JPS5845110A - Manufacture of synthetic zeolite using tuffaceous mineral as starting material - Google Patents

Abstract

PURPOSE:To obtain synthetic zeolite having a specified composition or a mixture of >=2 kinds of synthetic zeolite by treating a tuffaceous mineral contg. natural zeolite crystals or a glassy tuffaceous mineral with K or Na hydroxide, K or Na chloride or sodium aluminate. CONSTITUTION:An aqueous soln. of KOH is added to powder of tuffaceous mineral contg. natural zeolite crystals such as clinoptilolite or a glassy tuffaceous mineral and reacted under heating to form W type zeolite and/or chabazite. The product is separated by filtration, washed in water, and dried. By adding an aqueous soln. of KOH and KCl, P type zeolite, W type zeolite, Linde F type zeolite or a mixture of >=2 kinds of such zeolite is formed, and by adding an aqueous soln. of sodium aluminate and alkali metallic hydroxide, A type zeolite, P type zeolite, chabazite, herschelite, analcime or a mixture of >=2 kinds of such zeolite is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention uses tuff minerals containing natural zeolite crystals such as critunotyrolite and mordenite or amorphous glassy tuff minerals as starting materials, and processes powders of these minerals with alkali metal hydroxide. A-type zeolite (Na2O6A
t203 ・2SiOz-nH2O), X-type zeolite (Na2O, At203-2,5SiO2・nH2O)
, P-type zeolite [(Na2, K2O) At2o
3-3,. 3-5.38 IC++ -nH2O)
1. W-type zeolite (K2O-At203-38iO
2'-nH2O), Linde F type zeolite (K2O-A
t203-2SiO□-nH2O), chabasite (K
2O・At203' 48102 ・nH2O), anal'sime (Na2O・At203 ・4Si02
・nH2O), vergilite [(Na, K)4At4
The present invention relates to a method for producing synthetic zeolite using tuff-based minerals as a raw material to produce synthetic zeolite made of Si8024.nH2O] alone or in a mixture of two or more.

The first aspect of the present invention is to add W-type zeolite (K2O
・At20a・38102-nH2O), chabasite (K2O・At203・4S102・nH2O) alone or in a mixture is produced.This is a method for producing synthetic zeolite using tuff minerals as raw materials.

The second aspect of the present invention is to add aqueous solutions of potassium hydroxide and potassium chloride to powder of tuff-based minerals or glassy tuff-based minerals containing natural zeolite crystals such as clinoptilolite and mordenite, and subject them to a heating reaction treatment. By this, P-type zeolite [(Na20.20)・At203
・3.3~5.3S102・nH2O):], W-type zeolite (K2O-At203-3Si02-nH2O
), IJ 7 TeF type theolite (K2O-At203
・2S102・nH2O) is a method for producing synthetic zeolite using tuff-based minerals as a raw material, which is characterized by producing one or a mixture of two or more of them.

The third aspect of the present invention is to add sodium aluminate and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide to tuff minerals containing natural zeolite crystals such as critunotyrolite and mordenite or glassy tuff mineral powders. By adding an aqueous solution and performing a heating reaction treatment, A
type zeolite (Na2O,” At203-2Si02
- nH2O), P-type zeolite ((Na2O',
K2O) ・At203 ・3.3~5.3 SiO2
・nH2O], chabasite (K2O-At203"
4Si02- nH2O), /%-Silyte [(Na
, K)4A44Sig024-nH2O'),
Anal Rhinoceros A (Na2O-At2o3-4Si02-
This is a method for producing a synthetic zeolite using a tuff-based mineral as a raw material, which is characterized by producing one or a mixture of two or more of nH2O).

The fourth aspect of the present invention is to add aqueous solutions of sodium aluminate, sodium hydroxide, and sodium chloride to tuff-based minerals or glassy tuff-based mineral powders containing natural zeolite crystals such as critunotyrolite and mordenite, and heat reaction treatment. By doing so, type A zeolite (Na2O-A
t203-28iO2-nH2O), P-type zeolite [
(Na2o, Ni20)・At203・3.3~5, :3
5i02-nH2O'], X-type zeolite (Na20
-At203.2,55in2.nH2O) is produced alone or in a mixture of two or more of them.

