction tube set under predetermined conditions. Since the slurry has at least the artificial zeolite raw material whose silicate ratio is adjusted in the slurry and the alkaline aqueous solution, the turbulent flow generated when the slurry passes through the heated reaction tube and the alkali aqueous solution are extremely efficiently stirred. At this time, since the reaction tube is set to predetermined conditions over its entire length, the reaction starts immediately after the slurry is supplied to the heated reaction tube. As a result, the production reaction of the artificial zeolite is promoted, and the reaction time can be reduced and the production efficiency can be improved.

A second aspect of the present invention is the method for producing an artificial zeolite according to the first aspect, wherein an orifice is provided in the reaction tube.

According to the present invention, the provision of the orifice in the reaction tube facilitates the generation of a turbulent flow and produces a sufficient stirring action. As a result, the production reaction of the artificial zeolite can be further promoted.

A third aspect of the present invention is characterized in that, in the method for producing an artificial zeolite according to the first or second aspect, the artificial zeolite producing step is provided with a reaction tube length changing means. .

According to the present invention, since the reaction tube length changing means is provided, the production rate of the artificial zeolite depends on the type and concentration of the artificial zeolite raw material and the alkaline aqueous solution, the flow rate of the slurry, the setting conditions of the reaction tube, and the like. Can be easily controlled based on the production rate.

The invention according to claim 4 is the invention according to claims 1 to 3.
The method for producing an artificial zeolite according to any one of
It is characterized in that a predetermined amount of artificial zeolite is blended with the slurry.

According to the present invention, since a predetermined amount of artificial zeolite is previously blended into the slurry to be supplied to the reaction tube, the artificial zeolite becomes a seed crystal, and the generation of artificial zeolite occurs very easily. And the production efficiency can be improved.

[0015] The invention of claim 5 is the invention of claims 1 to 4.
The method for producing an artificial zeolite according to any one of
The artificial zeolite generation step, and furthermore, a step of separating the artificial zeolite from the slurry containing the generated artificial zeolite, and a step of converting the type of the artificial zeolite,
Dewatering the artificial zeolite.

According to the present invention, in addition to the above-described artificial zeolite production step, an artificial zeolite separation step, an artificial zeolite type conversion step, and an artificial zeolite dehydration step are provided. Can be manufactured.

According to a sixth aspect of the present invention, in the method for producing an artificial zeolite according to the fifth aspect, the respective steps have a pressure difference with each other, and the slurry and the artificial zeolite are pumped. .

According to the present invention, since a pressure difference is provided between the above steps, the slurry and the artificial zeolite can be easily pumped. As a result, the production of the artificial zeolite can be performed easily and efficiently.

According to a seventh aspect of the present invention, in the method for producing an artificial zeolite according to the fifth aspect, the step of dehydrating the artificial zeolite includes depressurizing the air and / or water vapor in the dehydration tank to reduce the pressure. Pressurizing and heating air and / or water vapor and returning it again to the coil in the dehydration tank where the artificial zeolite is present, evaporating the water in the artificial zeolite,
It is characterized in that water vapor is condensed and discharged in the coil to be dehydrated, and these operations are subsequently repeated.

According to the present invention, dehydration can be efficiently performed by utilizing heat generated when air and / or steam after suction is pressurized and heated.

In the apparatus for producing an artificial zeolite according to the present invention, a slurry containing an artificial zeolite raw material adjusted to a predetermined silicate ratio and an alkaline aqueous solution is continuously set in a reaction tube heated to a predetermined condition. It is characterized in that it has at least an artificial zeolite generating device that passes through it.

According to a ninth aspect of the present invention, in the apparatus for producing an artificial zeolite according to the eighth aspect, an orifice is provided in the reaction tube.

According to a tenth aspect of the present invention, in the apparatus for producing an artificial zeolite according to the eighth or ninth aspect, the artificial zeolite generating apparatus is provided with a reaction tube length changing means. .

According to an eleventh aspect of the present invention, in the apparatus for producing an artificial zeolite according to any one of claims 8 to 10, a method for adding an artificial zeolite to the slurry is provided.
It is characterized in that an addition port for an artificial zeolite or an addition port for an alkaline aqueous solution containing an artificial zeolite is provided anywhere from the mixing tank of the slurry to the inlet of the reaction tube.

According to a twelfth aspect of the present invention, there is provided the apparatus for producing an artificial zeolite according to any one of the eighth to eleventh aspects, wherein the artificial zeolite generating apparatus, the artificial zeolite separating apparatus, and the artificial zeolite type converting apparatus. And an artificial zeolite dehydrator.

According to a thirteenth aspect of the present invention, in the apparatus for manufacturing an artificial zeolite according to the twelfth aspect, each of the devices has a pressure detecting means and a pressure difference between the respective devices based on the pressure detecting means. It is characterized in that a pressure adjusting means to be provided is provided.

According to the present invention, each device is provided with the pressure detecting means and the pressure adjusting means for providing a pressure difference between the devices based on the pressure detecting means.
By these means, a pressure difference can be created between the steps. As a result, the slurry and the artificial zeolite can be easily pumped, and continuous production of the artificial zeolite can be performed easily and efficiently.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for producing an artificial zeolite and an apparatus for producing the same will be described with reference to the drawings.

FIG. 1 is a flowchart showing an example of the method for producing an artificial zeolite of the present invention, FIG. 2 is a flow sheet showing an example of an apparatus for producing an artificial zeolite of the present invention, and FIG. FIG. 4 is a configuration diagram illustrating an example of a zeolite generation device, FIG. 4 is an explanatory diagram illustrating a mode of turbulence in a reaction tube, and FIG. 5 is a configuration diagram illustrating an example in which an orifice is provided in the reaction tube. FIG. 6 is a configuration diagram illustrating an example of an artificial zeolite separation device, and FIG. 7 is a configuration diagram illustrating an example of an artificial zeolite dehydration device.

