Modified clinoptilolite capable of increasing ammonium absorption value and preparation method of modified clinoptilolite

Abstract

The invention relates to the technical field of zeolite materials, and particularly discloses modified clinoptilolite capable of increasing the ammonium absorption value and a preparation method of the modified clinoptilolite. The method comprises the following steps: by taking clinoptilolite as a raw material, mixing the clinoptilolite with kaolin, industrial salt, sodium hydroxide and water, feeding the mixture into a reaction kettle, heating, stirring and reacting, and subsequently dehydrating, washing, carrying out filter pressing and drying to obtain the modified clinoptilolite. The modified clinoptilolite is of an octahedral structure, micropores are increased, the surface area is increased, the ammonium absorption value of the modified clinoptilolite is increased to 380 mmol / 100 g or above from 148 mmol / 100 g before modification, the adsorbability of the modified clinoptilolite is greatly improved, and the modified clinoptilolite has good application prospects in the fields of building indoor decoration materials, building coatings, concrete, cement, waste gas and waste water treatment and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of zeolite materials, and particularly relates to a modified clinoptilolite with improved ammonium adsorption value and a preparation method thereof. BACKGROUND

[0002] Clinoptilolite is a mineral with a porous structure, and has unique adsorption, ion exchange and catalytic properties, and is widely used in construction, environmental protection, industry, agriculture and medical treatment and other fields. However, the performance of clinoptilolite still has room for further optimization, and in order to further improve the application scenarios of clinoptilolite and improve the utilization efficiency of clinoptilolite, the clinoptilolite needs to be modified by a specific process.

[0003] The modification treatment can change the original structure of clinoptilolite, increase the surface area and enhance the adsorption-related performance, so as to better meet the higher demands of various fields in harmful gas adsorption, material performance optimization and waste treatment and other aspects, make the application of clinoptilolite more efficient and practical, and be more suitable for various production and manufacturing scenarios. SUMMARY

[0004] The purpose of the present application is to provide a modified clinoptilolite with improved ammonium adsorption value and a preparation method thereof.

[0005] In order to achieve the above purpose, the present application provides the following technical scheme: A preparation method of a modified clinoptilolite with improved ammonium adsorption value, comprising the following steps: S1, raw material treatment: selecting clinoptilolite and kaolin as raw materials, and then calcining the clinoptilolite and kaolin, and grinding the calcined clinoptilolite and kaolin into powder; S2, batching and mixing: batching and mixing the pretreated clinoptilolite, kaolin, industrial salt, sodium hydroxide and water, clinoptilolite / kaolin / industrial salt / water = 190 / 250 / 120 / 1200, and material / alkali ratio 440 / 100; S3, reaction treatment: feeding the mixed material into a reaction kettle, heating and stirring, and when the pressure in the reaction kettle reaches 0.3 MPa, maintaining the pressure for 4 hours; S4, post-treatment: feeding the reacted material into a storage tank, and sequentially performing dehydration, washing, pressure filtration and drying to obtain the modified clinoptilolite.

[0006] Preferably, the equipment used in the preparation process includes a crusher, a Raymond mill, a reaction kettle, a calcination furnace, a pressure filter and a drying device.

[0007] Preferably, the instruments used for product detection include conventional analysis instruments, a scanning electron microscope and a BET specific surface area analyzer.

[0008] Preferably, the chemical composition of the clinoptilolite is: SiO268.37%, Al2O311.89%, Fe2O31.36%, TiO20.14%, CaO 3.04%, MgO 1.16%, K2O 2.31%, Na2O 0.76%, IL 10.62%; the chemical composition of the kaolin is: SiO248.51%, Al2O335.65%, Fe2O30.19%, TiO20.88%, CaO 1.34%, MgO 0.3%, K2O 0.03%, IL 13.14%.

[0009] Preferably, in the step S1, the calcination temperature of the clinoptilolite is 520℃, and the calcination temperature of the kaolin is 800℃.

[0010] Preferably, in the step S1, the clinoptilolite is ground into 80 mesh powder, and the kaolin is ground into 200 mesh powder.

[0011] Preferably, in the step S4, in the washing step, the material is washed to a pH value of 8-9.

