JPS6068052A - Zeolite composition suitable for separating oxygen and nitrogen and manufacture of its molded body - Google Patents

Abstract

PURPOSE:To obtain a zeolite composition suitable for the separation, purification, and concentration of gaseous oxygen and nitrogen by substituting Na of zeolite which is ion exchangeable with an alkaline earth metal. CONSTITUTION:>=0.7 equivalent fraction of Na contained in X-, Y-, or A type zeolite is ion exchanged with an alkaline earth metal. The powder or the small granules of said zeolite composition is mixed by a wet process with an inorganic and/or an organic binder (e.g. bentonite), and the mixture is molded, dried, and then calcined at 400-580 deg.C. The zeolite composition thus obtained is provided with a high adsorption ratio of N2/O2 and further with a high adsorption and desorption velocity, and is highly effective in separation, purification, and concentration of gaseous oxygen and nitrogen on the basis of the adsorption method.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel zeolite-based composition suitable for separating, purifying, or concentrating a mixed gas mainly consisting of oxygen and nitrogen gas by an adsorption method, and a molded product thereof. The purpose is to produce a specific composition of A-type zeolite, X-type zeolite, and Y-type zeolite substituted with divalent metals suitable for the separation and concentration of the above gases. An object of the present invention is to provide an active zeolite composition having the following properties and a method for producing the molded body.

Type A zeolite having a pore diameter of about 5 molecules and having a 5-molecular sieving action is widely used in the separation and purification of oxygen and nitrogen gases by adsorption methods. Commercially available M as a typical adsorbent
S-5A is exemplified. In order to improve the separation and concentration of the above-mentioned gases, the present inventor conducted repeated research to increase the adsorption and desorption rate of mainly oxygen and nitrogen gases with respect to the zeolite-based adsorbent. A composition in which sodium-type zeolite is replaced with a certain amount or more of divalent metal has a higher N2/
The Ox adsorption ratio is higher, and the gas adsorption and desorption rates are also higher. Therefore, the divalent metal-substituted zeolite composition is suitable for the separation and concentration of oxygen and nitrogen gases mentioned above based on the adsorption method. It was found that the 9JJ fruit was extremely high.

The present invention will be described in detail as follows.

The first invention relates to separation of oxygen and nitrogen gas,
The present invention also relates to a divalent metal-substituted zeolite composition that is effective for concentration. The present invention is.

It is composed of the following active zeolite composition suitable for the separation, purification, and concentration of oxygen and nitrogen gases obtained by replacing the ion-exchangeable sodium of zeolite with divalent metal ions (M). Immediately.

(1) The sodium contained in type X zeolite is 0.8 in calcium, strontium and/or barium.
A zeolite composition obtained by ion-exchanging an equivalent fraction or more.

NaCaX (Ca 2 O, 8) NaSr A zeolite composition which is ion-exchanged with barium at an equivalent fraction of g or more, or at an equivalent fraction of 0.7 or more.

NaCaY (Ca2O, 8) NaSrY (Sr≧0.9) NaBaY (Ha≧0.7) (3) A zeolite composition obtained by ion-exchanging the sodium contained in A-type zeolite with calcium at an equivalent fraction of 00 g or more. .

NaCaZ (Ca2O,9) However, the above X, Y, and Z represent X-type zeolite, Y-type zeolite, and A-type zeolite I, respectively, and the values in parentheses indicate the divalent value in the zeolite solid phase. It shows the equivalent fraction of metals (total amount of ion-exchangeable metals in the zeolite solid phase: R 1 M = 1 equivalent fraction).

X-type zeolite (NaX) with a pore size of about 10 people is subjected to an ion exchange reaction with divalent metal ions using an aqueous solution of water-soluble divalent metal chlorides, nitrates, etc. at room temperature to high temperature 20
2 in the three zeolite compositions of NaCa X, Na5rX, and NaBa
The content of IIIi metals is in each case at least 0
．． The presence of 8 equivalent fractions or more is also necessary to increase the separation efficiency of oxygen and nitrogen gases by selective adsorption.

