JP5626155B2 - Clinoptilolite and nitrogen adsorbent using the same - Google Patents

Description

  The present invention relates to clinoptilolite having excellent nitrogen adsorption properties.

  Clinoptilolite is a kind of naturally occurring zeolite, and the use of a gas adsorbent, a mixed gas adsorbent, and the like has been studied. However, naturally produced clinoptilolite has problems such as non-uniform composition and low purity, and thus has low adsorption characteristics (Patent Documents 1 and 2).

  On the other hand, synthetic clinoptinolite and a method for producing the same have been proposed in order to improve the problems of natural clinoptilolite.

In Non-Patent Document 1, an alkali source of sodium hydroxide and / or potassium hydroxide is added to a mixture having a SiO ₂ / Al ₂ O ₃ molar ratio of 8 or 10 prepared using colloidal silica, and the mixture is heated to 120 to 195 ° C. Clinoptilolite obtained by heating in the range has been reported. However, the disclosed clinoptilolite has low purity and low adsorption properties.

Reference 3 discloses (2.1 ± 0.5) Na ₂ O.Al ₂ O ₃ · (10.0 ± 2) composed of fine amorphous silica, alumina source, alkali and clinoptilolite seed crystals. A clinoptilolite obtained by heating a mixture of the composition of 0.0) SiO _2. (110.1 ± 50.0) H ₂ O at about 100-200 ° C. within about 240 hours is disclosed. However, the disclosed synthetic clinoptilolite has low crystallinity and also poor adsorption properties.

Moreover, the general _{formula, x (Na, K) 2} O · Al 2 O 3 · ySiO 2 · zH 2 O ( In the formula, x = 0.8~1.2, y = 8.0~12.0 , Z ≧ 0) and K / (K + Na) = 0.20 to 0.95, and has a plate-like crystal, and the content of the clinoptilolite crystal phase is 90% or more. Clinoptilolite has been disclosed (Patent Document 4). However, the disclosed clinoptilolite has insufficient nitrogen adsorption properties.

  When these conventional clinoptilolite cations are ion-exchanged with alkaline earth metals, the amount of nitrogen adsorption can be increased to some extent, but it is not sufficient, and the adsorption performance varies greatly depending on the ion exchange rate and is stable. There was a problem that a good adsorption performance could not be obtained.

  Thus, clinoptilolite excellent in nitrogen adsorption characteristics has not been obtained so far.

Japanese Patent Laid-Open No. 62-132727 JP 62-162519 A US Pat. No. 4,623,529 Japanese Patent No. 3677807

Nature, vol. 304, 21 July, P255, 1983

  The present invention provides clinoptilolite excellent in nitrogen adsorption characteristics.

  As a result of studying clinoptilolite excellent in nitrogen adsorption characteristics, the present inventor found that when specific clinoptilolite was ion-exchanged with Ca or Mg, nitrogen was changed with respect to the change in the ion exchange amount of Ca or Mg. The inventors have found that there is no change in adsorption characteristics and a high nitrogen adsorption amount, and the present invention has been completed.

  Hereinafter, the clinoptilolite of the present invention will be described.

  The clinoptilolite of the present invention is clinoptilolite ion-exchanged with Ca or Mg and clinoptilolite used as a base material thereof.

  In the Ca or Mg-exchanged clinoptilolite of the present invention, the maximum equilibrium adsorption amount of nitrogen at 25 ° C. and 0 mmHg to 5500 mmHg is 30 NmL / g or more, preferably 31 NmL / g (NmL is a standard state of gas) (Volume at 1 atmosphere, 25 ° C.).

  In the Ca or Mg-exchanged clinoptilolite of the present invention, Ca or Mg is preferably 40% or more, particularly 45% or more of the ion exchange site. The more the Ca or Mg occupying the ion exchange site, the better the adsorption characteristics. If Ca or Mg is 40% or more, the adsorption characteristics of nitrogen are likely to be improved. On the other hand, even if it exceeds 80%, there is no significant increase in nitrogen adsorption characteristics. Therefore, 80% or less of Ca or Mg in the ion exchange site is sufficient.

  The clinoptilolite used in the Ca or Mg-exchanged clinoptilolite substrate of the present invention preferably has a clinoptilolite crystal phase content of 90% or more, preferably 95% or more. . When the content of the clinoptilolite crystal phase is 90% or more, when used for applications such as adsorbents and catalysts, adsorption and side reactions other than the intended components are less likely to occur.

  When the Ca or Mg-exchanged clinoptilolite of the present invention and its base material clinoptilolite are powders, the degree of compression is preferably 15% or more and 40% or less, particularly preferably 15% or more and 30. % Or less, more preferably 15% or more and 25% or less.