[0012] A modified clinoptilolite, the modified clinoptilolite has an octahedral crystal structure.

[0013] The present application has the beneficial effects: The modified clinoptilolite prepared by the present application has good adsorption performance, can adsorb harmful gases in building interior decoration materials, can also improve the hiding power and wear resistance of building coatings, can also improve the workability of concrete, improve the strength of concrete, and shorten the setting time of concrete and cement, and has important significance. If processed into various products, it can also play a significant role in waste gas and wastewater treatment.

[0014] The above description is only a summary of the technical solutions of the present application, in order to more clearly understand the technical means of the present application, and can be implemented according to the content of the specification, as follows. The preferred embodiments of the present application are described in detail below with the help of the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0015] Figure 1 SEM atlas of the modified clinoptilolite of the present application; Figure 2 BET adsorption and desorption curve of the modified clinoptilolite of the present application; Figure 3 Local magnification SEM of the modified clinoptilolite of the present application; Figure 4 BET particle size distribution graph of the modified clinoptilolite of the present application. DETAILED DESCRIPTION

[0016] The technical solutions of the present application will be clearly and completely described below with reference to the drawings. Obviously, the described embodiments are only some of the embodiments of the present application, but not all of them. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of the present application.

[0017] In the description of the present application, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer" and the like indicate the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as limiting the present application. In addition, the terms "first", "second", "third" are only for descriptive purposes and cannot be understood as indicating or implying relative importance.

[0018] In the description of the present application, it should be noted that unless otherwise explicitly specified and limited, the terms "mounting", "connecting", "connecting" should be understood broadly, for example, it can be fixedly connected, or it can be detachably connected, or integrally connected; it can be mechanically connected, or it can be electrically connected; it can be directly connected, or it can be indirectly connected through an intermediate medium; it can be the communication inside two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0019] In addition, the technical features involved in the different embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0020] A preparation method of a modified clinoptilolite with improved ammonium adsorption value, comprising the following steps: S1, raw material treatment: selecting clinoptilolite and kaolin as raw materials, then calcining the clinoptilolite and kaolin, and grinding them into powder after calcination; S2, batching and mixing: batching and mixing the pretreated clinoptilolite, kaolin, industrial salt, sodium hydroxide and water; S3, reaction treatment: sending the mixed material into a reaction kettle for heating and stirring, and when the pressure in the reaction kettle reaches 0.3 MPa, maintaining the pressure for 4 hours; S4, post-treatment: sending the reacted material into a storage tank, and sequentially performing dehydration, washing, pressure filtration and drying to obtain modified clinoptilolite, and finally detecting the modified clinoptilolite, and the ammonium adsorption value of the modified clinoptilolite is ≥380 mmol / 100g.

[0021] Specifically, the equipment used in the preparation process includes a crusher, a Raymond mill, a reaction kettle, a calcining furnace, a filter press and a drying device.

[0022] Specifically, the instruments used for detection include conventional instruments, a scanning electron microscope and a BET analyzer.

[0023] Specifically, the chemical composition of the clinoptilolite is: SiO268.37%, Al2O311.89%, Fe2O31.36%, TiO20.14%, CaO3.04%, MgO1.16%, K2O2.31%, Na2O0.76%, IL10.62%; and the chemical composition of the kaolin is: SiO248.51%, Al2O335.65%, Fe2O30.19%, TiO20.88%, CaO1.34%, MgO0.3%, K2O0.03%, IL13.14%.

[0024] Specifically, in step S1, the calcination temperature of the clinoptilolite is 520°C, and the calcination temperature of the kaolin is 800°C.

[0025] Specifically, in step S1, the clinoptilolite is ground to 80-mesh powder, and the kaolin is ground to 200-mesh powder.

[0026] Specifically, in step S4, in the washing step, the material is washed to a pH value of 8-9.

[0027] A modified clinoptilolite, the structure of the modified clinoptilolite is octahedral, the number of fine pores and the surface area are both increased compared with the unmodified clinoptilolite, and the modified clinoptilolite is used in scenes such as building interior decoration materials, building coatings, concrete, cement, waste gas treatment products or wastewater treatment products.