The N210λ adsorption ratio for the thermally activated amount of the above three types having such compositions is improved and increased by 5 to 33% compared to that of NaX in all cases. Furthermore, the gas chromatographic characteristics of the X-type zeolite substituted with the three types of divalent metals mentioned above are characterized by being improved more than those of NaX. That is, when the air component was separated by gas chromatography (G, C1) using the above three types of NaM X activation amounts (M2O, 8 equivalent fraction), 1
The chromatographic separability of oxygen and nitrogen gas obtained by q was improved in a more favorable direction when using the NaXNaX active product, and the obtained gas chromatograph was further evaluated using ), and the resolution (R), but both of these values are different from those of the former three types of divalent metal substituents, and the latter Na
It was confirmed that there was a significant increase compared to X. Above S
,'Q.

and R ratings are W, Ljones and R, Kiesel.
bach, 8nal.

chem, 30.1590 (1958). The tendency for the S, Q, and R values to increase is due to the increase in the activation amount of the three types of NaMX (M2O, 8) mentioned above when separating or concentrating oxygen and nitrogen gases from air components etc. using the adsorption method. By using it as an adsorbent.

This means that not only the amount of adsorbent used can be reduced compared to the amount required for known adsorbents, but also the time required for the adsorption process and regeneration process of the adsorption bed can be significantly shortened.

In other words, by using NaM X of the present invention, there is an advantage that the above target gas can be obtained economically by adsorption method. In the present invention, the aforementioned three types of NaMX compositions are all limited to a richness≧0.8 equivalent fraction. M
In the range of equivalent fraction = 0.8 to 1°0, the S, Q, and R values are excellent compared to those of NaX, while below the above lower limit, S, Q decreases as M decreases. , and R
A tendency for the value to gradually decrease was observed. 1 from the point
The properties in the three types of zeolite compositions comprising NaM X of the present invention were limited to <0.8 or more as described above.

Next, the divalent metal-substituted Y-type zeolite composition of the present invention will be described. These compositions have a pore size of about 8 Y
Type zeolite is regularly ion-exchanged using a solution of water-soluble divalent metal chloride, nitric acid, etc.;
) can be obtained by carrying out. NaCa of the present invention
The optimum content m of divalent metals in the three types of zeolite solid phases of Y , NaSr Y + and NaBa Y is as follows.

That is, for the NaCaY composition, 6≧0.8+Na5rY
In the composition, tolerance ≧0.9. Furthermore, in the NaBaY composition, L
≧0.7 (equivalent fraction) is required to achieve separation efficiency for oxygen and nitrogen gases. Between the above-mentioned lower limit population fraction and the saturation value (M = 1), the air component was separated by the G, C, method using the activation amounts of the three types of zeolite 1-based compositions described above. It was observed that the peaks of oxygen and nitrogen gases were completely separated, and the S, Q, and R values related to G, C, and evaluation were improved compared to those of NaY. It was also confirmed that the adsorption and desorption of air components to the three types of NaMY compositions described above were carried out extremely quickly and under favorable conditions. Furthermore, below the lower limit value of M, the S, Q, and R values tend to gradually become smaller as the river decreases. Based on this reason, the numerical limitations of the load in the three types of NaMY composition of the present invention were carried out as described above.

Next, the type A zeolite composition substituted with calcium ions of the present invention will be described. Pore diameter: Pore diameter obtained by carrying out an ion exchange reaction at room temperature to high temperature (20 to 90°C) using a solution of water-soluble calcium chloride, nitrate, etc. on A-type zeolite. Approximately 5 Na
The optimum amount of solid phase calcium in the Ca Z zeolite composition is 6≧0. g equivalent fraction. Ca in NaCaZ=
Within the range of 0.9 to 1.0 equivalent fraction, the N2102 adsorption ratio (B-E-T method, 760 mm1! g i 25
C) tends to increase slightly in proportion to the calcium content, but this ratio is within the range of 3.18 to 3.3. The N2/02 adsorption ratio of the NaCa Z composition of the present invention (Ca≧00g equivalent fraction) is as follows:
-5A (powder) N210λ-3,0 (760mmH
g; 25°C).

The fact is that NaCa Z (Ca2O,9
) When air is used as a raw material gas and oxygen or nitrogen gas is separated or concentrated by the adsorption method using the composition, the difference in selective adsorption properties can be exhibited as described above, and the same type of adsorption is known. This clearly shows that the target gas can be easily obtained with higher efficiency compared to other agents.

The second invention is directed to separation and purification of oxygen and nitrogen gas, and ? The present invention relates to a method for molding a divalent metal-substituted zeolite composition that is effective for aggregation. That is.

A homogeneous mixture is obtained by wet blending the powder or small granules of the zeolite composition described above in the presence of an inorganic and/or organic binder.