As shown in FIG. 1, the artificial zeolite is prepared by preparing a slurry to be subjected to a reaction, and the artificial zeolite producing step / apparatus (hereinafter referred to as “step / apparatus” when referring to the step and / or apparatus. The same is applied.), An artificial zeolite separation step / apparatus, an artificial zeolite type conversion step / apparatus, and an artificial zeolite dehydration step / apparatus. After each of these steps / apparatuses, a washing step / apparatus can be added as required. Hereinafter, each process and each manufacturing apparatus will be described in order.

(1) Slurry The slurry to be used for the reaction of the artificial zeolite is a slurry containing an artificial zeolite raw material (hereinafter simply referred to as “artificial zeolite raw material”) adjusted to a predetermined silicate ratio and an alkaline aqueous solution. used.

The artificial zeolite raw material is made of a material containing both an aluminum component and a silicon component, or a material containing a mixture mainly containing one of the aluminum component and the silicon component. It can be adjusted to alum ratio.

Specific examples of the material containing an aluminum component include aluminum waste liquid, aluminum dross, alumite processing waste liquid, waste liquid such as aluminum sash cleaning liquid, waste aluminum can, waste aluminum foil and other aluminum-containing substances. . Specific examples of the material containing the silicon component include waste glass, silicon-containing substances such as waste silicon during the production of silicon wafers, rice, incinerated ash of grasses such as wheat, and alkaline extracts. . Further, specific examples of the material containing both the aluminum component and the silicon component include coal ash, municipal waste incineration ash, activated sludge incineration ash, incineration ash such as solidified fuel ash, papermaking sludge, casting sludge (waste sand). ), Ash molten slag,
Examples include tuff (eg, Oya stone), volcanic ash, and gravel debris. In addition, various kinds of lumps such as titanium lumps, copper lumps, nickel lumps, zinc lumps, and iron lumps may be mixed with the above materials.

Of these, coal ash called fly ash can be preferably used. This fly ash is fine ash particles which are collected by a dust collector when coal is pulverized and burned by a pulverized coal combustion boiler. The fly ash contains silicon oxide in the range of about 40 to 75% and about 15 to 3%.
Those containing aluminum oxide in the range of 5% are preferably used (Atsuo Hemi, Koshiaki Sakagami, "Artificial zeolite saves the earth", published by Japan Times Co., Ltd., 19
June 1999, p. 31).

The alkaline aqueous solution is indispensable for the artificial zeolite production reaction, and the type and concentration of the alkaline aqueous solution are appropriately selected according to the type of the artificial zeolite raw material described above. Specifically, a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution can be exemplified.

As shown in the flow sheet of FIG. 2, the slurry is prepared by mixing a predetermined amount of an artificial zeolite raw material such as fly ash and a predetermined amount of an aqueous alkali solution prepared to a predetermined concentration. , Into the slurry mixing tank 13 and mixed for a predetermined time to prepare. For example, when using an aqueous sodium hydroxide solution,
The aqueous sodium hydroxide solution diluted to 3.5N is mixed with 2 to 12 (more preferably 3 to
It is preferable to mix at a ratio of 8). The concentration of the aqueous alkali solution and the mixing ratio thereof are appropriately set in consideration of the type of the artificial zeolite raw material, the reaction conditions, the reaction time, the desired production amount, and the like.

The mixing means of the artificial zeolite raw material and the aqueous alkali solution is not particularly limited, but, for example, can be performed by a general propeller type stirring mixer. The slurry thus prepared is supplied to an artificial zeolite production step / apparatus by a supply pump. At this time, heating (for example, about 80 to 100 ° C.)
Preferably, they are supplied after being supplied.

Since the method for producing an artificial zeolite of the present invention is continuous, the injection and mixing of the artificial zeolite raw material and the aqueous alkali solution, and the supply of the slurry to the artificial zeolite production step / apparatus are performed by a valve operation. And so on. In the case where artificial zeolite is generated by a circulation type reaction tube described later, the slurry is supplied to the artificial zeolite generation step / apparatus after the artificial zeolite generated in the reaction tube is sent to the next step, and then the valve operation is performed. It is performed intermittently by the like.

(2) Artificial Zeolite Generation Step / Equipment The artificial zeolite generation step / equipment is a step / equipment for causing the supplied slurry to react with the artificial zeolite. The slurry is supplied continuously or intermittently, and the slurry continuously passes through the inside of the reaction tube 16 set at a predetermined temperature and pressure to generate an artificial zeolite reaction.

In the method and apparatus for producing an artificial zeolite of the present invention, the production step / apparatus of this artificial zeolite is the most characteristic part, and has at least this production step / apparatus. Therefore, if the method / apparatus for producing an artificial zeolite having the artificial zeolite generation step / apparatus includes a step / apparatus described in the present application in a pre-step / apparatus or a post-step / apparatus, It may include steps / apparatuses other than those described in the present application.

The term “continuous” as used in the artificial zeolite production step / apparatus refers to a mode in which the material is supplied and passed almost continuously, and a mode in which the supply and the flow are performed at regular intervals. Represents the case where. In the case where a slurry as described below is circulated in the reaction tube, the latter is performed, that is, the supply and the passage are performed continuously at regular intervals. There is also.

