JPH111318A - Production of zeolite granule with controlled pore size - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing zeolite granules 0.05-1 μm in pore size, sharp in pore size distribution and 10-50 m<2> /g in specific surface area. SOLUTION: The zeolite granules can be obtained through the following process: 100 pts.wt. of natural zeolite powder, or a mixture of 90 pts.wt. of natural zeolite powder and 10 pts.wt. of polyvinyl alcohol or a mixture of 80 pts.wt. of natural zeolite powder and 20 pts.wt. of bentonite is incorporated with 15-30 (pref. 18-25) wt.% of water as a binder followed by thoroughly mixing the stock powder with the water for 5-30 min through revolution of an agitating blade at 900-3,000 rpm using a rotary mixing-type granulator; the temperature of the resulting granules is then raised at a rate of 100 deg.C/h to 200-700 deg.C followed by baking the granules at that temperature for 1-2 h, thus obtaining the objective zeolite granules 0.05-1 μm in pore diameter, sharp in pore size distribution and 10-50 m<2> /g in specific surface area.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used for producing granulated zeolite having a pore diameter in a specific range.

[0002]

2. Description of the Related Art When zeolite is used industrially,
Zeolite powder is rarely used as it is, and is generally used as a columnar, spherical, plate-like or other suitable molded body. When manufacturing molded products,
Since the zeolite powder itself has no mutual bonding properties, clay minerals such as kaolinite and montmorillonite, alumina sol, silica sol, and the like are added for the purpose of imparting appropriate plasticity and bonding (strength). However, the zeolite molded body thus produced may have a zeolite component diluted by the amount of the binder added, or may have an undesired reaction of the binder, resulting in a decrease in the properties of the zeolite. . On the other hand, with respect to a method for producing a zeolite with controlled pores, sodium, potassium, etc. constituting the zeolite crystal are ion-exchanged to obtain a zeolite.
Although a method of changing the size of the micropore of about 5 mm is known, a method of simply controlling a mesopore or macropore of 0.1 μm or more is not known.

[0003] The zeolite granules produced by the conventional method tend to have a reduced gas adsorption ability, ion exchange ability, catalytic ability, etc. of the zeolite due to the addition of a binder. Regarding the control of the pores of zeolite, there is a control of the micropore size of the zeolite itself, but the control of the pores of about 1 μm is not performed. Further, although the pore control of the plate-like compact is performed as the pore control of the zeolite compact, there is no control of the granulated product.

[0004]

The problem to be solved by the present invention is that the pore diameter is controlled to 0.05 to 1 μm,
And the pore distribution is sharp and the specific surface area is 10 to 50 m ^2.
/ G of zeolite granules.

[0005]

The present invention solves the above-mentioned problems by providing a natural zeolite powder of 100 parts by weight,
Alternatively, a mixture of 90 parts by weight of natural zeolite powder and 10 parts by weight of polyvinyl alcohol, or 80 parts by weight of natural zeolite powder and 20 parts by weight of bentonite is used as a binder.
5-30%, preferably 18-25% of water is added, and the stirring blade is turned to 900-300 using a rotary mixing type granulator.
0r. p. m at a specific rotation speed, 5-30 minutes,
The raw material powder and water are mixed well and granulated to produce granulated zeolite. Next, the granulated body is heated to a specific temperature in the range of 200 to 700 ° C. at a heating rate of 100 ° C./Hr, and is baked at that temperature for 1 to 2 hours to obtain 0.05 to 1 hour.
An object of the present invention is to obtain a zeolite granule having a specific pore diameter in the range of μm, a sharp pore distribution, and a specific surface area of 10 to 50 m ² / g.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The pore diameter in the present invention is controlled by the synergistic effect of mixing by granulation and mass transfer by calcination.
It is possible to control the pores within the range of 0.05 to 1 μm. The addition ratio as granulation conditions is suitably 0 to 20% depending on the added component, and the rotation speed of the granulator is 900 to 3000 rpm. p.
m was appropriate, and the firing conditions were suitably 200 to 700 ° C.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described. Example 1 To 5 kg of natural zeolite having an average particle size of 10.24 μm, 25% of water was added as a binder, and a rotary mixing granulator was used. p. stirring at 20 rpm for 20 minutes,
Zeolite granules having a size of 0.1 to 1 cm were prepared.
Next, the granulated zeolite was heated at a heating rate of 100 ° C./H.
The temperature was raised to a specific temperature of 200 to 700 ° C. at r, and kept at that temperature for 2 hours, and then the furnace was released. The zeolite granules thus obtained were subjected to a pore distribution measurement by a mercury intrusion method (a mercury contact angle of 130 degrees and a surface tension of 484 dyne).
/ Cm) and specific surface area (BET one-point method, nitrogen adsorption method). FIG. 1 shows the measurement results of the pore diameter. In FIG. 1, the horizontal axis is the firing temperature [° C.] and the vertical axis is the pore diameter [μm]. In firing at 300 to 600 ° C,
It is recognized that the pore diameter tends to gradually increase as the firing temperature is increased. At 200 ° C., which is lower than 300 ° C., the same as at 300 ° C.
Even at 700 ° C. higher than 00 ° C., the same result as at 600 ° C. was obtained. Therefore, in order to produce a granulated product having a pore size of 0.05 to 0.3 μm, the rotational speed of the rotary mixing type granulator is set to 900 rpm. p. m to form a granulated body, which has been found to be fired at 300 to 600 ° C. FIG. 2 shows the specific surface area measurement results. In FIG. 2, the horizontal axis represents the firing temperature [° C.], and the vertical axis represents the specific surface area [m ² /
g]. The specific surface area value is slightly smaller than 38 m ² / g of the natural zeolite ore at any firing temperature, and the value decreases as the firing temperature increases. However, it is estimated that the gas adsorption capacity of zeolite has not decreased so much.