This is molded into a predetermined shape, the resulting molded product is subsequently dried, and finally fired at a temperature range of 400 to 580°C to produce a molded product of an activated zeolite composition. It's a method. Suitable inorganic binders used in the molding of the present invention include colloidal substances such as bentonite, diatomaceous earth, kaolin, colloidal silica, and colloidal alumina. On the other hand, preferred organic binders include crystalline cellulose such as methylcellulose, carboxymethylcellulose, and hydroxyethylcellulose, and molasses.

During wet molding, the above-mentioned inorganic and organic binders may be used alone or in combination. The water content required in the mixing process of the present invention is controlled by the physical properties of the divalent metal-substituted zeolite composition as the raw material.1 In normal cases, a water content of 20 to 50% is an appropriate amount. be. Next, the amount of binder used will naturally vary depending on the type of binder and the physical properties of the molding material.

When using only an inorganic binder, the appropriate amount is 6 to 36% based on the zeolite composition material, while when using only an organic binder, 1 to 5% is 3Mff.
The range is 1. By using the above-mentioned amounts of water and binder, an easily moldable mixture can be obtained, which can be used to mold products into spheres, columns, pellets, cylinders, plates, honeycombs, and other shapes. It can be processed into next,
The obtained molded body is dried at around 100°C to adjust its shape, and then the zeolite composition is prepared. :(Ha) A molded body of a divalent metal-substituted zeolite composition suitable for the purification and concentration of oxygen and nitrogen gases of the present invention is obtained by firing in a temperature range below the decomposition start temperature. The above calcination temperature varies depending on the type of zeolite composition of the present invention used, but in normal cases, 400 to 580°C is appropriate;
The most preferred firing temperature range is 50 to 560°C.

Next, specific aspects of the present invention will be explained based on examples, but the present invention is not limited to these examples unless the gist of the invention is exceeded.

2 (J can j row 222) In this example, the ion-exchangeable monolithium of X-type zeolite (Na
NaCaX (Ca2
The present invention relates to a method for producing an active olide composition of O,8), Na5rX (¥≧0.8), and NaBaX (Ba2O, 8 equivalent fraction). The starting material NaX type zeolite is 1.0ONa2 (
A dry fine powder having a chemical composition of λ03.2.29SiO2.X120 was used. This was thermally activated and the specific surface area (S, S, A) was measured, and 838 rd/g
I got it. For the above NaX, as shown in the treatment conditions in Table 1, 2M 5rCIz+ I M Ba C
Batch method ion exchange with b+ and 2M CaCl:L aqueous solution was carried out 3-4 times at 60 °C and kept under stirring for 4-5 h to obtain NaSrX, N, respectively.
It was converted to aBaX, and NaCaX. After completing the final treatment by the batch method, the NaM X was centrifuged and then washed with water. Washing with water was carried out until chlorine ions disappeared. The NaMX composition after water washing is 100-110°
After drying at C, it was made into a fine powder.

The composition and yield of the zeolite composition NaMX obtained in this example are listed in Table 1. If the zeolite composition obtained in this example is thermally activated to form an anhydride, an adsorbent suitable for separating and concentrating oxygen and nitrogen gases can be obtained.

Example 2 is a NaM Y-type obtained by replacing the ionically fertile ions and lium of Y-type zeolite (Na Y ) with a divalent metal (Mi+). This relates to an example of manufacturing a zeolite composition.Ion exchange was performed 3 to 4 times by a batch method as shown in Table 2 to obtain Na5rY (liver ≧0.9), NaCaY (C
a2O,8) and NaB'aY (Ba2O,7
Equivalent fraction) Zeolite 1-composition was prepared. The NaY zeolite used as the starting material in this example was 1.09 Na2
O.81203 ・3.98 SiO;z ・X112
A dry powder having a chemical composition of 0 (D) was used. The specific surface a (S, S, A) of this activated powder is 937 m/g
Met.

Example-3 is the separation of oxygen and nitrogen gases obtained by replacing ion-exchangeable sodium in A-type zeolite (NaZ) with calcium ions, 4n'11
, and a method for producing active zeolite l-compositions of NaCa Z (Ca2O, g optical fraction) suitable for concentration. In this example, the starting material NaZ zeolite was 1. Q2Na20-A1. o3 ・1.9
A dry powder with a chemical composition of 2S+02.XIIxO was used. The specific surface area of the activated powder (S, 'S,
A) was 665 rrr/g. The ion exchange in this example is.