  Here, the degree of compression is an index indicating the fluidity of the powder. The smaller the degree of compression, the better the fluidity of the powder. For this reason, when clinoptilolite with a degree of compression exceeding 40% is used, a so-called cross-linking phenomenon occurs in which the clinoptilolite is crushed and aggregated by its own weight when stored in a powder-filled state. The fluidity of the liquid drops, making it very difficult to discharge. On the other hand, the smaller the degree of compression, the better the fluidity, but if it is 15% or more, handling becomes sufficiently easy.

  The degree of compression can be obtained by the following equation.

C = ( A − P ) / A × 100 (1)
C: Compressibility P: Bulk density (g / cm ³ )
A: Tap density (g / cm ³ )

The Ca or Mg-exchanged clinoptilolite of the present invention and the base material clinoptilolite may have a bulk density of 0.20 g / cm ³ or more and 0.40 g / cm ³ or less in the case of powder. It is particularly preferably 0.25 g / cm ³ or more and 0.40 g / cm ³ or less, more preferably 0.30 g / cm ³ or more and 0.40 g / cm ³ or less. Fillability improves by making the bulk density within this range.

For the same reason, the tap density of the Ca or Mg exchange clinoptilolite and clinoptilolite which is a substrate of the present invention, the tap density is 0.30 g / cm ³ or more 0.45 g / cm ³ or less It is preferable.

  Here, the bulk density in the invention is a value referred to as a lightly loaded bulk density, which is a powder density in a state where powder is naturally dropped and filled, and the tap density is a value referred to as a heavy bulk density. The density of the powder in a state where the container filled with the sample is tapped from a certain height and filled.

  When the Ca or Mg-exchanged clinoptilolite of the present invention and the base material clinoptilolite are powders, the average secondary particle size (aggregated particle size) is preferably 15 μm or more, particularly preferably. Is preferably 30 μm or more, and more preferably 40 μm or more. When the average particle diameter is 15 μm or more, the cohesiveness of the powder is suppressed and the fluidity is improved.

As the average secondary particle diameter, an average particle diameter by SEM observation, a median diameter by volume distribution, or the like can be adopted, but a median diameter (D ₅₀ ) by volume distribution is preferable.

  The secondary particle size distribution of the Ca or Mg-exchanged clinoptilolite of the present invention and the base material clinoptilolite preferably has two peaks of 5 μm to 15 μm and 30 μm to 100 μm. By having such a so-called bimodal secondary particle size distribution, the filling property tends to be high.

  In the secondary particle size distribution, the ratio of the peak of 5 μm or more and 15 μm or less is preferably 3% or more and 50% or less, and particularly preferably 3% or more and 30% or less of the particle size distribution. Thereby, the powder filling property is further enhanced.

  The secondary particle size distribution of the powder is preferably a particle size distribution measured by a laser diffraction / light scattering method.

  The particle shape contained in the Ca or Mg-exchanged clinoptilolite of the present invention and the base material clinoptilolite is preferably granular aggregated particles in which plate-like particles are aggregated. Thereby, the handling characteristic as a powder improves.

  Next, the Ca or Mg-exchanged clinoptilolite of the present invention and the method for producing the base material clinoptilolite will be described.

The Ca or Mg-exchanged clinoptilolite of the present invention is, for example, from an amorphous aluminosilicate gel obtained from an alkali silicate and an aluminum salt, water, sodium hydroxide and / or potassium hydroxide in a molar ratio,
_{SiO 2 / Al 2 O 3 =} 8~20
OH / SiO ₂ = 0.25 to 0.50
K / (K + Na) = 0.20-0.80
H ₂ O _/ SiO ₂ = 10~100
It is preferable to produce a mixture (hereinafter referred to as a raw material mixture) consisting of the following, and after heating to 100 to 200 ° C. with stirring, ion exchange is performed with a solution containing Ca or Mg.

  As the alkali silicate, an aqueous solution of sodium silicate, potassium silicate, silica sol or the like is preferably used. Furthermore, amorphous silica, silica gel, kaolinite, diatomaceous earth and the like, which are solid silica sources, are preferably used after being dissolved in an alkali component.

  As the aluminum salt, an aqueous solution of sodium aluminate, potassium aluminate, aluminum chloride, nitrate, sulfate or the like is preferably used. Furthermore, it is preferable to use a solid aluminum source such as aluminum hydroxide by dissolving it with a mineral acid or an alkali component.

