JPH0674128B2 - Method for producing ZSM-5 zeolite using humus - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing ZSM-5 zeolite using humus.

[Conventional technology]

Zeolite is a general term for a group of crystalline aluminosilicates, which are naturally produced as minerals, but until now, those that have the same crystal structure as natural products and those that do not naturally occur have been synthesized. There is a wide variety. Also industrially
Since 1980, attention has been paid to the catalytic action using the solid acidity and the pores, and many synthetic studies and applied studies have been conducted in various fields. ZSM-5 zeolite is one of the synthetic zeolites invented under such circumstances, and has a powder X-ray diffraction pattern as shown in Table 1.

The method of synthesizing ZSM-5 zeolite is disclosed in, for example, US Pat. No. 3,702,886, US Pat. No. 3,894,106, US Pat. No. 3,928,483, and British Patent No. 1,402,981. Recently, a method of synthesizing an organic compound mainly containing an organic base as shown in Table 2 has become widely known.

[Problems to be Solved by the Invention] However, the organic compounds shown in Table 2 were used.
The method of synthesizing ZSM-5 zeolite has the following problems.

(1) Since a large amount of expensive amines such as tetrapropylammonium is used, the synthesis of ZSM-5 zeolite is expensive.

(2) Since toxic amines are used, the working environment is apt to deteriorate, and the waste water after the production of ZSM-5 zeolite cannot be easily treated. For this reason, there is a problem that the cost is inevitably increased in order to maintain a good working environment.

(3) There is a drawback that the synthesis takes several days and the synthesis time becomes long.

The present invention has been made to solve such conventional problems, and its purpose is to (1) ZSM
-5 zeolite can be manufactured at low cost, (2) can maintain a good working environment, and (3) can be used to synthesize ZSM-5 zeolite in a relatively short time. 5 to provide a method for producing zeolite.

[Means for solving problems]

The production method according to the present invention comprises a humus separated from soil organic matter or lime and at least one source material of a silicon oxide source material, an aluminum oxide source material, an alkali or alkaline earth metal oxide source material and water. Is prepared, and the reaction mixture is subjected to hydrothermal synthesis until zeolite crystals are formed.

The term "soil organic matter" as used herein is a general term for organic matter existing in soil, and includes all biological remains in the soil and their decomposition / humification products, and is classified as shown in Table 3.
[From Kononova, MM, Ichiro Kanno et al., “Soil Organic Matter”, New Scientific Literature Publication Society (1966), Kyoichi Kumada “Chemistry of Soil Organic Matter” 2nd Edition, Academic Publishing Center (1981). ] To separate humus from soil, extract it with an aqueous alkaline solution. Humic acid is a collection of amorphous polymeric substances having various molecular sizes and having an average molecular weight of tens of thousands. This humic acid is a substance that can be precipitated from NaOH soil extract with a strong acid and is sparingly soluble in water.
The color is dark brown to blackish brown. Fulvic acid is a substance that is soluble in both alkali and acid, and has less carbon content and more oxygen than humic acid. Furthermore, it has a low molecular weight and a high content of carboxyl groups. Humin is one in which humic acid or the like releases carbon dioxide gas and water to polymerize or condense, thereby being further stabilized. Although it does not dissolve in a dilute alkaline solution, it is eluted with about 10% NaOH solution and treated again with an oxidizing agent such as nitric acid to give nitrohumic acid, which differs from the initial humic acid in its properties. Has become.

Humus content in soil ranges from 1% to 40%. Table 4 shows the humus content in the case of allophane as an example. [Clay Handbook, edited by The Japan Clay Society, Gihodo (1967). ] Humic substances such as humic acid and fumin are also contained in lime. Table 5 shows the components of lime by the rational analysis. [Wataru Funasaka, Chikao Yokogawa “Kimekagaku” Kyoritsu Publishing (1964). ] Bitumen (bituminous material) contains pitch, asphalt, etc., and is extracted with an organic solvent. It is said to be due to the modification of resin, fats and oils and waxes in the raw plant.

The humus used in the present invention is mainly extracted from clay minerals such as volcanic ash soil, black mud soil and colloidal soil, and lime such as lignite and peat. Humic acid and nitrohumic acid can be obtained by adding HCl, H ₂ SO ₄ , HNO ₃ or the like to the above-mentioned humus extract and filtering and separating the formed precipitate. In addition, industrial humic acid soda, which has been dried and granulated into products, sodium nitrohumate made by oxidizing lignite with nitric acid, and humic acid reagent can also be used. Fulvic acid is obtained by heating, concentrating and drying the supernatant after the humic acid fractionation. Fumin is obtained as a mixture with an inorganic component by drying a component insoluble in an aqueous sodium hydroxide solution of soil.

