CN110790282B - Method for synthesizing mordenite with silicon-aluminium ratio of 20-26 - Google Patents
Method for synthesizing mordenite with silicon-aluminium ratio of 20-26 Download PDFInfo
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- CN110790282B CN110790282B CN201911143357.4A CN201911143357A CN110790282B CN 110790282 B CN110790282 B CN 110790282B CN 201911143357 A CN201911143357 A CN 201911143357A CN 110790282 B CN110790282 B CN 110790282B
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/26—Mordenite type
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Abstract
A method for synthesizing mordenite with a silicon-aluminum ratio of 20-26, which comprises the following steps: injecting and stirring tap water to form a stirring water environment; adding reagents according to the following molar weight ratio under a stirring water environment; 14.6 to 24.4 portions of sodium hydroxide; 0.9-1 of aluminum sulfate; 29.5-40 parts of silicon dioxide; wherein the molar ratio of the water is 500-800; putting mordenite seed crystals; providing a temperature environment according to a preset temperature curve, thereby preparing the mordenite with the silicon-aluminum ratio of 20-26.
Description
Technical Field
The application relates to the field of mordenite preparation, in particular to a method for synthesizing mordenite with a silicon-aluminum ratio of 20-26.
Background
Mordenite is a zeolite with a high silica-alumina ratio, is widely applied to the fields of petrochemical industry such as catalytic cracking, dewaxing pour point depression, methanol oxidation and the like, and has wide application prospects in the fields of fine chemical industry, building materials, environmental protection and the like.
Since mordenite has better reaction activity in the reaction processes of catalysis, isomerization and the like due to higher silicon-aluminum ratio, the improvement of the silicon-aluminum ratio is always the research focus of researchers since the artificial synthesis of mordenite.
Mordenite is generally synthesized by dynamic crystallization. The influencing factors mainly comprise raw materials, alkalinity of a reaction system, a solvent, anions, a mineralizer, a template agent, crystallization temperature, crystallization time and the like. In the industrial production process, various organic templates are excessively used, so that the economic cost is increased, and the pressure of environmental protection is also caused.
The inventor works in the national institute of petrochemical and chemical industry for many years, and continues to engage in the synthesis experiment of the mordenite with high silica alumina ratio from the machine edge after retirement, and finds a method for preparing the mordenite with high silica alumina ratio, which has the advantages of cheap and easily obtained raw materials, no use of any template agent, mild crystallization conditions and easy industrial popularization.
Disclosure of Invention
Based on this, it is necessary to provide a stable preparation method for the problem that the mordenite with high silica-alumina ratio is difficult to be industrially prepared.
A method for synthesizing mordenite with a silicon-aluminum ratio of 20-26 is characterized by comprising the following steps:
injecting and stirring tap water to form a stirring water environment;
adding reagents according to the following molar weight ratio under a stirring water environment;
14.6 to 24.4 portions of sodium hydroxide;
0.9-1 of aluminum sulfate;
29.5-40 parts of silicon dioxide;
wherein the molar ratio of the water is 500-800;
putting mordenite seed crystals;
and providing a temperature environment according to a preset temperature curve.
In one embodiment, the mordenite seed crystal is Na-type mordenite, and the adding proportion is 1%.
In one embodiment, the temperature environment is uniformly heated to 155-185 ℃ from room temperature within 2 hours and is kept for 18-48 hours.
In one embodiment, the agitated aqueous environment is 160 rpm.
The application also provides a method for synthesizing mordenite with the silicon-aluminum ratio of 20-26, which is characterized by comprising the following steps:
injecting and stirring tap water to form a stirring water environment;
adding reagents according to the following molar weight ratio under a stirring water environment;
4.3-9.5 parts of sodium oxide;
0.9-1 of alumina;
29.5-40 parts of silicon dioxide;
wherein the molar ratio of the water is 550-800;
putting mordenite seed crystals;
and providing a temperature environment according to a preset temperature curve.
In one embodiment, the mordenite seed crystal is Na-type mordenite, and the adding proportion is 1%.
In one embodiment, the temperature environment is uniformly heated to 155-185 ℃ from room temperature within 2 hours and is kept for 18-48 hours.
In one embodiment, the agitated aqueous environment is 160 rpm.
The embodiment provided by the application has at least the following beneficial effects:
high silica to alumina ratio mordenites between 20 and 26 can be prepared according to the process conditions provided.
Detailed Description
For convenience of presentation, the reagents and reaction vessels used in the experiments are first briefly described below.
