Preparation method of acid-ultrasonic synergistic activated attapulgite and application of acid-ultrasonic synergistic activated attapulgite in dye wastewater treatment

Abstract

The invention relates to the technical field of attapulgite, and provides a preparation method of acid-ultrasonic synergistically activated attapulgite and application of the acid-ultrasonic synergistically activated attapulgite in dye wastewater treatment, the preparation method of the acid-ultrasonic synergistically activated attapulgite comprises the following steps: S1, pretreatment: purifying attapulgite less than or equal to 2mm, and drying at 105 DEG C after purification; s2, a sulfuric acid solution with the concentration of 1-2 mol / L is prepared and mixed according to the solid-to-liquid ratio of 1: 8-1: 10, and ultrasonic treatment is carried out for 120-160 min under the conditions of 40-60 kHz and 120-150 W / L at the temperature of 40-60 DEG C; s3, filtering and washing until the pH value is 3-5; and S4, drying at 110 DEG C, and calcining at 200-400 DEG C for 1-2 hours.

Description

Technical Field

[0001] This invention relates to the field of attapulgite technology, specifically to a method for preparing acid-ultrasound synergistically activated attapulgite and its application in dye wastewater treatment. Background Technology

[0002] Dye wastewater is complex in composition, highly chromatic, and highly toxic, making traditional treatment methods such as coagulation sedimentation and biological treatment ineffective. Adsorption methods offer advantages such as simple operation and high treatment efficiency, and attapulgite is a potential adsorbent material. However, the adsorption capacity and rate of natural attapulgite for dyes are limited, necessitating modification to improve its performance.

[0003] Acid solution modification can increase specific surface area and surface acidic sites; ultrasonic treatment has a cavitation effect, which can promote particle dispersion and ion diffusion. Combining acid solution modification with ultrasonic treatment is expected to significantly improve activation efficiency and adsorption performance, but existing technologies lack systematic process parameters and application schemes.

[0004] Therefore, we propose a method for preparing acid-ultrasound synergistic activation of attapulgite and its application in dye wastewater treatment. Summary of the Invention

[0005] (a) Technical problems to be solved

[0006] To address the shortcomings of existing technologies, this invention provides a method for preparing acid-ultrasound synergistically activated attapulgite and its application in dye wastewater treatment, thus solving the aforementioned technical problems.

[0007] (II) Technical Solution

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] A method for preparing acid-ultrasound synergistically activated attapulgite, characterized by comprising the following steps:

[0010] S1. Pretreatment: Purify attapulgite clay with a thickness of ≤2mm, and dry it at 105℃ after purification.

[0011] S2. Prepare a 1-2 mol / L sulfuric acid solution, mix it with a solid-liquid ratio of 1:8-1:10, and treat it under ultrasonic treatment at 40-60 kHz and 120-150 W / L for 120-160 min at a temperature of 40-60℃.

[0012] S3, filter, wash to pH 3-5;

[0013] S4, after drying at 110℃, is calcined at 200-400℃ for 1-2 hours.

[0014] Further, step S1 includes adding water to attapulgite to prepare a slurry with a mass concentration of 5-10%, stirring and dispersing, gravity settling for 6-8 hours, taking the upper slurry, centrifuging to dehydrate, drying at 10000-15000 r / min for 10-15 min at 100-110℃ to obtain purified attapulgite.

[0015] Furthermore, the attapulgite soil is mixed with water to prepare a slurry with a mass concentration of 5%. After stirring and dispersing, it is allowed to settle by gravity for 6 hours. The upper slurry is then taken, centrifuged and dehydrated, and dried at 10000 r / min for 10 min at 105℃ to obtain purified attapulgite soil.

[0016] Furthermore, step S2 includes preparing a 1 mol / L sulfuric acid solution, mixing it at a solid-liquid ratio of 1:10, and treating it under ultrasound at 60 kHz and 120 W / L for 120 min at a temperature of 40 °C.

[0017] Furthermore, the present invention also provides the application of the above-mentioned acid-ultrasound synergistic activation of attapulgite in the treatment of dye wastewater.