The fifth aspect of the present invention is to add aqueous solutions of sodium aluminate, potassium hydroxide, and potassium chloride to a powder of a tuff mineral or a glassy tuff mineral containing natural zeolite crystals such as clinoptilolite and mordenite, and then heat the mixture. By reaction treatment, chabasite (20,
This is a method for producing synthetic zeolite using tuff-based minerals as a raw material, which is characterized by producing At203=4sio2-nH2O).

In mineralogy, zeolites are called Fluorine Group 5, and are crystalline hydrated aluminosilicates of alkali metals or alkaline earth metals with a three-dimensional crystal structure, and are either naturally occurring or synthesized. . The general formula of the composition is MeO
It is represented by -At203-msi02-nH2O (where Mθ is an alkali metal or alkaline earth metal element).

Many natural zeolites contain various glue-like clay minerals, quartz, etc., so their properties as zeolites, such as molecular sieving effect, adsorption capacity, and ion exchange capacity, are lower than those of synthetic zeolites, and they are also heterogeneous. It is difficult to control the catalytic action.

Therefore, synthetic zeolites are exclusively used for industrial applications such as those mentioned above. Synthetic zeolites generally have a composition of Na2O-At203-SiO□-H20.
It is crystallized from the composition 5'/l/ of K2O-At203-8i02-H2O.

The present invention focuses on the EIiO2 and Al2O2 components in naturally occurring tuff-based minerals containing zeolite crystals such as clinoptilolite and mordenite, or non-i-crystal glassy tuff-based minerals with a similar chemical composition. By subjecting tuff-based mineral powder to a heat reaction treatment at a relatively low temperature with an aqueous solution of additives as described above, a synthetic zeolite having a specific chemical composition is produced singly or as a mixture of two or more types, thereby producing This makes it possible to economically produce synthetic zeolite through a simpler reaction treatment than with natural tuff minerals, which are inexpensive and abundantly available.

Next, the present invention will be explained by examples.

The types of naturally occurring tuff minerals used as raw materials in each example and the components determined by chemical analysis are shown in Table 1 below.
It is as shown in.

Actual Example 1 The six raw materials Nα1-N16 shown in Table 1 were air-dried and then ground to a particle size of 149μ or less.

For Tani raw material powder 57, the concentration of potassium hydroxide water bath solution was changed to 1 mol, 2 mol, and 3-mol f61ei each 100 ml.
and heated them in a 300-inch Erlenmeyer flask equipped with a reflux condenser, and while refluxing in a boiling state,
The reaction mixture was allowed to react for 8 hours, and then filtered using a glass filter with a 3G mesh. .

Wash with water until the pH of the θ-1 solution becomes 9 to 10, and add 95uO
The amount of dry matter and the product were measured by X-ray diffraction, and the results are shown in Table 2 below.

Example 2 As in Example 1, potassium hydroxide 1 mol, 2 mol, 3 mol and potassium chloride 1 mol,
100 me of a mixed aqueous solution of 2 mol and 3 mol was added and reacted for 24 hours while refluxing in a boiling state using a 300-meter Erlenmeyer flask equipped with a reflux condenser, and the following treatment was performed in the same manner as in Example 1. The results are shown in Table 3 below, and P-type zeolite, W-type zeolite, and Linder-type zeolite were obtained.

Table-3 P: P-type zeolite ((Na20.20)AA20
3・3.3-5', 3Si02・2H20) W: W
Type zeolite (N20/At203/3SiO2-/5
H20) F: Linder type zeolite (N20/At2
03.2SiO2.3H20) Example 3 To each of the same raw material powders 52 used in Example 1, sodium aluminium 52, sodium hydroxide 52 and water FA) me
was added, and reacted for 6 hours under boiling reflux using the same reactor as in Example 1, and then treated in the same manner as in Example 1. As a result, the floor 1 raw material contained sodalite, (Na4A
t3Si30,2) and A-type zeolite (Na20-A
t203-2Si02-nH2O)8.12
Even with the obtained 4°Nα2 raw material, 8.12 of the same product as the Nα1 raw material was obtained.