As shown in FIG. 3 and FIG. 4, the reaction of forming the artificial zeolite is caused by the action of turbulence generated when the slurry passes through the reaction tube 16 under a predetermined pressure and temperature condition. Due to this turbulence, the artificial zeolite raw material in the slurry and the aqueous alkaline solution are extremely efficiently stirred.

The degree of turbulence varies depending on the solid-liquid ratio of the slurry, that is, the ratio between the solid artificial zeolite raw material and the liquid alkaline aqueous solution, and the types of the raw materials and the like, and is arbitrarily set. The preferred degree of turbulence is Reynolds number 2,000 to 1,000,000, more preferably 8,000 to
It is 50,000, more preferably 10,000 to 30,000, and the production reaction of the artificial zeolite can be performed more efficiently. The Reynolds number is appropriately adjusted depending on factors such as the flow rate of the slurry, the inner diameter of the reaction tube 16, the density of the slurry, the viscosity and the kinematic viscosity. Therefore, setting of conditions, setting of the reaction tube 16 and the like are performed in consideration of these.

The reaction tube 16 can be provided with an orifice. The mode of the orifice is not particularly limited. The provision of the orifice facilitates generation of turbulence and adjustment of the Reynolds number. As an example, an orifice having the form shown in FIG. 5 can be provided.

The reaction tube 16 is made up of the flow sheet of FIG.
As shown in the block diagram of FIG. 5, a tube of a predetermined length having a predetermined inner diameter selected in consideration of the Reynolds number. The length and inner diameter are not particularly limited, and are arbitrarily designed based on the production amount and the reaction rate.

In order to facilitate the production of artificial zeolite, the reaction tube 16 is adjusted to a predetermined pressure by a pressure adjusting means, and is adjusted to a predetermined temperature by the following heating means. The relationship between the pressure and the temperature is preferably set based on a saturated vapor pressure curve.

The specific range of pressure and temperature applied to the slurry to produce the artificial zeolite is, based on a saturated vapor pressure curve, a pressure of about 8 kg / cm ² (about 0.8 kg / cm ² ).
MPa) ・ From a temperature of about 175 ° C, a pressure of about 16 kg / cm
^The temperature is preferably in a range of ² (about 1.6 MPa) and a temperature of about 200 ° C., but may be outside the above range and is not particularly limited. The reaction tube 16 has a material and dimensions (thickness, etc.) that can withstand setting the slurry to be subjected to the reaction under the above-described pressure and temperature conditions.

The heating may be performed by any of the heating medium oil 17, steam, heating furnace, etc.
There is no particular limitation. According to such a heating means, since the reaction tube 16 is heated at a uniform temperature over the entire length, a sufficient temperature is given to the slurry from the time when the slurry is supplied into the reaction tube 16. In addition, sufficient agitation based on turbulence is also provided. As a result, the reaction can be started immediately after the slurry is supplied to the reaction tube 16, the reaction for producing the artificial zeolite is promoted, and the reaction time can be shortened and the production efficiency can be improved. The flow sheet in FIG. 2 shows an example of a means for heating the reaction tube 16 with the heat medium oil 17. The heating medium oil 17
Is circulated by a circulation pump, and is heated to a predetermined temperature in between. In addition to such a circulation type, various methods such as a method in which a reaction tube is immersed in an oil bath can be adopted.

The speed of the slurry passing through the inside of the reaction tube 16 can be adjusted by using a pump or a pumping means described later in detail.

The artificial zeolite production step / apparatus includes:
A reaction tube length changing means can be provided. Reaction tube 16
Is set to predetermined conditions in its entire length, and immediately after the slurry is supplied to the reaction tube 16, the reaction is started by effective stirring by turbulence, but the artificial zeolite raw material and the alkaline aqueous solution are respectively changed by the reaction tube length changing means. Even if the artificial zeolite production rate can be changed depending on the type and concentration of the slurry, the slurry flow rate, and the setting conditions of the reaction tube (temperature, time, degree of turbulence, etc.), the reaction time based on the production rate Can be easily controlled.

The reaction tube length changing means includes a reaction tube 16
A method of shortening or lengthening the length of the reaction tube 16 by the piping operation described above can be adopted. Examples of the piping operation of the reaction tube 16 include a method in which a three-way valve is provided in the reaction tube 16 for each fixed length, and the operation is performed by opening and closing the valve.

Further, depending on the type and concentration of the artificial zeolite raw material, it may take time to produce the artificial zeolite, and the designed length of the reaction tube 16 may be insufficient. In such a case, in order to allow the slurry to react in the reaction
It is preferable to return the slurry that has reached the outlet of the reaction tube 16 to the inlet of the reaction tube 16 again. In this way, by circulating the slurry in a reaction tube having an excellent reaction promoting action, even when using an artificial zeolite raw material of a type in which an artificial zeolite is hardly generated, an artificial zeolite can be easily generated. it can. Further, by employing such a circulation means, there is an advantage that the length of the reaction tube can be reduced. In order to circulate the slurry, means for branching a flow path such as a three-way valve near the outlet of the reaction tube 16 are provided, and means for branching a flow path such as a three-way valve near the entrance of the reaction tube 16 are provided. Means such as connection between them by a bypass pipe can be adopted.

