阅读说明：本技术 一种由煤矸石微波水热晶化合成方沸石的方法 (Method for synthesizing analcite from coal gangue through microwave hydrothermal crystallization ) 是由 王永祯 李琪 王勇 王晓敏 于 2021-02-10 设计创作，主要内容包括：本发明公开了一种由煤矸石微波水热晶化合成方沸石的方法,先通过CaO球磨煤矸石进行活化,再利用微波合成仪消解活化溶出硅铝酸盐,进一步采用水热法合成方沸石分子筛。选材经济、成本低,固体废物的高附加值利用；合成方法简易,以微波辅助水热合成法实现合成,经洗涤、离心、干燥,制得方沸石,数据翔实精确,且合成过程不污染环境。(The invention discloses a method for synthesizing analcime by microwave hydrothermal crystallization of coal gangue. The material is economical, the cost is low, and the solid waste is utilized with high added value; the synthetic method is simple, the synthesis is realized by microwave-assisted hydrothermal synthesis, and the analcime is prepared by washing, centrifuging and drying, the data is precise and detailed, and the synthetic process does not pollute the environment.)

1. A method for synthesizing analcime by microwave hydrothermal crystallization of coal gangue is characterized by comprising the following steps:

(1) preparing ball-milling activated coal gangue:

mixing the coal gangue and calcium oxide in a ball milling tank according to the mass ratio of 2-10: 1, and performing positive and negative alternate ball milling for 1-10 hours to obtain ball-milled activated coal gangue powder for later use;

(2) microwave digestion and activation of coal gangue

Mixing sodium hydroxide and ball-milled activated coal gangue according to the mass ratio of 4-16: 1, adding 40ml of ultrapure water, placing the mixture into a microwave reaction kettle, magnetically stirring, performing microwave activation for 40-120 min at the temperature of 100-160 ℃, and dissolving active aluminosilicate from the coal gangue for later use;

(3) preparation of silicon-aluminum composite solution

Putting the activated aluminosilicate solution obtained by the activation in the step (2) into a polytetrafluoroethylene reaction kettle, adding tetraethoxysilane to prepare a composite solution with the silicon-aluminum ratio of 2-3: 1, and continuing stirring and aging at room temperature for 2-4 h;

(4) preparation of analcime

Preparing synthetic analcite from the aged sol obtained in the step (3) under hydrothermal conditions of crystallization temperature of 120-160 ℃ and crystallization time of 24-72 hours; and after the reaction kettle is taken out, filtering the solution after reaction, filtering out the crystal material, washing until the pH value is less than or equal to 8, centrifuging the washed crystal material, and drying at the temperature of 80-100 ℃ for 12-24 h to obtain the analcime molecular sieve.

2. The method for synthesizing analcite from coal gangue through microwave hydrothermal crystallization according to claim 1, wherein: the granularity of the ball-milling activated coal gangue powder is 100-200 meshes.

3. The method for synthesizing analcite from coal gangue through microwave hydrothermal crystallization according to claim 1, wherein: the constant temperature crystallization reaction is implemented in a stainless steel reaction kettle.

4. The method for synthesizing analcite from coal gangue through microwave hydrothermal crystallization according to claim 1, wherein: during centrifugation, the speed is 7000r/min, and the centrifugation time is 5 min.

Technical Field

The invention relates to a method for synthesizing analcime by microwave hydrothermal crystallization of coal gangue, belonging to the field of utilization of coal gangue and preparation of analcime.

Background

Analcite is a feldspar-like mineral having high hydrothermal stability, high selectivity and good ion exchange properties. The analcime can be used for producing ion sieves, rubber and plastic auxiliaries, soil conditioners, heavy metal extractants, silicon-aluminum compounds, bactericides, special oxidants and the like. Because of the excellent characteristics, the synthesis and application research of the analcime has been reported, so that the analcime material has good industrial application prospect.