[0018] (III) Beneficial Effects

[0019] This invention provides a method for preparing acid-ultrasound synergistically activated attapulgite and its application in dye wastewater treatment, which has the following beneficial effects: After acid activation of attapulgite, long-term ultrasonic treatment at low power density deeply cleans the pores and enhances acid etching efficiency. While improving performance, it avoids damage to the crystal structure of attapulgite, maintains the mechanical stability of the material, and results in a more developed pore structure. The adsorption capacity for dyes such as methylene blue and methyl orange is ≥120mg / g; the adsorption rate is fast, and rapid decolorization is possible; the process is simple and suitable for large-scale production. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] Raw material description: Attapulgite clay (i.e., original attapulgite soil), sourced from Xuyi, Jiangsu Province, particle size 200 mesh, specific surface area 126.3 m². 2 / g, main oxide composition, by mass percentage: SiO2 58.2%, Al2O3 9.5%, Fe2O3 6.2%, Na2O 0.07%, K2O 1.12%, CaO 1.21%, MgO 11.0%, MnO 0.61%, TiO2 0.48%, loss on ignition: 11.2%.

[0022] Example 1

[0023] A method for preparing acid-ultrasound synergistically activated attapulgite soil includes the following steps:

[0024] S1. Pretreatment: Attapulgite with an average particle size of 2 mm is purified by adding water to prepare a slurry with a mass concentration of 5%. After stirring and dispersing, the slurry is allowed to settle by gravity for 6 hours. The upper slurry is taken, centrifuged and dehydrated at 10000 r / min for 15 min, and dried at 105℃ to obtain purified attapulgite.

[0025] S2. Prepare a 1 mol / L sulfuric acid solution, mix it at a solid-liquid ratio of 1:10, and treat it under ultrasonic treatment at 60 kHz and 120 W / L for 120 min at 40 ℃.

[0026] S3, filter, wash to pH 3-5;

[0027] S4, after drying at 110℃, is calcined at 250℃ for 2 hours, then crushed, ground, and sieved to obtain 200-mesh acid-ultrasonic synergistic activated attapulgite.

[0028] Example 2

[0029] A method for preparing acid-ultrasound synergistically activated attapulgite soil includes the following steps:

[0030] S1. Pretreatment: Attapulgite with an average particle size of 2 mm is purified by adding water to prepare a slurry with a mass concentration of 5%. After stirring and dispersing, the slurry is allowed to settle by gravity for 6 hours. The upper slurry is taken, centrifuged and dehydrated at 10000 r / min for 15 min, and dried at 105℃ to obtain purified attapulgite.

[0031] S2. Prepare a 1 mol / L sulfuric acid solution, mix it at a solid-liquid ratio of 1:10, and treat it under ultrasonic treatment at 40 kHz and 150 W / L for 160 min at 40 ℃.

[0032] S3, filter, wash to pH 3-5;

[0033] S4, after drying at 110℃, is calcined at 250℃ for 2 hours, then crushed, ground, and sieved to obtain 200-mesh acid-ultrasonic synergistic activated attapulgite.

[0034] Comparative Example 1

[0035] A method for preparing acid-ultrasound synergistically activated attapulgite soil includes the following steps:

[0036] S1. Pretreatment: Attapulgite with an average particle size of 2 mm is purified by adding water to prepare a slurry with a mass concentration of 5%. After stirring and dispersing, the slurry is allowed to settle by gravity for 6 hours. The upper slurry is taken, centrifuged and dehydrated at 10000 r / min for 15 min, and dried at 105℃ to obtain purified attapulgite.

[0037] S2. Prepare a 1 mol / L sulfuric acid solution, mix it with a solid-liquid ratio of 1:10, and treat it under ultrasonic treatment at 60 kHz and 500 W / L for 30 min at 40 ℃.

[0038] S3, filter, wash to pH 3-5;

[0039] S4, after drying at 110℃, is calcined at 250℃ for 2 hours, then crushed, ground, and sieved to obtain 200-mesh acid-ultrasonic synergistic activated attapulgite.

[0040] Comparative Example 2

[0041] A method for preparing acid-ultrasound synergistically activated attapulgite soil includes the following steps:

[0042] S1. Pretreatment: Attapulgite with an average particle size of 2 mm is purified by adding water to prepare a slurry with a mass concentration of 5%. After stirring and dispersing, the slurry is allowed to settle by gravity for 6 hours. The upper slurry is taken, centrifuged and dehydrated at 10000 r / min for 15 min, and dried at 105℃ to obtain purified attapulgite.