Example 2 In Example 1, the rotational speed of the rotary mixing type granulator was set to 900
r. p. m instead of 3000r. p. m, zeolite granules were produced in the same manner as in Example 1. FIG. 3 shows the measurement results of the pore diameter of the zeolite granules thus obtained. The pore diameter tended to increase as the firing temperature increased. 0.05 ~
To produce granules having a pore diameter of 0.5 μm,
The rotation speed of the rotary mixing type granulator is set to 3000 rpm. p. It was clarified that a granulated body was prepared at m and fired at a specific temperature of 200 to 700 ° C. FIG. 4 shows the measured values of the specific surface area. Although the specific surface area tended to decrease as the firing temperature increased, it cannot be said that the specific surface area decreased significantly as compared with the value of the raw zeolite ore, so it is considered that the gas adsorption ability did not significantly decrease.

Example 3 Zeolite granulation was carried out in the same manner as in Example 1 except that a mixture of 90 parts by weight of natural zeolite powder and 10 parts by weight of polyvinyl alcohol was used instead of 100 parts by weight of natural zeolite powder. Body manufactured. FIG. 5 shows the pore diameter measurement results of the zeolite granules thus obtained. By baking at a specific temperature of 200 to 700 ° C., a granule having a pore diameter of 0.5 to 1 μm was obtained. Granules having pore diameters slightly larger than the pore diameters of the granules obtained in Examples 1 and 2 were obtained. FIG. 6 shows the measured values of the specific surface area. 20 m ² /
g or more, slightly lower than the value of the ore, but no significant decrease in adsorption capacity was observed.

Example 4 In Example 1, 80 parts by weight of natural zeolite powder and bentonite 20 were used instead of 100 parts by weight of natural zeolite powder.
A granulated zeolite was produced in the same manner as in Example 1 except that the mixture in parts by weight was used. FIG. 7 shows the measurement results of the pore diameter of the zeolite granules thus obtained. 2
In the firing at 00 to 400 ° C., a pore diameter of 0.05 μm is obtained.
In addition, a granule having a pore diameter of 0.07 μm was obtained by firing at 500 to 700 ° C. FIG. 8 shows the specific surface area measurement results. As in Examples 1, 2, and 3, the specific surface area value decreased with an increase in the firing temperature, but no significant decrease was observed.

With respect to the zeolite granules obtained in Examples 1, 2, 3, and 4, Table 1 shows the production conditions, the results of measuring the pore diameter and the specific surface area.

[0012]

According to the present invention, it has a pore diameter in the range of 0.05 to 1 μm, a sharp pore distribution, and a decrease in properties such as specific surface area with respect to the raw zeolite ore. Obtained no zeolite granules, this zeolite granules by using the controlled pores according to the purpose, gas adsorbents, as well as existing fields such as water treatment,
It is expected to be applied to various separation materials and catalyst carriers.

[Brief description of the drawings]

FIG. 1 is a diagram showing the relationship between the firing temperature of a granulated zeolite and pore diameter in Example 1 of the present invention.

FIG. 2 is a diagram showing the relationship between the firing temperature and the specific surface area of the zeolite granules in Example 1 of the present invention.

FIG. 3 is a relationship diagram of FIG. 1 in a second embodiment of the present invention.

FIG. 4 is a relationship diagram of FIG. 2 in a second embodiment of the present invention.

FIG. 5 is a relationship diagram of FIG. 1 in a third embodiment of the present invention.

FIG. 6 is a relationship diagram of FIG. 2 in a third embodiment of the present invention.

FIG. 7 is a relationship diagram of FIG. 1 in a fourth embodiment of the present invention.

FIG. 8 is a relationship diagram of FIG. 2 in a fourth embodiment of the present invention.

[Table 1]

Claims (1)

[Claims] 1. A zeolite powder having an average particle size of 0.1 to 100 μm as it is, or an organic water-soluble polymer substance or a clay mineral is added thereto, and an appropriate amount of water is added thereto as a binder, followed by a rotary mixing method. Granulate with a granulator, particle size 0.1
to produce granules with a size of mm to 2 cm,
By calcining at 00 ° C., the pore size becomes 0.05 to 1
μm, the pore size distribution is sharp, and the specific surface area is 10 to 50 m ² / g similar to that of the zeolite ore.
A method for producing a zeolite granule having a controlled pore size, characterized by obtaining a zeolite granule as described above.