The procedure was carried out four times using a 2.5 M CaC1z aqueous solution at 60° C. for 4 hours under stirring to obtain a NaCa Z composition having a composition as shown in Table 2. This thermally active article has the characteristics described below and has been found to be excellent as an oxygen and nitrogen adsorbent.

Table 3 shows the N2 of the zeolite composition obtained according to the present invention.
102 adsorption ratio. Typically 1 lh 1 of the NaM X type zeolite I-composition of the present invention
The table shows how the 02 adsorption ratio is improved compared to NaX used as the starting material. The Nx10z adsorption ratio of the NaX active product of Comparative Example-1 was 2.81 (7
60 fin Hg i 25°C), but the Nz/Q2 adsorption ratio of the active product of the NaMX type zeolite 1-composition of Example-1 obtained by ion exchange is 2.94.
~3.75, and therefore the above adsorption ratio is within the range of Na
It was found that f1 was improved by 5 to 33% in MX compared to NaX. Furthermore, IJaCa Z of Example-3
Nz/C of active product of (Ca-ri, 9165 equivalent fraction)
lz adsorption ratio is 3.18, while the same commercial product MS-
5A (Comparative Example-2) is within the range of 2.9 to 3.0. Therefore, the former shows a 6 to 10% higher adsorption ratio than the latter. The above facts clearly indicate that when the active ingredient of the zeolite composition of the present invention is used as an adsorbent for the purpose of separating and concentrating oxygen and nitrogen gases, the separation efficiency is further increased.

Actual difference 2↓1 This example relates to the second invention, and relates to a method for producing a molded body of an activated zeolite composition suitable for purification and concentration of oxygen and nitrogen gases. be.

As a material for the zeolite composition for molding, NaCa Z composition (Ca=0
．． 9186; Na=0.0814 equivalent fraction) 60 kg of dry powder was used. 13.8 kg of bentonite fine powder and 1.2 kg of methyl cellulose were added to the above-mentioned zeolite composition material and mixed for 2 hours and 30 minutes using a V mixer to prepare a mixture. next.

Water was added to the above mixture and mixing was carried out for 3 hours and 50 minutes. Moisture in the mixture at the end of mixing is 35-36%
was held. Next, using the mixture, wet molding was performed to prepare 1/16" pellets, and the resulting 1/16"
'Drying of the pellets was carried out at 100-110<0>C. After further adjusting the length of the dried pellets using a flasher, the above pellets were finally heated to a temperature of 530 to 550°C.
A molded body of an active zeolite composition was obtained by firing for 4.5 hours.

In this molding, the fired 1/16" pellets are 45
kg was obtained. In addition, 1/16″ obtained in this example
The physical properties of the molded body were as follows.

Average strength of 1/16″ beret: τ=3.04kg/p
Apparent density of ellet 1/16″ pellet: T = 1.
3081/16″ S, S, A: 56
Nz102 adsorption ratio of 9rrr/g1/16” pellet:
3.17 (760fl1g; 25°C) N of the fired 1/16" pellets obtained in this example
The 210U adsorption ratio is <3.17 as mentioned above, while the Nx102 adsorption ratio of commercially available MS-5A, 1/16' pellets is 2.93. Looking at this, it is clear that the 1/16" pellets obtained in this example are more effective in separating and concentrating oxygen and nitrogen gases than commercially available products. Single molded product, NaCaZ, 1/16″
G, C, and C tests were conducted using crushed pellets with a particle size distribution of 40 to 60 mesh, but the peaks of oxygen and nitrogen in the air were completely separated, and the obtained S, Q It was found that both the R value and the R value were excellent.

Next, the NaM 1/16'' berene I- was prepared by firing. Furthermore, NaX used as a starting material in Example-1
(1,0ONazOHAIJ3・2.29SiO=・
XH□0) powder and NaY (1,09NaxO・Al2O3・3.9
8SiOx ・XIl, 0) The molding of the powder was carried out according to Example 4, and the molded body was finally heated at 530 to 550°C.
．． By firing for 5 hours, activated NaX・
1/16" pellets and NaY 1/16" pellets were prepared. Prototype Na5rX ・1/16
"Pellets, NaCaX・1/16" pellets and NaX・1/16''Veresol-, Na5rY・1/
16" pellet, NaBaY・1/16" pellet, N
aCaY・1/16″ bellet and NaY・1
/16" pellets were crushed into coarse particles, which were then classified into 8 categories, and those in the particle size range of 40 to 60 meso were used as G, C, test samples. G, C, For testing, Gas chromatography filling tube (3φ x 2000m
) was filled with 8 to 9 g of a molded body (40 to 60 mesh) of the above zeolite composition. Caram aging 2
After carrying out the test at 60° C. for 15 hours, G and C tests were conducted under the GC9 measurement conditions listed in Tables 4 and 5 using air as the test gas and helium as the carrier gas.