[0043] S2. Prepare a 1 mol / L sulfuric acid solution, mix it at a solid-liquid ratio of 1:10, and treat it under ultrasound at 60 kHz and 500 W / L for 60 min at a temperature of 40℃.

[0044] S3, filter, wash to pH 3-5;

[0045] S4, after drying at 110℃, is calcined at 250℃ for 2 hours, then crushed, ground, and sieved to obtain 200-mesh acid-ultrasonic synergistic activated attapulgite.

[0046] Application Example 1

[0047] This material was used for treating methylene blue wastewater, which was prepared by adding deionized water to methylene blue, with a concentration of 273.7 mg / L. In simulated wastewater treatment, attapulgite was activated by acid-ultrasound synergistic treatment at a dosage of 2 g / L, with stirring at 30°C for 60 min.

[0048] The acid-ultrasound synergistic activation of attapulgite in Example 1 showed an adsorption capacity of approximately 132 mg / g and a removal rate of 96.5%.

[0049] The acid-ultrasound synergistic activation of attapulgite in Example 2 showed an adsorption capacity of approximately 127.4 mg / g and a removal rate of 93.1%.

[0050] Comparative Example 1: Acid-ultrasound synergistic activation of attapulgite showed an adsorption capacity of approximately 92.5 mg / g and a removal rate of 67.6%.

[0051] Comparative Example 2: Acid-ultrasound synergistic activation of attapulgite showed an adsorption capacity of approximately 83.8 mg / g and a removal rate of 61.24%.

[0052] Application Example 2

[0053] This method was used for treating methyl orange wastewater, which was prepared by adding deionized water to methyl orange at a concentration of 400 mg / L. In simulated wastewater treatment, attapulgite was activated by acid-ultrasound synergistic activation at a dosage of 3 g / L, and stirred at 25°C for 90 min.

[0054] The acid-ultrasound synergistic activation of attapulgite in Example 1 showed an adsorption capacity of approximately 120 mg / g, with a removal rate still ≥90%.

[0055] The acid-ultrasound synergistic activation of attapulgite in Example 2 showed an adsorption capacity of approximately 115 mg / g and a removal rate of 86.3%.

[0056] Comparative Example 1 showed that acid-ultrasound synergistic activation of attapulgite had an adsorption capacity of approximately 86.4 mg / g and a removal rate of 64.8%.

[0057] Comparative Example 2: Acid-ultrasound synergistic activation of attapulgite showed an adsorption capacity of approximately 74.4 mg / g and a removal rate of 55.8%.

[0058] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Unless otherwise specified, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0059] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing acid-ultrasound synergistically activated attapulgite, characterized in that, Includes the following steps: S1. Pretreatment: Purify attapulgite clay with a thickness of ≤2mm, and dry it at 105℃ after purification. S2. Prepare a 1-2 mol / L sulfuric acid solution, mix it with a solid-liquid ratio of 1:8-1:10, and treat it under ultrasonic treatment at 40-60 kHz and 120-150 W / L for 120-160 min at a temperature of 40-60℃. S3, filter, wash to pH 3-5; S4, after drying at 110℃, is calcined at 200-400℃ for 1-2 hours.

2. The method for preparing acid-ultrasound synergistically activated attapulgite clay according to claim 1, characterized in that, Step S1 includes adding water to attapulgite to prepare a slurry with a mass concentration of 5-10%, stirring and dispersing, gravity settling for 6-8 hours, taking the upper slurry, centrifuging to dehydrate, drying at 10000-15000 r / min for 10-15 min at 100-110℃ to obtain purified attapulgite.

3. The method for preparing acid-ultrasound synergistically activated attapulgite clay according to claim 2, characterized in that, The process involves adding water to attapulgite to prepare a slurry with a mass concentration of 5%, stirring and dispersing it, then allowing it to settle by gravity for 6 hours. The upper slurry is then collected, centrifuged to remove water, and dried at 10000 r / min for 10 min at 105℃ to obtain purified attapulgite.

4. The method for preparing acid-ultrasound synergistically activated attapulgite clay according to claim 1, characterized in that, Step S2 includes preparing a 1 mol / L sulfuric acid solution, mixing it at a solid-liquid ratio of 1:10, and treating it under ultrasound at 60 kHz and 120 W / L for 120 min at a temperature of 40 °C.

5. The application of acid-ultrasonic synergistic activated attapulgite prepared by any of the methods described in claims 1-4 in the treatment of dye wastewater.