For the Nα3 raw material, only sodalite was obtained, and for the N114 raw material, a mixture of sodalite and A-type zeolite was obtained at 8.1 fI.

When the amount of sodium aluminate was b, ie 2.52, all the products were sodalite.

Example 4 To each of the same raw material powders 52 used in Example 1, 57 sodium aluminate, 52 sodium hydroxide, 3 t of sodium chloride, and 50 ml of water were added, and the following was carried out using the same apparatus 6 as in Example 1, and treated under the same reaction conditions. Tokoro, NIL l
The raw material is P-type zeolite (Na2o-At2o3.3.
3-5.3 si○2・2H20), A-type zeolite (
, Na2O・At203・2S102・nH2O),
type zeolite (Na2OeAt203-2.5 Sin
□・nH2O) was obtained at 8.09%, N[L2 raw material gave a P-type zeolite and A-type zeolite at 7.92% was obtained.3, Na:3 raw material was P-type. A mixture of approximately equal amounts of zeolite and type A zeolite (8.32 g) was obtained.

Na・1 raw materials include P-type zeolite, A-type zeolite, and
An approximately equal mixture of type zeolites was obtained.

For jm 5 raw materials, only P-type zeolite obtained 8.22.
When the sodium aluminate was made to have a concentration of /2, that is, 2.57, the formation of sodalite was observed in all samples, and type A zeolite disappeared.

Example 5 The same six types of raw material powders used in Example 1 were added to 5V, 1.5 r of sodium aluminate, 57 g of sodium hydroxide, and 100 mj of water! and 2. in the same apparatus as in Example 1.
After standing still for 1 hour, the mixture was brought to a boiling state and refluxed, and reacted for 6 hours. P-type zeolite was obtained in the range of 5.61 to 6.17 for any of the raw materials from 1 to N116 except for the raw material for Nα4.

In particular, the crystal development using the N[L5 raw material was good. In addition, the formation of A-type zeolite was also observed in the Nα4 raw material.

Implementation 116 Sodium hydroxide 52 and sodium aluminate 2.5f or 5.5f were added to the same six raw material powders 52 as used in Example 1. After adding Og and 100 of water, the mixture was allowed to stand for 24 hours in the same apparatus as in Example 1, and then refluxed under boiling for 24 hours.

In the reaction system with 2.52% sodium aluminate added, Nα
All raw materials from 1 to M6 are P-type zeolite only 4.7f
-5.0t, and the crystallinity was better developed than that of the P-type zeolite produced in Example 5.

Add 5.02 ml of sodium aluminate to 1 t in the reaction system.
4IIL], Nα2, N (the raw material for L3 is a mixture of P-type zeolite and sodalite 5.7'9 to 6.1 y
With the raw material of 3° Na·l obtained, 5.29% of a mixture of A-type zeolite and P-type zeolite was obtained. 6. Only P-type zeolite is used as the raw material for Nα5 (mordenite). I got Ov.

In addition, P-type zeolite 8 with good crystallinity is used as a raw material for 1α and 6.
．． I got 92.

Example 7 'To NILI raw material (large capacity, clinoptilolite) powder 1 () 7, add sodium aluminate 52 or 109, sodium aluminate 109 and water 300ml, and mix it into an electromagnetic stirrer type round shape. Reaction temperature + 5 using autoclave
+1"C for 21 hours with stirring, followed by -Kh (11 treated as in Example I).

When sodium aluminate 52% was added, P-type zeosite 10% was obtained. Also Alminoba Natriuno, 1
If 0v is added, aluminic acid is added) IJum 5S/
Type 1 zeolite 11.59 which has better crystallinity than the case where 11.59 is added is a4)/this.