  It is preferable to obtain an amorphous aluminosilicate gel by mixing an aqueous solution of an alkali silicate and an aluminum-containing aqueous solution. Although mixing conditions are not specifically limited, It can illustrate that the temperature at the time of mixing shall be room temperature-100 degreeC.

  Moreover, it is preferable to add acid components, such as an alkali component of sodium hydroxide or potassium hydroxide, sulfuric acid, and hydrochloric acid, as needed.

  The obtained amorphous aluminosilicate gel is preferably filtered and washed as necessary to remove by-product salts.

  Next, it is preferable to obtain a raw material mixture from water, sodium hydroxide and / or potassium hydroxide, and the obtained amorphous aluminosilicate gel.

The composition of the raw material mixture is SiO ₂ / Al ₂ O ₃ = 8 to 20 in molar ratio.
OH / SiO ₂ = 0.25 to 0.50
K / (K + Na) = 0.20-0.80
H ₂ O _/ SiO ₂ = 10~100
It is preferable that

By setting the OH / SiO ₂ molar ratio within this range, it becomes difficult to generate zeolite other than clinoptilolite or mineral (by-product) other than zeolite. Similarly, the production of zeolite other than clinoptilolite can be suppressed by setting the K / (K + Na) molar ratio to 0.20 or more and 0.80 or less.

  The obtained raw material mixture is heated and crystallized.

  The crystallization temperature is preferably 100 ° C. or higher and 200 ° C. or lower. When the crystallization temperature is 100 ° C. or higher, the progress of crystallization is easily promoted. On the other hand, the higher the crystallization temperature, the easier the crystallization rate becomes, but if it is 200 ° C. or less, it has a sufficient crystallization rate. Therefore, the crystallization temperature that does not require a special reaction vessel such as a high-temperature high-pressure type reaction vessel is preferably 200 ° C. or lower.

  The crystallization time is not particularly limited as long as crystallization proceeds, but for example, it is preferably about 1 to 15 days.

  The crystallization operation is preferably performed under stirring. When crystallization is performed with stirring, not only the crystallization speed is increased, but also a clinoptilolite single phase is easily obtained.

  In crystallization, it is preferable to add seed crystals. The crystallization time can be greatly shortened by adding seed crystals to the raw material mixture. The seed crystal is preferably clinoptilolite, and either natural clinoptilolite or synthetic clinoptilolite can be used. The amount of seed crystals is preferably 1% to 20% by weight of the raw material mixture. When the amount of the seed crystal is 1% by weight or more, the effect of shortening the crystallization time is obtained, and when it is 20% by weight or less, the effect of shortening the obtained crystallization time is sufficient.

  After the crystallization is completed, the produced crystals are separated from the mother liquor, washed with water, and dried to obtain crystal powder, whereby Na, K type clinoptilolite as a base material can be obtained.

  The obtained Na, K type clinoptilolite is preferably represented by the following formula.

_{x (K, Na) 2 O} · Al 2 O 3 · ySiO 2 · zH 2 O
(However, x = 0.8 to 1.2, y = 7.0 to 12.0, z ≧ 0, K / (K + Na) = 0.
20-0.95)
In the above general formula, y (SiO ₂ / Al ₂ O ₃ molar ratio) is 7.0 to 12.0.
When it is 7 or more, the heat resistance of clinoptilolite is improved, and when it is 12.0 or less, a single phase of clinoptilolite is easily obtained.

In the above general formula, K / (K + Na) = 0.20 to 0.95 is preferable,
It is particularly preferable that K / (K + Na) = 0.5 to 0.7.

  By the above production method, clinoptilolite satisfying the above-mentioned powder physical properties (compressibility, bulk density, tap density, secondary particle size, etc.) can be obtained, and clinoptilo satisfying such powder physical properties. The light exhibits high nitrogen adsorption performance.

The obtained K, Na type clinoptilolite is obtained by treating a part of K ⁺ or Na ⁺ with Ca ²⁺ , Mg using a known method such as treatment with a solution containing Ca ²⁺ or Mg ²⁺ for ion exchange. ^{It can} be ion-exchanged into ²⁺ and then activated to obtain Ca or Mg type clinoptilolite. The powder physical properties of the Ca or Mg-exchanged clinoptilolite are those maintaining the powder physical properties of the K, Na type clinoptilolite.

  The clinoptilolite of the present invention is an adsorbent that has high nitrogen adsorption performance and can hardly exhibit high adsorption ability because the nitrogen adsorption amount hardly changes depending on the ion exchange amount of Ca or Mg. .