Reagent:
silicon powder, a domestic industrial product, and a main component of silicon dioxide, wherein the dry basis content is more than 99 percent, and the water content is 7.25 percent.
Silica sol, technical grade, 30% of silicon dioxide and 0.4% of sodium oxide.
Aluminum sulfate, domestic industrial grade product, water content 9.2%.
Sodium hydroxide, a domestic industrial grade product, with the content more than or equal to 99 percent.
Water, domestic tap water.
Deionized water, technical grade.
A synthesis device: 2L of a quick-opening rotary stirring reaction kettle.
In the examples, XRD data was measured using a DX-2700 model X-ray diffraction analyzer manufactured by Haoyuan instruments, Inc., Dandong, China.
Table 1 shows the synthetic experiment record table of mordenite with high silica-alumina ratio
In the examples provided herein, a temperature environment is provided according to a preset temperature profile to effect crystallization of the mordenite zeolite. The temperature environment is that the temperature is raised to 155-185 ℃ at the temperature raising rate of about 70 ℃/hour, and the temperature is kept for 18-48 h.
In the examples provided herein, applicants have found that high alkalinity conditions favor high silica to alumina ratios of mordenite.
In the examples provided herein, the dissolution of silica powder and the reduction of scale formation in the reaction kettle can be accelerated by doping with sodium fluoride.
When the stirring speed is 120-140 rpm, the kettle wall is easy to scale. When the stirring speed reaches 160 revolutions per minute, the phenomenon of scaling on the kettle wall is easily eliminated, the scaling on the kettle bottom is easily caused, but the whole scaling phenomenon is weakened, and meanwhile, the scaling can be reduced by adding sodium fluoride.
In summary, the present application provides a method for synthesizing mordenite with a silicon-aluminum ratio of 20-26, which comprises the following steps:
a method for synthesizing mordenite with a silicon-aluminum ratio of 20-26, which comprises the following steps:
injecting and stirring tap water to form a stirring water environment;
adding reagents according to the following molar weight ratio under a stirring water environment;
14.6 to 24.4 portions of sodium hydroxide;
0.9-1 of aluminum sulfate;
29.5-40 parts of silicon dioxide;
wherein the molar ratio of the water is 500-800;
putting mordenite seed crystals;
and providing a temperature environment according to a preset temperature curve.
Providing a temperature environment according to a preset temperature curve, thereby preparing the mordenite with the silicon-aluminum ratio of 20-26.
Further, in another embodiment provided herein, the mordenite seed crystal is Na-type mordenite, and the adding proportion is 1%.
The mordenite seed crystal is put into the reactor to play a role in rapid crystallization. The mordenite seed crystal is not easy to act when the adding proportion is less than 0.5 percent, and the production cost is not reduced when the adding proportion of the mordenite seed crystal is more than 2 percent. Experiments prove that the mordenite seed crystal feeding proportion is 1%, and the effect is optimal.
Further, in another embodiment provided herein, the temperature environment is uniformly heated from room temperature to 155-185 ℃ within 2 hours and maintained for 18-48 hours.
The temperature environment is heated up to 155-185 ℃ from room temperature in 2 hours by the temperature raising rate of about 70 ℃/hour and is kept for 18-48 hours.
The proper temperature environment facilitates the crystallization of the mordenite crystals.
Further, in yet another embodiment provided herein, the agitated aqueous environment is 160 rpm.
When the stirring speed is 120-140 rpm, the kettle wall is easy to scale. When the stirring speed reaches 160 revolutions per minute, the phenomenon of scaling on the kettle wall is easily eliminated, the scaling on the kettle bottom is easily caused, but the whole scaling phenomenon is weakened, and meanwhile, the scaling can be reduced by adding sodium fluoride.
Further, the application also discloses a method for synthesizing the mordenite with the silicon-aluminum ratio of 20-26, which comprises the following steps:
injecting and stirring tap water to form a stirring water environment;
adding reagents according to the following molar weight ratio under a stirring water environment;
4.3-9.5 parts of sodium oxide;
0.9-1 of alumina;
29.5-40 parts of silicon dioxide;
wherein the molar ratio of the water is 550-800;
putting mordenite seed crystals;
and providing a temperature environment according to a preset temperature curve.
Further, in another embodiment provided herein, the mordenite seed crystal is Na-type mordenite, and the adding proportion is 1%.