Example 8 2.52 ml of sodium aluminate, 57 potassium hydroxide, and 100 ml of water were added to 52 each of the same NIL 3 and Nα5 raw materials used in Example 1, and the mixture was allowed to stand for 24 hours in the same apparatus as Example 1. After that, the mixture was subjected to a reflux reaction in a boiling state, followed by filtration, washing, and drying.

The raw material for N13 is chabasite (K2O, At203,
4SiO2.6H20) 6.59 was obtained. Also, the fifth ingredient is chabasai) 6. I got Of. ' Example 9 The same Nα4 and Nα6 used in Example 1 were used.
Sodium aluminate 5f, potassium hydroxide 52 and water 100- were added to each of the four raw material powders α1, Nα2, Nα3, N[1,5], and the mixture was placed in the same apparatus as in Example 1.
After being allowed to stand for 4 hours, reflux reaction was carried out in a boiling state for 24 hours, and then the same treatment as in Actual Stream Side 1 was performed.

Bar/lite ((Na+K)4At48ig02412H20 with good crystallinity regardless of the raw material used)
:] 8.6-9. Obtained in the range of.

Example 1O Nα1 raw material (large capacity, clinoptilolite) powder 10
Add 11 mouthfuls of sodium aluminate, or 10 f, 102 m of potassium hydroxide, and 300 me of water, and use a cylindrical autoclave for electromagnetic stirring to bring the reaction temperature to 15 m.
The reaction was carried out with stirring at 0'C for 21 hours, and then the same treatment as in Example 1 was carried out.

When sodium aluminate 57 was added, analcyme (Na20-At203-4SiO2-
2H20) 12.4 S' was obtained. In addition, when sodium aluminate H19 was added, Vergilite [(Na
, K)4At4Si8024・+2H20]17.2
I got y.

Ten 1) J11 Example 11゜Nu l raw material (kritnotyrolite from Otani) powder 1
07 3 mol potassium hydroxide water bath dk and 3 mol JA
M chloride potassium aqueous solution mixed solution 300. m7! In an electromagnetically stirred cylindrical autoclave, J'1 was stirred and stirred at 150''C for 21 hours, and then the same treatment as in Example 1 was carried out. K2O・At2O-28i○2・3H
20) '6.1 f/ was obtained.

Example 12 5 tons of sodium aluminate, 3.7 f of sodium chloride, and 50 me of water were added to 5 vol of Nα5 raw material (mordenite) powder. ! ; Boiling reaction was carried out for 6 hours using the same reactor, followed by filtration, washing and drying to obtain chabasite 6.12.

Patent Applicant Murakashi Lime Industry Co., Ltd. Ooya Procedural Amendment November 2, 1981 (To the Commissioner of the Japan Patent Office (To the Patent Office Examiner) 1. Indication of the case 1982 Patent Application No. 142862 2. Title of the invention, method for producing synthetic zeolite using pseudogray minerals as raw materials 3. Relationship with the amended case Applicant 4. Agent address: 1-1 Z, Minami-Aoyama-chome, Minato-ku, Tokyo. Contents of the amendment (1): The description of the "Claims" from the fifth line of the first page of the specification to the third line of the third page of the specification is corrected to the attached sheet.

(2), page 8, line 13 of the specification “51o2・At2o
3" is corrected to "5102.At203".

``2. Claims (1) W-type is produced by adding an aqueous solution of potassium hydroxide to a powder of a tuff-based mineral or a glassy tuff-based mineral containing natural zeolite crystals such as clinoptilolite and mordenite and subjecting it to a heating reaction treatment. Zeolite (K2O-hQ2
o3-35io2-nH2O), chabasite (K2O
-ht2o3-45io2'nH2O) alone or as a mixture.

(2) P-type zeolite is produced by adding aqueous solutions of potassium hydroxide and potassium chloride to the powder of tuff-based minerals or glassy tuff-based minerals containing natural zeolite crystals such as clinoptilolite and mordenite, and subjecting them to a heating reaction treatment. [(Na20.2o)・At2033.3-5.
3S1o2・nH2O)], W-type zeolite (K2O-
At203-3Si02・nH2O), Linde F type zeolite (K2O・At203・2S102・nH2O'
) A method for producing synthetic zeolite using tuff-based minerals as a raw material, characterized by producing either alone or in a mixture of two or more.