Particle size distribution of clinoptilolite obtained in Example 1 X-ray diffraction pattern of clinoptilolite obtained in Example 1 Equilibrium nitrogen adsorption amount of Ca-exchanged clinoptilolite obtained in Example 1 Particle size distribution of clinoptilolite obtained in Comparative Example 1 Equilibrium nitrogen adsorption of Ca-exchanged clinoptilolite obtained in Comparative Example 1

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

(Composition analysis)
The sample was dissolved in a hydrofluoric acid solution and nitric acid, and measured with ICP-AES (OPTIMA 3000 DV manufactured by PERKIN ELMER).

(Crystal content of clinoptilolite)
The crystal content of clinoptilolite was measured by X-ray diffraction. For the measurement, a diffraction peak at 2θ = 3 to 40 ° was measured using an X-ray diffractometer (MXP3 manufactured by Mac Science). From the obtained X-ray diffraction pattern, it was determined from the ratio of the clinoptilolite peak to the impurity phase peak. The clinoptilolite was identified using X-ray diffraction data of HEU-type zeolite described in COLLECTION OF SIMULATED XRD POWDER PATTERNS FOR ZEOLITES, Fifth Revised Edition 2007, ELSEVIA, pages 206 to 207.

(Particle size distribution and average particle size)
The particle size distribution and average particle size of the sample were measured using a particle size distribution measuring device (Microtrac HRA (Nikkiso Co., Ltd.)). A predetermined amount of the sample was added while circulating pure water, and the volume distribution was measured by a laser diffraction method to obtain the particle size distribution and the average particle size (D ₅₀ ).

(Electron microscope observation)
The aggregation state and particle morphology of the obtained clinoptinolite powder were measured with an electron microscope (SEM;
Observation was performed using a JSM-6390LV electron microscope manufactured by JEOL Ltd.

(Bulk density)
Prior to the measurement of the bulk density, the sample was hydrated at 25 ° C. and in a moisture of 80%, and the moisture adsorption amount of the clinoptilolite powder was made constant.

  The bulk density was measured using a powder tester PT-R type (manufactured by Hosokawa Micron Co., Ltd.) for the sample after the moisture adsorption amount was made constant. In the measurement, the sample was naturally dropped and measured in a container so as to be exactly 100 ml, and the bulk density (P) was determined from the weight and volume (100 ml) of the sample at that time.

(Tap density)
Tap density measurement is the same as the bulk density measurement for samples with a constant water adsorption amount.
Measurement was performed using a powder tester PT-R type (manufactured by Hosokawa Micron Corporation). The sample was dropped naturally, tapped 180 times with a stroke length of 18 mm, measured in a container so that it would be exactly 100 ml, and the weight of the sample at that time was divided by the volume (100 ml) and tapped. The density (A) was determined.

(Compression degree)
The degree of compression (C) (%) was determined from the measured bulk density (P) and tap density (A) based on the following formula.

C = ( A − P ) / A × 100 (1)
C: Compressibility P: Bulk density (g / cm ³ )
A: Tap density (g / cm ³ )

(Equilibrium adsorption amount)
The equilibrium adsorption amount of nitrogen was measured using BELLSORP HP (manufactured by Nippon Bell Co., Ltd.) at an adsorption temperature of 25 ° C. at each pressure of 0 mmHg to 5500 mmHg.

(BET specific surface area)
The BET specific surface area measured BELLSORP 28SA (made by Nippon Bell Co., Ltd.).

Example 1
Amorphous aluminosilicate gel prepared from pure water, aqueous sodium hydroxide, aqueous potassium hydroxide, sodium silicate and aluminum sulfate was mixed so as to have the following composition to obtain a raw material mixture.

SiO ₂ / Al ₂ O ₃ = 12
OH / SiO ₂ = 0.34
K / (K + Na) = 0.65
H ₂ O / SiO ₂ = 20

  2% of natural clinoptilolite was added as a seed crystal to the obtained raw material mixture, and heated at 150 ° C. for 72 hours with stirring. After cooling, it was filtered, washed and dried to obtain clinoptilolite.

The obtained clinoptilolite is SiO ₂ / Al ₂ O ₃ = 9.6, (Na, K) ₂ O /
Al ₂ O ₃ = 0.97 and K / (K + Na) = 0.88.

  As a result of SEM observation, the obtained clinoptilolite was in the form of a granular powder in which plate-like particles were aggregated. The average secondary particle size is 46.3 μm, and the secondary particle size distribution has peaks at 9 μm and 50 μm, which is a so-called bimodal particle size distribution, and the 9 μm peak is the particle size distribution. Of 13%.