These humus are used alone or in a mixture of two or more kinds. The effect is exhibited when the amount of these humus added to the reaction mixture in the synthesis of ZSM-5 zeolite is at least 0.001 wt% or more based on the reaction mixture, but 0.01 wt% or more is desirable to obtain a sufficient effect. Also, it is economically undesirable to add more than necessary, so 10 wt
% Is the limit, and 0.01-5 wt% is preferable.

Typical examples of the silicon oxide source material (silica source) are silica gel, colloidal silica, silica sol, crystalline sodium silicate, water glass, silicic acid anhydride, finely powdered silicic acid,
Examples include powdered silica glass and amorphous aluminosilicate natural minerals that have been dealuminated by acid treatment. Typical examples of the aluminum oxide source material (alumina source) include aluminum hydroxide, sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum chloride and activated alumina.
Furthermore, natural minerals that depend on nature as an aluminosilicate and that originally contain a silica source and an alumina source can also be used. Typical examples include kaolin, colloidal soil, Kanto loam soil, volcanic ash soil, and silica-alumina gel. Typical examples of the alkami or alkaline earth metal oxide source material (aqueous alkali cation solution) include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like.

Hydrothermal synthesis is preferably carried out while maintaining the reaction mixture at a temperature of 80 to 220 ° C.

[Example 1] (1) Extraction of humus Kanuma soil from Tochigi prefecture was collected as volcanic ash soil, and this original soil 10
5000 g of 8% NaOH aqueous solution was added to 00 g (moisture content 68%), and the mixture was heated and leached at 90 ° C. for 5 hours. The composition of the leachate filtered from the original soil is Al ₂ O ₃ 0.146wt%, SiO ₂ 0.017wt%, NaOH
The content was 7.9 wt% and the C content was 0.029 wt%. The amount of humus was estimated to be 0.05 wt% from the C content.

(2) Synthesis of Na-type ZSM-5 87.89 g of precipitated silica (97.5% SiO ₂ ) manufactured by Kanto Kagaku, Al
_{(NO 3) 3 · 9H 2} O26.69g, water 434g, NaOH11.8g, was formulated exudate 140g obtained in the above (1) 1 autoclave. The composition of this composition is _{4.7Na 2 O-37SiO 2 -1Al 2} O 3 -860H 2 O in a molar of oxides, humus content was 0.01 wt%. The autoclave was kept at 175 ° C and crystallized at 300 rpm for 24 hours. The obtained crystalline product was separated from the mother liquor by filtration, washed with water and dried at 150 ° C. for 1.5 hours. The powder X-ray diffraction pattern of this Na-type product is shown in FIG. This makes ZS
It was confirmed to be M-5 zeolite. The measurement conditions for X-ray diffraction are Cu tube, Ni filter, 30kV, 20m.
A, 1000 cps, TC1, 4 / min., 2 cm / min.

Example 2 precipitated silica _{(95.7% SiO 2) 91.66g,} Al (NO 3) 3 · 9H 2
O.27.32 g, NaOH 24.02 g, water 583 g, and sodium humate hydrate (manufactured by Teishi Stone Ternite) 0.40 g were mixed in one autoclave. The composition of the composition was 5Na ₂ O-41SiO ₂ -1Al ₂ O ₃ -950H ₂ O in terms of mol of oxide, and the concentration of sodium humate was 0.055 wt%.
The Na-type product obtained by crystallization and separation in the same manner as in Example 1 showed the same X-ray diffraction pattern as in FIG. 1, and was confirmed to be ZSM-5 zeolite.

Example 3 as a water glass "J silicate soda No. 3" (SiO ₂ 29%, manufactured by Nippon Chemical _{Industrial) 75.62g, Al (NO 3)} 3 · 9H 2 O6.83g, 60%
8.80 g of HNO ₃ , 0.20 g of sodium nitrohumate (manufactured by Nippon Heavy Chemical Industry Co., Ltd.), and 250 g of water were mixed in an autoclave at high speed. The composition of the composition was 6Na ₂ O-41SiO ₂ -1Al ₂ O ₃ -1800H ₂ O in terms of oxide, and the concentration of sodium nitrohumate was 0.059 wt%. Na obtained by crystallization and separation in the same manner as in Example 1
The product of the type shows the same X-ray diffraction pattern as in FIG.
It was confirmed to be M-5 zeolite.