When the artificial zeolite is generated in such a circulation type reaction tube, the artificial zeolite generated in the reaction tube is once sent to the next step, and then a valve operation is performed to supply a new slurry into the reaction tube. Is preferred. Such a system can be said to be a mode in which the continuous reaction of the artificial zeolite is performed in a batch system. In the case of employing such a mode, the production capacity can be further improved by arranging two or more circulation-type reaction tubes. In this case, after the artificial zeolite generated in each circulation-type reaction tube is sent to the next step, the slurry is supplied to each circulation-type reaction tube. In the artificial zeolite production method / apparatus of such an embodiment, a plurality of compact circulation-type reaction tubes are arranged, and slurry is intermittently supplied into the reaction tubes at regular intervals. The slurry is supplied again after the artificial zeolite is continuously generated and the generated artificial zeolite is sent to the next step. As a result, even if a type of artificial zeolite raw material that requires a long time to generate the artificial zeolite is used, it is particularly preferable to further increase the production capacity.

Incidentally, in an artificial zeolite raw material containing a soluble aluminum component and a soluble silicon component (hereinafter referred to as "aluminosilicate") at a predetermined arsenic ratio, (a) aluminosilicate produced by the reaction in the raw material particles The rate at which the salt diffuses from the inside of the raw material particles into the aqueous alkali solution is rate-determining, and (b) the artificial zeolite formation reaction composed of aluminosilicate is performed on the surface of the particles, and the generation reaction rate is It has been found that it depends on the concentration of the alkaline aqueous solution and the concentration of the aluminosilicate in the alkaline aqueous solution.

In the present invention, the rate of diffusion of the aluminosilicate and the rate of the artificial zeolite generation reaction on the particle surface are controlled by the turbulent flow in the reaction tube 16 set to uniform conditions over the entire length. It is facilitated by action and takes place continuously.

That is, the stirring in the reaction tube 16 increases the chance of contact between the hydroxide ion of the aqueous alkali solution and the generated aluminosilicate, and thus the generated aluminosilicate is quickly removed from the surface of the raw material. Can be. Therefore, the diffusion of the aluminosilicate from the inside of the raw material particles into the alkaline aqueous solution (diffusion, which is a rate-determining reaction) can be promoted, and the rate can be increased. Therefore, the concentration of the aluminosilicate in the alkaline aqueous solution increases, and the speed of the artificial zeolite generation reaction is also accelerated. Moreover, the reaction tube 16
Is set to a condition such as a uniform temperature over the entire length, so that the reaction starts immediately after the raw material is supplied to the reaction tube 16 and the speed at which the aluminosilicate diffuses and the speed of the artificial zeolite generation reaction are reduced. Is promoted.

Further, ultrasonic vibration can be applied to the slurry to further promote the reaction for producing artificial zeolite. Since the ultrasonic vibration has the same action as the microscopic strong stirring, it increases the chance of contact between the hydroxide ion of the alkaline aqueous solution and the generated aluminosilicate as described above. Can be quickly removed from the surface of the raw material. Therefore, the diffusion of the aluminosilicate from the inside of the raw material particles into the alkaline aqueous solution (diffusion, which is a rate-determining reaction) can be promoted, and the rate can be increased.

As a means for further accelerating the formation reaction of the artificial zeolite, it is preferable to mix a predetermined amount of the artificial zeolite with the slurry. The artificial zeolite to be blended becomes an inducing factor for accelerating the crystal formation reaction, and acts as a so-called seed crystal. As a result, crystal formation of the artificial zeolite is promoted, so that the synthesis reaction time can be shortened and the production efficiency can be improved.

The amount of the artificial zeolite to be blended varies depending on the soluble aluminum component and the soluble silicon component of the artificial zeolite raw material constituting the slurry, but cannot be specified unconditionally. However, when coal ash is used as the artificial zeolite raw material, the artificial zeolite is not used. For 100 parts by mass of the raw material, 1.0
It is preferable to contain up to 5.0 parts by mass of an artificial zeolite.

At present, the action of promoting the crystal formation of the artificial zeolite by adding the seed crystal is presumed as follows. That is, the addition of the seed crystal causes the aluminosilicate around the seed crystal to grow on the seed crystal. Therefore, the concentration of the aluminosilicate existing around the artificial zeolite raw material decreases due to the contact between the seed crystal and the artificial zeolite raw material. The decrease in the concentration of these components on the surface of the artificial zeolite raw material promotes the diffusion of the aluminosilicate from inside the raw material particles into the aqueous alkali solution, thereby increasing the rate (diffusion-controlled reaction rate). Thus, it is considered that the production reaction of the artificial zeolite can be further promoted.

As means for previously containing a predetermined amount of artificial zeolite in the slurry supplied to the reaction tube 16, the addition port of the artificial zeolite or the addition port of the alkaline aqueous solution containing the artificial zeolite is connected to the slurry mixing tank 13.
To the inlet of the reaction tube 16. The seed crystal may be an artificial zeolite contained in the aqueous alkali solution taken out of the reaction tube 16 or an artificial zeolite taken out of each subsequent step / apparatus or pipe. The artificial zeolite-containing solution or artificial zeolite thus taken out is added through an addition port provided at the above-mentioned position (see FIG. 2).

From the above, in the present invention, artificial zeolites of constant quality can be efficiently and efficiently obtained. The concentration of the aqueous alkali solution in the slurry and the concentration of the aluminosilicate in the aqueous alkaline solution are as follows:
As described above, since the rate of the artificial zeolite production reaction is affected, the adjustment of the concentration is performed in the artificial zeolite production step /
An artificial zeolite-containing solution is sampled from the outlet after the apparatus, and the concentration of the alkaline aqueous solution and the concentration of the aluminosilicate contained therein are measured. / This is performed by the supply amount of the alkaline aqueous solution collected by the apparatus.

The process for producing the artificial zeolite described above /
The artificial zeolite produced by the device is contained in the aqueous alkaline solution and sent to the next artificial zeolite separation step / device. In addition, a water cooling device can be provided between the artificial zeolite separation step / apparatus, and thereby, the heated slurry can be cooled.