In 2011, zea kunjuan and others (zea kunjuan, lie gorgeous, Jingzhen, research on hydrothermal synthesis of analcime [ J ] scientific and technological innovation and application, 2016 (35): 23-25.) use chemical silicon dioxide and aluminum powder as raw materials, utilize hydrothermal synthesis technology to research the influence of different raw material ratios, different reaction temperatures and different reaction times on analcime synthesis, and perform morphology and thermal analysis characterization on an analcime sample synthesized under the optimal conditions. In 2013, Qichanlin et al (Qichang, Zhang Weimin, Wang Xiao Qi, et al.) the hydrothermal synthesis of zeolite and its use for Pb in aqueous solution^{2 +}The adsorption of (J) John of Jinan university (Nature science edition), 2013, 27(1): 59-62) uses aluminium powder and silicon powder as raw materials to synthesize analcime by hydrothermal method, and researches the Pb pair of synthetic zeolite²⁺The adsorption of (1). The traditional analcime synthesis mainly uses chemical reagents as raw materials, and often needs to add an organic template agent, so that the cost of zeolite synthesis is high.

Disclosure of Invention

The invention aims to provide a method for synthesizing analcite by microwave hydrothermal crystallization synthesis of coal gangue, which takes the coal gangue as a raw material, does not add a template agent, successfully synthesizes the analcite by adopting a microwave hydrothermal crystallization method, and develops a new way for the synthesis of the analcite.

The invention provides a method for synthesizing analcime by microwave hydrothermal crystallization of coal gangue, which comprises the following steps:

(1) preparing ball-milling activated coal gangue:

mixing the coal gangue and calcium oxide in a ball milling tank according to the mass ratio of 2-10: 1, wherein the time of positive and negative alternate ball milling can be 1-10 h, and obtaining ball milling activated coal gangue powder (100-200 meshes) for later use;

(2) microwave digestion and activation of coal gangue

Mixing the ball-milled activated coal gangue and sodium hydroxide, placing the mixture into a microwave reaction kettle, magnetically stirring, carrying out microwave activation at the digestion temperature of 100-160 ℃ for 40-120 min, and dissolving active aluminosilicate from the coal gangue for later use;

(3) preparation of silicon-aluminum composite solution

Putting the activated aluminosilicate solution obtained by the activation in the step (2) into a polytetrafluoroethylene reaction kettle, adding tetraethoxysilane to prepare a composite solution with the silicon-aluminum ratio of 2-3: 1, and continuing stirring and aging at room temperature for 2-4 h;

(4) preparation of analcime

Preparing synthetic analcite from the aged sol obtained in the step (3) under hydrothermal conditions of crystallization temperature of 120-160 ℃ and crystallization time of 24-72 h; and after the reaction kettle is taken out, filtering the solution after reaction, filtering out the crystal material, washing until the pH value is less than or equal to 8, centrifuging the washed crystal material, and drying at 80-100 ℃ for 12-24 h to obtain the analcime molecular sieve. During centrifugation, the speed is 7000r/min, and the centrifugation time is 5 min.

The invention adopts CaO ball milling activation, and can better excite the activity of the coal gangue.

The invention adopts a microwave synthesizer to carry out activation digestion, and more effectively dissolves out aluminosilicate.

The constant temperature crystallization reaction is implemented in a stainless steel reaction kettle.

The invention has the beneficial effects that:

the invention synthesizes the analcime by taking the coal gangue as the raw material, not only solves the problem of environmental pollution caused by the coal gangue, but also can improve the economic and social benefits of the zeolite product. The method utilizes solid waste coal gangue to synthesize a high value-added product, is prepared by a microwave hydrothermal synthesis method, has the advantages of wide raw material source, low synthesis cost and environmental protection, and is suitable for adsorption separation application.

Drawings

FIG. 1 is an XRD pattern of an X-ray diffractometer on the analcime molecular sieve prepared in example 1 of the present invention.

FIG. 2 is an SEM image of the analcime molecular sieve prepared in example 1 of the present invention.

FIG. 3 is a schematic representation of TG of the analcime molecular sieve prepared in example 1 of the present invention.

Detailed Description

The present invention is further illustrated by, but is not limited to, the following examples.

Example 1:

chemical substance material: coal gangue, sodium hydroxide, ethyl orthosilicate and ultrapure water. The preparation amounts of the combination are as follows: measured in grams and milliliters.