  As a result of X-ray diffraction, there was no peak other than clinoptilolite, and the crystal content of clinoptilolite was 100%. The results are shown in Table 1, the particle size distribution of secondary particles is shown in FIG. 1, and the X-ray diffraction diagram is shown in FIG.

  The obtained clinoptilolite was excellent in fluidity, and no cross-linking phenomenon occurred during handling and storage.

Add 5 to 20 times equivalent of CaCl ₂ solution (200 mL) to 5 g of the resulting clinoptilolite, and perform ion exchange by performing the operation of stirring at 60 ° C. for 2 hours once or twice, at 350 ° C. for 2 hours under reduced pressure. To obtain Ca type clinoptilolite.

  Table 2 shows the ratio of Ca in the ion exchange site of the obtained clinoptilolite and the maximum equilibrium adsorption amount of nitrogen at 25 ° C. and 0 to 5500 mmHg. The maximum equilibrium adsorption amount of nitrogen at a Ca exchange rate of 49.0% is 31.9 NmL / g, and the maximum equilibrium adsorption amount of nitrogen at a Ca exchange rate of 66.9% is 31.6 NmL / g, depending on the Ca exchange rate. There was almost no change in the maximum equilibrium adsorption amount.

  FIG. 3 shows the equilibrium adsorption amount of nitrogen at 25 ° C. and 0 to 5500 mmHg in clinoptilolite having a Ca exchange rate of 66.9%.

Comparative Example 1
Clinoptilolite was produced according to Patent Document 4. A mixture of sodium hydroxide, potassium hydroxide and aluminum hydroxide, pure water and white carbon (Nippal VN3 manufactured by Tosoh Silica Industry) were mixed to obtain the following composition to obtain a raw material mixture.
SiO ₂ / Al ₂ O ₃ = 11
OH / SiO ₂ = 0.30
K / (K + Na) = 0.50
H ₂ O / SiO ₂ = 25

  The obtained raw material mixture was put into an autoclave and heated at 150 ° C. for 144 hours with stirring. After cooling, it was filtered, washed and dried to obtain clinoptilolite powder.

The obtained clinoptilolite is SiO ₂ / Al ₂ O ₃ = 8.4, (Na, K) ₂ O /
Al ₂ O ₃ = 0.73 and K / (K + Na) = 1.0.

  When the purity was determined by X-ray diffraction, there was no peak other than clinoptilolite, and the crystal content of clinoptilolite was 100%. As a result of SEM observation, the obtained clinoptilolite had an irregular powder shape in which plate-like particles were dispersed individually. The average secondary particle size was 10.9 μm, and the secondary particle size distribution was a monomodal particle size distribution with a peak at 10 μm. The results are shown in Table 1, and the particle size distribution is shown in FIG.

  In the clinoptilolite of Comparative Example 1, a crosslinking phenomenon occurred during storage, the particle shape changed, and the fluidity of the powder was low.

Add 5 to 20 times equivalent of CaCl ₂ solution (200 mL) to 5 g of the resulting clinoptilolite, and perform ion exchange by performing the operation of stirring at 60 ° C. for 2 hours once or twice, at 350 ° C. for 2 hours under reduced pressure. To obtain Ca type clinoptilolite.

  Table 2 shows the Ca exchange rate of the obtained clinoptilolite and the maximum equilibrium adsorption amount of nitrogen at 25 ° C. and 0 to 5500 mmHg. The maximum equilibrium adsorption amount of nitrogen at a Ca exchange rate of 46.5% is 29.8 NmL / g, the maximum equilibrium adsorption amount of nitrogen at a Ca exchange rate of 60.2% is 27.7 NmL / g, and the Ca exchange rate is 66. The maximum equilibrium adsorption amount of nitrogen at 9% was 21.6 NmL / g, and the maximum equilibrium adsorption amount significantly decreased as the Ca exchange rate increased.

  FIG. 5 shows the equilibrium adsorption amount of nitrogen at 25 ° C. and 0-5500 mmHg in clinoptilolite having a Ca exchange rate of 66.9%.

  The clinoptilolite of the present invention can be used as an adsorbent that adsorbs nitrogen.

Claims (3)

Compression degree of 40% to 15%, a bulk density of 0.20 g / cm ³ or more 0.40 g / cm ³ or less, yet tap density is less than 0.30 g / cm ³ or more 0.45 g / cm ³ Kurinopuchi Lolite. 2. The clinoptilolite according to claim 1 , wherein the average secondary particle diameter is 15 μm or more, and the secondary particle diameter distribution has two peaks of 5 μm or more and 15 μm or less and 30 μm or more and 100 μm or less. Clinoptilolite of claim 1 or 2 plate-like particles are agglomerated particles of granular agglomerated.

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