(3) Artificial Zeolite Separation Step / Apparatus The artificial zeolite separation step / apparatus is a step / apparatus for separating and extracting an artificial zeolite from an alkaline aqueous solution having an artificial zeolite. Device.

This separation process / apparatus is based on the theory of sedimentation separation utilizing a difference in specific gravity, in which a solid artificial zeolite and a liquid alkaline aqueous solution are separated in a separation tank 22.
The solid-liquid separation can be continuously performed in the inside. At this time, it is preferable to collect and reuse the alkaline aqueous solution after the separation, so that waste can be reduced. The reuse here is performed by returning the recovered alkaline aqueous solution to, for example, the slurry mixing tank 13 or returning to the middle of the pipe connecting the artificial zeolite generation step / device and the artificial zeolite separation step / device. .

At the time of preparing the slurry, foreign substances and unburned carbon and other fine particles previously mixed into the raw material are removed from the separation tank 2.
It floats on top of 2 and is discharged outside. In order to facilitate the separation of such fine particles, air can be introduced to perform gentle stirring.

The separated artificial zeolite is subjected to the following steps /
Sent to the device.

(4) Artificial Zeolite Type Conversion Step / Equipment The artificial zeolite type conversion step / equipment is a step / equipment for exchanging cations adsorbed on the artificial zeolite with desired cations.

The produced artificial zeolite is usually treated with an aqueous alkali solution composed of sodium hydroxide.
When the artificial zeolite is directly dehydrated, a sodium-type artificial zeolite can be obtained.

This type conversion step / apparatus is a step / apparatus for converting an artificial zeolite of sodium type into an artificial zeolite of a different type by ion exchange with another cation. Specifically, in the case of the calcium type, the ion exchange is performed in an aqueous solution of a calcium salt such as calcium chloride.In the case of the iron type, the ion exchange is performed in an aqueous solution of an iron salt such as iron chloride to obtain an aluminum type. When performing the ion exchange in an aqueous solution of aluminum salt such as aluminum chloride,
In the case of magnesium type, ion exchange with magnesium salt aqueous solution such as magnesium chloride, and in the case of potassium type, ion exchange in potassium salt aqueous solution such as potassium chloride to convert to artificial zeolite of each type. can do.

Each of these various types of artificial zeolites can be used for a variety of applications, so that artificial zeolites of a type corresponding to the application can be easily produced.

As shown in the flow sheet of FIG. 2, the mold conversion step / apparatus is provided with a calcium salt aqueous solution tank, an iron salt aqueous solution tank, an aluminum salt aqueous solution tank, a magnesium salt aqueous solution tank, and the like. By putting the aqueous solution of the above into a mold conversion tank, it is possible to easily perform ion exchange to convert to a desired mold.

The artificial zeolite charged into the mold conversion step / apparatus is one which has been washed at least once after exiting the artificial zeolite separation step / apparatus.
For example, cleaning can be performed by a solid-liquid separation type cleaning step / apparatus.

The converted artificial zeolite is sent to an artificial zeolite dehydration step / apparatus through a washing step / apparatus provided as necessary.

(5) Artificial Zeolite Dehydration Step / Equipment The artificial zeolite dehydration step / equipment is a step / equipment for dehydrating the converted type artificial zeolite into a product. Since the converted artificial zeolite still contains a large amount of water, it is necessary to dehydrate it to a predetermined amount of water.

The artificial zeolite dewatering step / apparatus in the present invention is based on a dehydration theory using a heat pump system. That is, the air and / or steam in the dewatering tank 42 is sucked and decompressed, and the air and / or steam after suction is pressurized and heated, and the coil in the dewatering tank 42 in which the artificial zeolite is present (referred to as a heating coil). Then, the moisture in the artificial zeolite was evaporated, and water vapor was condensed and discharged in the coil to be dehydrated. These operations were repeated to dehydrate the artificial zeolite. Since the artificial zeolite needs to contain a certain amount of water according to the usage mode, the degree of dehydration is adjusted as appropriate. In the present invention, the degree of the dehydration can be adjusted by the processing time of the artificial zeolite in the dehydration tank 42.

By such means, dehydration can be efficiently performed by utilizing heat generated when air and / or steam after suction is pressurized.

(6) Other Steps or Apparatus (i) In the method for producing an artificial zeolite and the apparatus for producing the artificial zeolite of the present invention, the slurry or the artificial zeolite is used during the period from the artificial zeolite production step / article to the artificial zeolite dehydration step / apparatus. For the transfer, a method of opening to the atmosphere using a pump or a pressure feeding method using a pressure difference can be preferably adopted. In the present invention, in particular, a pressure feeding method using a pressure difference can be preferably used.

The pumping system is a system in which a slurry or an artificial zeolite is automatically transferred from a higher pressure to a lower pressure by giving a pressure difference between each process / apparatus. Therefore, the transfer speed can be arbitrarily set by adjusting the pressure difference and the size of the tube. Therefore, the slurry or the artificial zeolite can be easily pumped while controlling the transfer speed thereof, and the production of the artificial zeolite can be performed easily and efficiently.

In particular, in the present invention, since the stirring action of the slurry in the reaction tube in the artificial zeolite production step / apparatus greatly affects the production reaction of the artificial zeolite, the speed of the slurry is arbitrarily and easily adjusted by the pressure feeding method. This has a special effect that the production reaction of the artificial zeolite can be easily controlled.