A method for hydrothermally synthesizing analcime molecular sieve by using microwave activation comprises the following steps:

preparing a mixed solution: 0.4g of CaO ball-milling coal gangue and 1.6g of sodium hydroxide are weighed, and then 40ml of ultrapure water is added into a polytetrafluoroethylene container.

② placing the polytetrafluoroethylene container with the mixed solution in a reaction kettle, and reacting and activating for 40min at 160 ℃ in a microwave reactor to dissolve out active aluminosilicate.

③ after the reaction is stopped, taking the obtained active aluminosilicate solution, adding 2.4ml of tetraethoxysilane into a polytetrafluoroethylene reaction kettle, stirring and aging for 4 hours.

Fourthly, after aging is finished, the polytetrafluoroethylene container is placed in a stainless steel reaction kettle, the stainless steel reaction kettle is sealed, and then the reaction kettle is placed in an oven to react for 72 hours at 160 ℃.

Taking out the reaction kettle after the crystallization reaction. The solution after the reaction is filtered, the crystalline material is filtered off and then washed until the pH is less than or equal to 8.

Sixthly, centrifugation and drying: the washed crystalline material was centrifuged at 7000r/min for 5min and the resulting crystalline material was dried under vacuum at 100 ℃.

Analysis and test: XRD, SEM and TG analysis tests are carried out on the obtained crystal material.

FIG. 1 is an XRD pattern of an X-ray diffractometer on the analcime molecular sieve prepared in example 1 of the present invention, which was compared with the crystal structure card database PDF #41-1478, confirming that the synthesized analcime molecular sieve is type C. As can be seen from the figure, the peak value of the crystalline material is sharp, the crystallinity is high, and the structure is stable.

FIG. 2 is an SEM image of the analcime molecular sieve prepared in example 1 of the present invention, in which the synthesized analcime crystal size is about 20 microns. The shape is a quadrangle spheroid, four-membered rings of a framework structure are not on the same plane, the two parts are high and low, the crystal outline is clear, and the crystal outline is the external outline of the typical analcime.

FIG. 3 is a schematic representation of TG of the analcime molecular sieve prepared in example 1 of the present invention. The thermogravimetry is carried out in an air atmosphere, the heating rate is 10 ℃/min, and the graph shows that the apparent weight loss exists between 200 ℃ and 400 ℃, which is the process of removing crystal water of analcime, the weight loss is not obvious after 400 ℃ to 800 ℃, the total weight loss basically tends to be stable, and the total weight loss is about 7.68 percent and is close to the theoretical crystal water content of 8.2 percent.

Example 2:

in order to further embody the advantages of the technical scheme of the invention, the inventor conducts a conditional study on the adding amount of the sodium hydroxide and respectively synthesizes the sodium hydroxide according to the parameters in the table 1.

TABLE 1

Note: in the table, low crystallinity means poor crystallinity and non-uniform particles of the test product; pure phase means that the test product is a target product, and has uniform particles and uniform particle size.

In the embodiment, the influence of NaOH as an alkaline activator on the dissolution of aluminosilicate in coal gangue is researched by changing the dosage of NaOH, and the result shows that pure phase zeolite cannot be synthesized by increasing the amount of alkali, and when the dosage is 1.6g, the synthesis effect is optimal, the crystal is pure, and the granularity is uniform.

Example 3:

the inventor explores the temperature and synthesizes the analcime by adopting different temperatures respectively, and the final result shows that the analcime with good crystallinity can be successfully synthesized by adopting the crystal material of 160 ℃. Specific experimental parameters are shown in table 2:

TABLE 2

Note: in the table, low crystallinity means poor crystallinity and non-uniform particles of the test product; pure phase means that the test product is a target product, and has uniform particles and uniform particle size.

In this example, by studying the research on the synthetic analcime with different crystallization temperatures, it is found that 160 ℃ is the optimum temperature for the nucleation and growth of analcime crystal, and the obtained analcime crystal has high crystallinity, uniform particle size and uniform particle size.