As shown in Table 4, in the G and C tests using the activation amounts of Na5rX and NaCa It was observed that the S, Q, and R values obtained using these two types of molded bodies were increased compared to these values of the NaX molded body of Comparative Example-1.

Even if the carrier gas flow rate was increased by 4.5 times, NaSr
S when using X molded body.

The Q and R values remained unchanged. Furthermore, the S, Q, and R values when using the NaCa These facts indicate that the NaMX (M=Sr, Ca) molded body is suitable as an adsorbent for separating and concentrating oxygen and nitrogen gases. Table 5 relates to G, C, and tests using the activation amount of the NaM Y molded body. Under the indicated C, C, and measurement conditions, the NaMY molded body (M = Sr, Ba + 'C
a) The S, Q, and R values obtained during use are those of Comparative Example-3.
It was found that these values were superior to those obtained when using the NaY molded body. Adsorption and desorption of oxygen and nitrogen gas to NaMX type adsorption type intermediate adsorbent and MY type adsorbent are performed using G, C,
From the data, it is clear that the above type of adsorbent' has the characteristic of exhibiting high efficiency when separating and purifying the above gas by adsorption method, since it can be carried out more quickly compared to known adsorbents. It is.

In short, one aspect of the present invention is the separation of oxygen and nitrogen gases.

Seven zeolite compositions suitable for purification and concentration (Na
MX, NaMY (M=Ca, Sr, Ba) and Na
The adsorption method of the present invention is recognized to be widely used in the gas field.

(Margin below) Table 2, Swelling sequence of NaMY and NaCa Z-type zeolite compositions (Examples-2 and 3) Table 3, Nz/(b absorption ratio of zeolite compositions) Table 4, G, C , - test (
The value in parentheses indicates the equivalent fraction.

*A molded body of the indicated zeolite composition is crushed to give 40
~60 mesoyu for the official.

Claims (1)

[Scope of Claims] 1. X-type zeolite, Y-type zeolite or A-type zeolite 1~ The sodium contained in the alkaline earth metal is 0
．． A zeolite-based composition suitable for separating oxygen and nitrogen that has been ion-exchanged at an equivalent fraction of 7 or more. 2. The zeolite composition according to claim 1, wherein the alkaline earth metal is calcium, strontium and/or barium. 3. The zeolite composition according to claim 1, wherein the sodium contained in the X-type zeolite is ion-exchanged with calcium, strontium and/or barium in an equivalent fraction of 0.8 or more. 4. Sodium contained in Y-type zeolite is at least 0.8 equivalent fraction of calcium or 0.9 g of strontium
The zeolite composition according to claim 1, which is ion-exchanged with barium in an equivalent fraction or more, or 0.7 equivalent fraction or more with barium. 5. The zeolite composition according to claim 1, wherein the sodium contained in the A-type zeolite is ion-exchanged with calcium in an equivalent fraction of 00 g or more. 6. Sodium contained in X-type zeolite, Y-type zeolite and/or A-type zeolite is alkaline earth metal and is 0.
．． Powder or small granules of a zeolite composition that has been ion-exchanged at an equivalent fraction of 7 or more. Wet mix with inorganic and/or organic binders. After molding the mixture, it is dried and
A method for producing a molded body made of a zeolite composition suitable for separating oxygen and nitrogen, characterized by firing at a temperature of °C. 7. A method for producing a molded body comprising a zeolite composition according to claim 6, wherein the alkaline earth metal is calcium, strontium J1 and/or barium. 8. Zeolite-based composition according to claim 6, in which the sodium contained in X-type zeolite is ion-exchanged with calcium, sulfur and/or barium in an equivalent fraction of 0.8 or more. How to assemble a molded body. 9. Sodium contained in Y-type zeolite is 0.8 equivalent fraction or more for calcium or 0.8 equivalent fraction for strontium.
7. A method for preparing a molded body made of a zeolite composition according to claim 6, which is ion-exchanged with barium at an equivalent fraction of 0.7 or more. 10. A method for preparing a molded body made of a zeolite composition according to claim 6, wherein the storium contained in the A-type zeolite is ion-exchanged with calcium at an equivalent fraction of 0.1 g or more.