Example 4 Example 3 was repeated except that 0.30 g of a mixture of fulvic acid and fumine was used instead of sodium nitrohumate in Example 3.
The same operation was performed. The composition of the composition is 6Na ₂ O-41SiO ₂ -1Al ₂ O ₃ -1800H ₂ O in terms of oxide mole, and the concentration of the mixture of fulvic acid and fumin is 0.089w.
It was t%. The Na-type product obtained by crystallization and separation by the same method as in Example 1 showed the same X-ray diffraction pattern as in FIG. 1, and was confirmed to be ZSM-5 zeolite.

Example 5 (1) Naturally dried colloidal soil from Tochigi prefecture (water content 20 wt
%) 600 g, 1500 ml of 10N HNO ₃ solution was added, and the mixture was reacted at 80 ° C. for 1 hour to elute the contained alumina content and iron content in the acid solution. After the reaction, the colloidal soil thoroughly washed with a large amount of water was separated from the mother liquor by filtration. This acid-treated colloidal soil is heated at 150 ℃ for 24 hours.
The chemical composition after drying for hours was as follows.

SiO ₂ -86.5 Al ₂ O ₃ -1.19% Fe ₂ O ₃ -0.42% Moisture -10.45% SiO ₂ / Al ₂ O ₃ molar ratio 123 (2) Synthesis of Na-type ZSM-5 49.30 g of the nitric acid-treated colloidal soil, _{al (NO 3) 3 · 9H} 2 O9.04g,
10 g of NaOH, 295 g of water, and 0.20 g of sodium humate (manufactured by Teishi Stone) were prepared in one autoclave. The composition of the composition was 5Na ₂ O-40SiO ₂ -1Al ₂ O ₃ -950H ₂ O in terms of molar ratio of oxide, and the concentration of sodium humate was 0.055 wt%.
The Na-type product obtained by crystallization and separation in the same manner as in Example 1 showed the same X-ray diffraction pattern as in FIG. 1, and ZSM-5
It was confirmed to be zeolite.

[Comparative example]

Precipitated silica _{91.66g, Al (NO 3) 3} · 9H 2 O27.32g, NaOH2
4.02g and 583g of water were compounded in 1 autoclave. The composition of this composition was _{7Na 2 O-41SiO 2 -1Al 2} O 3 -950H 2 O in a molar of oxides.

The powder X-ray diffraction pattern of the Na-type product obtained by crystallization and separation in the same manner as in Example 1 is shown in FIG. This product was a mordenite zeolite, not a ZSM-5 zeolite.

〔The invention's effect〕

As described above, according to the present invention, since humus is used as one of the compositions of the reaction mixture, the following effects can be obtained.

(1) In place of conventional expensive amines, a large amount of natural substances, that is, soil organic substances, can be used, and ZSM-5 zeolite can be synthesized at low cost.

(2) No need to use conventional toxic amines,
A good working environment can be maintained. Further, since amines do not exist in the waste water after the production of ZSM-5 zeolite, the waste water can be easily treated.

(3) ZSM-5 zeolite can be synthesized in a relatively short time.

(4) ZSM-5 crystals have a stronger effect of forming crystals than amines, and therefore, addition of a small amount of them exerts a sufficient effect.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a powder X-ray diffraction pattern showing that the product obtained in Example 1 is ZSM-5 zeolite, and FIG. 2 is the product obtained in Comparative Example 1. Is a powder X-ray diffraction pattern showing that is a mordenite zeolite.

Claims (3)

[Claims] 1. Humus separated from soil organic matter or lime,
Silicon oxide source material, aluminum oxide source material,
Process for producing ZSM-5 using humus, characterized in that a reaction mixture consisting of an alkali or alkaline earth metal oxide source substance and water is prepared and the reaction mixture is hydrothermally synthesized until zeolite crystals are formed. . 2. The reaction mixture has a SiO ₂ / Al ₂ O ₃ molar ratio of 8 or more, The molar ratio is 0.01 to 0.35, the H ₂ O content is 60 to 99 mol%, and the humus content to the reaction mixture is 0.001 to 10 Wt% (where M is an alkali or alkaline earth metal ion and n is a valence). The method for producing a ZSM-5 zeolite using humus according to claim 1, characterized in that 3. The humus is at least one of humic acid, fulvic acid, humic acid, nitrohumic acid and alkali metal salts of the acid, and the humus is characterized in that: ZSM using humus of
5 Manufacturing method of zeolite.