The continuous production apparatus for artificial zeolite provided with such a pumping system includes pressure detecting means provided in each apparatus,
And pressure adjusting means for providing a pressure difference between the respective devices based on the pressure detecting means. For example, the pressure can be detected by a pressure detection unit including a pressure sensor, and the pressure between each process / apparatus can be adjusted by a pressure adjustment unit including a pressure adjustment system 51 using liquid or air. In particular, a pressure adjustment system by air supply is preferable, and air can be taken in and out of each device to easily and safely adjust the internal pressure.

(Ii) In the present invention, not only the reaction tube 16 of the artificial zeolite production step / apparatus but also the inner diameter of each pipe and the transfer so that turbulence occurs when slurry or artificial zeolite is transferred. It is preferable to set the speed. In this way, by designing to generate turbulent flow in the pipe between each process / equipment, it is possible to mix the washing water and the ion exchange solution in the middle of the pipe and to sufficiently agitate them for processing. it can.

For example, between the artificial zeolite generation step / apparatus and the artificial zeolite separation step / apparatus, by adding water to the collected aqueous alkali solution and mixing the diluted aqueous solution, sufficient agitation is performed in the middle of the piping, The solid-liquid separation in the artificial zeolite separation step / apparatus can be easily performed. Further, artificial zeolite can be more efficiently washed by mixing washing water between the artificial zeolite separation step / equipment and the artificial zeolite washing step / equipment, and the piping after the type conversion step / equipment. Further, by mixing the ion exchange solution before the artificial zeolite type conversion step / apparatus, ion exchange can be facilitated and the type conversion efficiency can be improved.

(Iii) Sensors such as a slurry concentration sensor, an alkali concentration sensor, an ion sensor, a liquid level sensor, and a moisture sensor are provided as necessary in each process / apparatus as an auxiliary device for enabling continuous production. be able to. Based on signals detected by such sensors, concentration adjustment and liquid level adjustment by material supply can be performed.

(Iv) In the present invention, the recycling and reuse of the washing water is achieved. In the present invention, since the washing step / apparatus is usually provided after the separation step / apparatus or the mold conversion step / apparatus, the water after washing contains a large amount of sodium ions. Such washing water can be reused as washing water using a permeable membrane or the like.

(V) In the present invention, recycling of the alkaline aqueous solution is attempted. The aqueous alkali solution separated after the separation step / apparatus is collected and returned to the slurry mixed layer, so that it can be reused.

(7) Artificial Zeolite An artificial zeolite is manufactured through the above-described steps / devices. The artificial zeolite herein refers to a zeolite artificially produced by reacting an artificial zeolite raw material with an aqueous alkali solution. Its main component is phillipsite, but may contain a small amount of faujasite, zeolite A, hydroxysodalite and the like.

According to the method and apparatus for producing an artificial zeolite of the present invention, an artificial zeolite can be produced efficiently. The components other than zeolite include unburned carbon, iron, other impurities, and intermediate products up to zeolite.

As described above, as described in (1) to (7),
The method and apparatus for producing an artificial zeolite of the present invention is a continuous production method and apparatus by contact with a heated reaction tube. According to such an invention, by the action of turbulence generated when the slurry passes through the reaction tube 16, Since the artificial zeolite raw material and the aqueous alkali solution in the slurry are extremely efficiently stirred, the reaction for producing the artificial zeolite is promoted, and the reaction time can be reduced and the production efficiency can be improved.

[0090]

The present invention will be described more specifically below with reference to examples of embodiments of the present invention. The gist of the present invention is not limited to the following embodiments.

As shown in FIGS. 1 and 2, the artificial zeolite is prepared by mixing an artificial zeolite raw material adjusted to a predetermined silicate ratio and an alkaline aqueous solution in a slurry preparation step / apparatus 2, and the resulting slurry is artificially mixed. Zeolite production process /
An artificial zeolite is manufactured by sequentially passing through the apparatus 3, the separation step / apparatus 4, the washing step / apparatus 5, the mold conversion step / apparatus 6, the washing step / apparatus 7, and the dehydration step / apparatus 8.
Hereinafter, description will be made in order.

First, a slurry is prepared in the slurry preparing step / apparatus 2. The raw material of slurry is raw material silo 1
The coal ash stored in 1 and the 48% aqueous sodium hydroxide solution stored in the aqueous alkaline solution tank 12 are used. The predetermined amount and the dilution water are sent to the slurry mixing tank 13 to
Dilute to 3% (about 3.5N) aqueous sodium hydroxide solution and stir with a mixer to prepare a slurry.
This slurry is obtained by adjusting the coal ash and the aqueous sodium hydroxide solution to a predetermined ratio, and considering the reaction for producing the artificial zeolite, the ratio is 2 to 12% of the aqueous sodium hydroxide solution with respect to the coal ash 1. And more preferably 3 to 8. Next, the prepared slurry is supplied to a slurry supply tank 1 in which a constant amount is constantly maintained.
4 and continuously supplied to the artificial zeolite generator 15 while stirring. In addition, the piping for supplying the slurry
It is economical to supply the slurry by contacting it with the outlet pipe of the artificial zeolite generator 15 (for example, 85 ° C.), and it is preferable from the viewpoint of promoting the reaction.

In the artificial zeolite generator 15, a reaction tube 16 for causing the supplied slurry to react while being stirred by turbulent flow is arranged in a spiral shape as shown in FIG. 3, for example. Around the reaction tube 16, the slurry in the reaction tube is heated at a predetermined reaction temperature (for example, 175 ° C.).
In order to obtain a predetermined pressure (for example, about 8 kg / cm ² ),
The oil 17 at a predetermined temperature (for example, 200 ° C.) is circulated. The inlet side of the reaction tube 16 is raised to a predetermined pressure by a pump on the slurry supply side, and is controlled so that the slurry flows at an arbitrary speed toward the outlet side of the reaction tube 16. Here, the inner diameter of the reaction tube was, for example, 1.5 inches (about 38 mm). The artificial zeolite reacts by passing the slurry through such a reaction tube 16,
Generate.