The mordenite seed crystal is put into the reactor to play a role in rapid crystallization. The mordenite seed crystal is not easy to act when the adding proportion is less than 0.5 percent, and the production cost is not reduced when the adding proportion of the mordenite seed crystal is more than 2 percent. Experiments prove that the mordenite seed crystal feeding proportion is 1%, and the effect is optimal.
Further, in another embodiment provided herein, the temperature environment is uniformly heated from room temperature to 155-185 ℃ within 2 hours and maintained for 18-48 hours.
The temperature environment is uniformly heated to 155-185 ℃ from room temperature within 2 hours and kept for 18-48 hours. The proper temperature environment facilitates the crystallization of the mordenite crystals.
Further, in yet another embodiment provided herein, the agitated aqueous environment is 160 rpm.
When the stirring speed is 120-140 rpm, the kettle wall is easy to scale. When the stirring speed reaches 160 revolutions per minute, the phenomenon of scaling on the kettle wall is easily eliminated, the scaling on the kettle bottom is easily caused, but the whole scaling phenomenon is weakened, and meanwhile, the scaling can be reduced by adding sodium fluoride.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (6)
1. A method for synthesizing mordenite with a silicon-aluminum ratio of 20-26, which is characterized by comprising the following steps:
injecting and stirring tap water to form a stirring water environment;
adding reagents according to the following molar weight ratio under a stirring water environment;
14.6 to 24.4 portions of sodium hydroxide;
0.9-1 of aluminum sulfate;
29.5-40 parts of silicon dioxide;
wherein the molar ratio of the water is 500-800;
putting mordenite seed crystals;
providing a temperature environment according to a preset temperature curve;
wherein, the silicon-aluminum ratio of the silicon dioxide to the aluminum sulfate in the raw materials is 14.75-22.22;
the stirred aqueous environment was 160 rpm.
2. A mordenite synthesis method as claimed in claim 1, wherein the mordenite seed crystal is Na-type mordenite at a charging ratio of 0.5% -2%.
3. A mordenite synthesis process as claimed in claim 1, wherein the temperature environment is uniformly heated from room temperature to 155-185 ℃ for 18-48 hours.
4. A method for synthesizing mordenite with a silicon-aluminum ratio of 20-26, which is characterized by comprising the following steps:
injecting and stirring tap water to form a stirring water environment;
adding reagents according to the following molar weight ratio under a stirring water environment;
4.3-9.5 parts of sodium oxide;
0.9-1 of alumina;
29.5-40 parts of silicon dioxide;
wherein the molar ratio of the water is 550-800;
putting mordenite seed crystals;
providing a temperature environment according to a preset temperature curve;
wherein, the silicon-aluminum ratio of the silicon dioxide to the aluminum oxide in the raw material is between 14.75 and 22.22;
the stirred aqueous environment was 160 rpm.
5. A mordenite synthesis method as claimed in claim 4, wherein the mordenite seed crystal is Na-type mordenite at a charging ratio of 0.5% -2%.
6. A mordenite synthesis process as claimed in claim 4, wherein the temperature environment is uniformly heated from room temperature to 155-185 ℃ for 18-48 hours.
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Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3677973A (en) * | 1970-03-16 | 1972-07-18 | Universal Oil Prod Co | Transalkylation of alklaromatic hydrocarbons in contact with a zeolite catalyst composition |
| JPS5939715A (en) * | 1982-08-26 | 1984-03-05 | Toyo Soda Mfg Co Ltd | High silica mordenite and its manufacture |
| JPS6121908A (en) * | 1984-07-10 | 1986-01-30 | Toyo Soda Mfg Co Ltd | Molded body of synthetic mordenite having high silica content |
| JPS6121910A (en) * | 1984-07-10 | 1986-01-30 | Toyo Soda Mfg Co Ltd | Preparation of molded body of synthetic mordenite having high strength |
| JPS63147860A (en) * | 1986-12-10 | 1988-06-20 | 東ソー株式会社 | Manufacture of high silica high strength synthetic mordenite formed body |
| CN1020039C (en) * | 1989-09-06 | 1993-03-10 | 中国石油化工总公司 | Synthesis of mercerized zeolite with high silicon content |
| CN1052454C (en) * | 1997-06-06 | 2000-05-17 | 中国石油化工总公司 | Synthesis of mordenite with high silicon aluminum ratio |
| CN1212269C (en) * | 2002-10-16 | 2005-07-27 | 中国石油化工股份有限公司 | High silicon mordenite and preparing method thereof |
| CN102602958B (en) * | 2012-04-13 | 2013-09-18 | 华东师范大学 | Preparation method of mesoporous mordenite |
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