[0028] Illustration: Figure 1 The SEM image of the modified clinoptilolite is shown. It can be seen that the microscopic morphology is an irregular agglomerated structure. Figure 2 The adsorption and desorption curve of the modified clinoptilolite is a type III isotherm, indicating that the pores formed belong to weak interaction between substances, which is consistent with the agglomerated structure. Figure 1 The agglomerated structure is consistent with the SEM image.

[0029] As shown in Figure 3 , the microscopic morphology of the modified clinoptilolite is further determined, and the sample is locally magnified and photographed by SEM. Figure 3 It can be seen that there are a large number of small pores inside the agglomerated particles, and the size of the particles is about 1 μm. In addition, as Figure 4 shown, the BET test shows that the average pore diameter is 20.7218 nm, and the pore size distribution range is shown in the figure, and the content of mesopores with a pore diameter of 4 nm is the most.

[0030] Embodiment:

[0031] The clinoptilolite with chemical composition of SiO2 68.37%, Al2O3 11.89%, Fe2O3 1.36%, TiO2 0.14%, CaO 3.04%, MgO 1.16%, K2O 2.31%, Na2O 0.76%, and IL 10.62% is selected as the raw material, and the kaolin with chemical composition of SiO2 48.51%, Al2O3 35.65%, Fe2O3 0.19%, TiO2 0.88%, CaO 1.34%, MgO 0.3%, K2O 0.03%, and IL 13.14%, industrial salt, and sodium hydroxide are selected as the modification material, the proportioning ratio is clinoptilolite / kaolin / industrial salt / water = 190 / 250 / 120 / 1200, and the material-sodium hydroxide ratio is 440 / 100. In addition, the industrial salt and hydrochloric acid are also selected as the modification material of the clinoptilolite to make a comparative experiment. The experimental results show that the kaolin, industrial salt, and sodium hydroxide as the modification material have the best effect on improving the ammonium adsorption value of the clinoptilolite. Finally, the reagent materials for detecting the performance of the modified clinoptilolite are selected as the analytical pure sodium hydroxide, hydrochloric acid, potassium chloride, ammonium chloride, silver nitrate, ammonium nitrate, formaldehyde solution, and phenolphthalein reagent. The required equipment includes a crusher, a Raymond mill, a reaction kettle, a calcining furnace, a filter press, and a drying device, and the required detection instrument adopts a conventional instrument, a scanning electron microscope, and a BET analyzer.

[0032] Start preparation: First, the raw material is pretreated: the clinoptilolite is placed in the calcining furnace, calcined at 520 DEG C for 2h, taken out, crushed by the crusher, and then ground to 80 mesh powder by the Raymond mill for standby; the kaolin is placed in the calcining furnace, calcined at 800 DEG C for 2h, taken out, crushed by the crusher, and then ground to 200 mesh powder by the Raymond mill for standby.

[0033] Powdered clinoptilolite, powdered kaolin, industrial salt, sodium hydroxide, and water were mixed in a ratio of clinoptilolite / kaolin / industrial salt / water = 190 / 250 / 120 / 1200, with a material-to-alkali ratio of 440 / 100. The mixture was then thoroughly stirred in a mixing device to obtain a homogeneous mixture. This mixture was then fed into a reaction vessel, and heating and stirring were initiated. When the pressure inside the reaction vessel reached 0.3 MPa, this pressure and temperature were maintained for 4 hours. After the reaction, the material was transferred to a storage tank for dehydration and washing until the pH of the washing liquid reached 8-9. The mixture was then filtered using a filter press and subsequently dried in a drying device to obtain the modified clinoptilolite product. Finally, the product was tested using a testing instrument. The modified clinoptilolite structure was ultimately found to have changed from a silicon-oxygen tetrahedron to an octahedron, with increased micropores and surface area, resulting in an increase in ammonium adsorption value from 148 mmol / 100g to over 380 mmol / 100g. When this modified clinoptilolite was applied to interior building materials, its adsorption capacity for harmful indoor gases was significantly enhanced.

[0034] The table below shows the ammonium adsorption values ​​of clinoptilolite ore under different modification process conditions.