In the artificial zeolite producing apparatus shown in FIG. 3, a reaction tube length changing means for changing the reaction tube 16 into, for example, three-stage switching is adopted.

The alkaline aqueous solution containing the generated artificial zeolite contacts the above-mentioned pipe for supplying the slurry while being sent to the artificial zeolite separation device 21 through the pipe, and is further heat-exchanged by the cooler 18 to be cooled. Is done. Further, in the middle of the pipe, there is provided an input port 19 for inputting a solution obtained by adding water to an alkaline aqueous solution recovered from the artificial zeolite separation step / apparatus.

[0096] The artificial zeolite-containing alkaline aqueous solution sent to the artificial zeolite separation device 21 separates from the liquid portion composed of an aqueous sodium hydroxide solution by the solid portion composed of the artificial zeolite settling in the separation tank 22. The artificial zeolite in the solid part is sent to the next washing device 26 from the outlet below the separation tank. At this time, it is transported by the pumping method,
For the purpose of metering control of slurry-like artificial zeolite,
A pump can be used together.

The liquid portion of the aqueous sodium hydroxide solution is recovered from an outlet 24 separated by several partitions 23. The recovered aqueous sodium hydroxide solution is sent to the slurry mixing tank 13 again, or
9 Above the separation tank 22, an air port 25 is provided, and the pressure from the pressure adjusting system 51 is used to adjust the internal pressure of the decomposition tank 22 to control the state of pressure feeding.

[0098] The artificial zeolite sent to the artificial zeolite washing device 26 is added with washing water in the middle of the piping.
When passing through the piping, the artificial zeolite to which the cleaning water has been added is stirred by a turbulent flow effect occurring in the piping, and is then charged into the cleaning tank 27 in a sufficiently washed state. The washing device 26 has the same form as that of the separation device 21. The washed artificial zeolite is settled and transferred to the next type conversion device 31 by a pump from an outlet below the washing tank. The washing liquid is collected from a discharge part 28 separated by some partition walls 2, filtered if necessary, and returned to a washing water supply tank 29. The internal pressure of the cleaning tank 27 is also adjusted by the same configuration as the decomposition tank 22.

To the artificial zeolite sent to the artificial zeolite type conversion device 31, one of various aqueous solutions for type conversion is added along the piping. In addition, when it is made into an artificial zeolite of a sodium type, it is sent as it is to the dehydrating device 41 in the next step. The artificial zeolite to which the aqueous solution for mold conversion has been added is stirred by the turbulent flow generated in the pipe when passing through the pipe, and is charged into the mold conversion tank 32 in a sufficiently ion-exchanged state. This type conversion device 31
Is also the same form as the separation device 21 and the washing device 26,
The washed artificial zeolite sediments and is transferred to the next washing device 36 by a pump from an outlet below the mold conversion tank.
The processing liquid is recovered from a discharge part 33 separated by some partition walls 23, filtered if necessary, and converted into a conversion liquid circulation tank 34.
Is returned to. The internal pressure of the mold conversion tank 32 is also adjusted by the same configuration as that of the decomposition tank 22 and the like, and the state of the pumping is controlled.

The artificial zeolite sent to the artificial zeolite cleaning device 36 is added with washing water in the middle of the piping.
The artificial zeolite to which the washing water has been added is stirred by the turbulent flow effect occurring in the piping when passing through the piping, and is charged into the cleaning tank 37 after being sufficiently washed. The cleaning device 36 has the same form as the above-described cleaning device 26, in which the washed artificial zeolite is settled and transferred to the next dehydrating device 41 by a pump from an outlet below the cleaning tank. The cleaning liquid is supplied to the discharge part 3 separated by several partitions 23.
8 and, if necessary, filtered and returned to the wash water supply tank 39. The internal pressure of the cleaning tank 37 is also adjusted by the same configuration as that of the above-mentioned cleaning tank 27, and the state of pressure feeding is controlled.

The artificial zeolite sent to the artificial zeolite dehydrator 41 is dehydrated in the dehydration tank 42. First, air and / or water vapor in the dehydration tub is sucked, and the air and / or water vapor is pressurized and heated by the compressor 43, and returned to the heating coil in the dehydration tub 42 where the artificial zeolite is present. The water in the artificial zeolite is evaporated by the heating coil. The water vapor returned into the heating coil is condensed and discharged. The artificial zeolite is dehydrated by the principle of such a heat pump, and transferred to the product silo 46 from below the dehydration tub to obtain the artificial zeolite.

[0102]

As described above, according to the method and the apparatus for producing the artificial zeolite of the present invention, the artificial zeolites in the slurry are turbulently generated when the slurry passes through the heated reaction tube. Since the zeolite raw material and the aqueous alkali solution are stirred very efficiently, the reaction of the artificial zeolite is promoted, and the reaction time can be reduced and the production efficiency can be improved. In addition, since the solid-liquid ratio of the slurry, the reaction time, the reaction temperature, etc. can be easily adjusted, it is possible to easily respond to changes in the supply amount and production amount, and continuous operation and automatic operation are possible. Become.

The method and apparatus for producing an artificial zeolite having the above effects can reduce the size of the entire apparatus and reduce the cost for plant construction. In addition, operating costs and maintenance costs can be significantly reduced. Furthermore, since it can be manufactured continuously and efficiently, mass production is possible, and it is possible to easily cope with an increase or decrease in the production amount.