(3) Aqueous solutions of sodium aluminate and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are added to tuff-based minerals containing natural zeolite crystals such as clinoptilolite and mordenite, or glassy tuff-based mineral powders. By adding and heating reaction treatment, type A zeolite (Na 20 ・Az203 ・2 S io 2
'nH20'), P-type zeolite C (Na20
, to 20)-ht2o3-3.3~5.38iO2"
nH2O, ), chabasite (K2O-At203・
4S102・nH2O), vergilite [(Na, K)
4At4SiBO24' nH2OJ, analcyme (
A method for producing synthetic zeolite using tuff-based minerals as a raw material, characterized by producing one or a mixture of two or more of Na20, At203, 4SiO2, nH20).

(4) By adding aqueous solutions of sodium aluminate, sodium hydroxide, and sodium chloride to tuff-based minerals or glassy tuff-based mineral powders containing natural zeolite crystals such as clinoptilolite and mordenite, and subjecting them to a heating reaction treatment. , 'A-type zeolite (Na20-At2
03.2Si02.nH2O), P-type zeolite ((N
azO+K2O)・At20. -3.3~5.35i
n2-nH2OJ, X-type zeolite (Na20/At2
05.2.5Sio2.nH2O) alone or in a mixture of two or more thereof.

Claims (5)

[Claims] (1) W-type zeolite (K2O・AA2
03.3Si02.nH2O), chabasite (K2O
-At203-48iO□-nH2O) alone or as a mixture. (2) P-type zeolite is produced by adding aqueous solutions of potassium hydroxide and potassium chloride to the powder of tuff-based minerals or glassy tuff-based minerals containing natural zeolite crystals such as clinoptilolite and mordenite, and subjecting them to a heating reaction treatment. C(Na201 K2O)4tz033.3-5.
35iO2-nH2O)'), W-type zeolite (,K2
O-At203-3SiO2-nH2), Linde F type theolite (K2O・At203・2Sio2・nH2O
) A method for producing synthetic zeolite using tuff-based minerals as a raw material, the method comprising producing one or a mixture of two or more of the following. (3) Aqueous solutions of sodium aluminate and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are added to tuff-based minerals or glassy tuff-based mineral powders containing natural zeolite crystals such as clinoptilolite and mordenite, and heated. By reaction treatment, type A zeolite (Na20-At203-2Si02-nH2O
), P-type zeolite ((Na2O, ni20) ・AA
20a・3.3~5.3SiO2-nH2'O], Chichasasa1toK2O・At203・4Si02・nH2
O), vergilite ((Na, K)4At4si8o2
4-nH2O), analcyA (Na20-At2
03.4Si02.nH2O) alone or in a mixture of two or more thereof. A method for producing synthetic zeolite using tuff-based minerals as raw materials. (4) By adding aqueous solutions of sodium aluminate, sodium hydroxide, and sodium chloride to tuff-based minerals or glassy tuff-based mineral powders containing natural zeolite crystals such as clinoptilolite and mordenite, and subjecting them to a heating reaction treatment, A-type zeolite (Na20/At203
・2S10□-nH2O), P-type zeolite ((Na2
0. 20)-At203・3.3~5.3Si02・
2H20], X-type zeolite (Na2O-At203-
2.55in2-nH2O) alone or in a mixture of two or more thereof. (5) Aqueous solutions of sodium aluminate, potassium hydroxide, and potassium chloride are added to the powder of tuff-based minerals or glassy tuff-based minerals containing natural zeolite crystals such as critunotyrolite and mordenite, and the mixture is subjected to a heating reaction treatment. By this, Chabasite (K2O・At203・
A method for producing synthetic zeolite using a tuff-based mineral as a raw material, characterized by producing 4Si02.nH2O).