[0035]

[0036] Table 1 shows the experimental data of ammonium adsorption value of clinoptilolite ore under different modification process conditions, including temperature, pH adjustment, and salt leaching. After modification treatment with the above-mentioned processes, the ammonium adsorption value of clinoptilolite ore remained relatively unchanged. However, after modification treatment with kaolin, industrial salt, and sodium hydroxide using the present invention, the ammonium adsorption value of clinoptilolite ore can reach over 380 mmol / 100g, as shown in Table 2. Based on the data in this table, it can be seen that the modified clinoptilolite ore treated by the present invention has a significantly improved ammonium adsorption value compared to the original clinoptilolite ore, thereby improving the working efficiency and application scenarios of clinoptilolite ore.

[0037] In summary The modified clinoptilolite prepared by this invention can improve indoor air quality; adding modified clinoptilolite to architectural coatings can enhance the coating's hiding power and abrasion resistance; applying modified clinoptilolite to concrete and cement can improve the workability and strength of concrete, while also shortening the setting time of concrete and cement; after being processed into products of specific shapes, modified clinoptilolite can be used for waste gas and wastewater treatment, exhibiting adsorption effects on harmful components in waste gas and pollutants in wastewater; the modified clinoptilolite prepared by this invention has better treatment efficiency and effect than unmodified clinoptilolite.

[0038] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0039] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A process for preparing a modified clinoptilolite with an increased ammonium uptake value, characterized in that, The method comprises the following steps: S1, raw material processing: selecting clinoptilolite and kaolin as raw materials, then calcining the clinoptilolite and kaolin, and grinding the calcined clinoptilolite and kaolin into powder; S2, batching and mixing: batching and mixing the pretreated clinoptilolite, kaolin, industrial salt, sodium hydroxide and water, with a clinoptilolite / kaolin / industrial salt / water ratio of 190 / 250 / 120 / 1200 and a material / sodium hydroxide ratio of 440 / 100; S3, reaction processing: feeding the mixed material into a reaction kettle, heating and stirring, and maintaining the pressure in the reaction kettle at 0.3 MPa for 4 hours; S4, post-processing: feeding the reacted material into a storage tank, and sequentially performing dehydration, washing, pressure filtration and drying to obtain modified clinoptilolite.

2. The method for preparing modified clinoptilolite with improved ammonium adsorption value according to claim 1, characterized in that, The equipment used in the preparation process includes a crusher, a Raymond mill, a reaction kettle, a calcining furnace, a filter press and a drying device.

3. The method for preparing modified clinoptilolite with improved ammonium adsorption value according to claim 1, characterized in that, The instruments used for product detection include conventional analysis instruments, a scanning electron microscope (SEM) and a BET specific surface area analyzer.

4. The method for preparing modified clinoptilolite with improved ammonium uptake value according to claim 1, characterized in that, The clinoptilolite has a chemical composition of SiO2 68.37%, Al2O3 11.89%, Fe2O3 1.36%, TiO2 0.14%, CaO 3.04%, MgO 1.16%, K2O 2.31%, Na2O 0.76% and IL 10.62%; and the kaolin has a chemical composition of SiO2 48.51%, Al2O3 35.65%, Fe2O3 0.19%, TiO2 0.88%, CaO 1.34%, MgO 0.3%, K2O 0.03% and IL 13.14%.

5. The method for preparing modified clinoptilolite with improved ammonium uptake value according to claim 1, characterized in that, In the step S1, the clinoptilolite is calcined at a temperature of 520°C, and the kaolin is calcined at a temperature of 800°C.

6. The method for preparing modified clinoptilolite with improved ammonium uptake value according to claim 1, characterized in that, In the step S1, the clinoptilolite is ground into 80-mesh powder, and the kaolin is ground into 200-mesh powder.

7. The method for preparing modified clinoptilolite with improved ammonium adsorption value according to claim 1, characterized in that, In the step S4, the material is washed to a pH value of 8-9 in the washing step.

8. A modified clinoptilolite obtainable by the process according to any one of claims 1 to 7, characterized in that The modified clinoptilolite has an octahedral crystal structure.

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