[Brief description of the drawings]

FIG. 1 is a flowchart showing an example of a method for producing an artificial zeolite of the present invention.

FIG. 2 is a flow sheet showing an example of an apparatus for producing an artificial zeolite of the present invention.

FIG. 3 is a configuration diagram illustrating an example of an artificial zeolite generation device.

FIG. 4 is an explanatory diagram showing a mode of a turbulent flow in a reaction tube.

FIG. 5 is a configuration diagram showing an example in which an orifice is provided in a reaction tube.

FIG. 6 is a configuration diagram showing an example of an artificial zeolite separation device.

FIG. 7 is a configuration diagram showing an example of an artificial zeolite dehydrator.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Continuous production apparatus of artificial zeolite 2 ... Slurry preparation process / device 3 ... Generation process / device 4 ... Separation process / device 5 ... Cleaning process / device 6 ... Type conversion process / device 7 ... Cleaning process / device 8 ... Dehydration process / Apparatus 11 Raw silo 12 Alkaline aqueous solution tank 13 Slurry mixing tank 14 Slurry supply layer 15 Artificial zeolite generator 16 Reaction tube 17 Oil 18 Cooler 19 Input port 21 Artificial zeolite separator 22 Separation Tank 23 ... Partition walls 24, 28, 33, 38 ... Discharge part 25 ... Air port 26, 36 ... Artificial zeolite washing device 27, 37 ... Washing tank 29, 39 ... Washing water supply tank 31 ... Artificial zeolite type conversion device 32 ... type Conversion tank 34 ... Conversion liquid circulation tank 41 ... Artificial zeolite dehydrator 42 ... Dehydration tank 43 ... Compressor 46 ... Product silo 51 ... Pressure adjustment system

 ──────────────────────────────────────────────────続 き Continuing from the front page (71) Applicant 500344404 Frontier International Co., Ltd. 4th floor of 518 Ishikawa Building, 518 Waseda Tsurumakicho, Shinjuku-ku, Tokyo (72) Inventor: Akio Hemi 645-20, Kurizumicho, Matsuyama-shi, Ehime ( 72) Inventor Etsuro Sakagami 6-11-14 Minami Naruse, Machida-shi, Tokyo (72) Inventor Toshio Shimada 1858-18, Kiso-cho, Machida-shi, Tokyo (72) Inventor Kazuo Matsuoka 22-, Ibukino, Midori-ku, Yokohama-shi, Kanagawa-ken 23 F term (reference) 4G073 AA02 CZ01 CZ08 FB04 FB30 FB33 FD01 FD20 FD21 UA01 UA06 UA09

Claims (13)

[Claims] 1. An artificial zeolite producing step in which a slurry containing an artificial zeolite raw material and an aqueous alkali solution adjusted to a predetermined sulphone ratio is set to predetermined conditions and continuously passes through a heated reaction tube. A method for producing an artificial zeolite, comprising: 2. The method for producing an artificial zeolite according to claim 1, wherein an orifice is provided in the reaction tube. 3. The method for producing an artificial zeolite according to claim 1, wherein a reaction tube length changing means is provided in the artificial zeolite producing step. 4. The method for producing an artificial zeolite according to claim 1, wherein a predetermined amount of the artificial zeolite is blended with the slurry. 5. The artificial zeolite producing step, the step of separating the artificial zeolite from the slurry containing the produced artificial zeolite, the step of converting the type of the artificial zeolite, and the step of dehydrating the artificial zeolite. The method for producing an artificial zeolite according to any one of claims 1 to 4, comprising: 6. The method for producing an artificial zeolite according to claim 5, wherein each of the steps has a pressure difference therebetween, and the slurry and / or the artificial zeolite are pumped. 7. The step of dehydrating the artificial zeolite,
The air and / or steam in the dehydration tank is sucked and decompressed, and the air and / or steam after suction is pressurized and heated and returned to the coil in the dehydration tank where the artificial zeolite is present, and the moisture in the artificial zeolite is removed. 6. The method for producing an artificial zeolite according to claim 5, wherein water vapor is condensed and discharged in the coil while being evaporated and dehydrated, and these operations are subsequently repeated. 8. At least an artificial zeolite generating apparatus for continuously passing a slurry containing an artificial zeolite raw material and an aqueous alkali solution adjusted to a predetermined arsenic ratio under a predetermined condition in a heated reaction tube. An apparatus for producing an artificial zeolite, comprising: 9. The apparatus for producing an artificial zeolite according to claim 8, wherein an orifice is provided in the reaction tube. 10. The artificial zeolite producing apparatus according to claim 8, wherein the artificial zeolite generating apparatus is provided with a reaction tube length changing means. 11. An artificial zeolite addition port or an artificial zeolite-containing alkaline aqueous solution addition port for adding an artificial zeolite to the slurry may be provided at any position between the slurry mixing tank and the reaction tube inlet. The apparatus for producing an artificial zeolite according to any one of claims 8 to 10, wherein the apparatus is provided. 12. The artificial zeolite generating apparatus, the artificial zeolite separating apparatus, the artificial zeolite-type conversion apparatus, and the artificial zeolite dehydrating apparatus. 2. The apparatus for producing an artificial zeolite according to claim 1. 13. The apparatus according to claim 13, wherein each of the devices includes a pressure detecting unit;
13. The apparatus for producing an artificial zeolite according to claim 12, further comprising pressure adjusting means for providing a pressure difference between the respective devices based on the pressure detecting means.