Ferric oxide modified dolomite composite material as well as preparation method and application thereof
By mixing iron trioxide with dolomite, an iron trioxide modified dolomite composite material with high efficiency adsorption performance was prepared, which solved the problem of insufficient adsorption performance of dolomite adsorption materials when dealing with complex dye wastewater, and achieved high efficiency Remove dye contaminants and have good recycling and regeneration characteristics.
Patent Information
- Application Number
- CN202411587325.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-08
- Publication Date
- 2025-02-11
AI Technical Summary
The existing dolomite adsorption materials have weak adsorption properties when treating complex dye wastewater, and there are problems such as fragility, carbon deposition inactivation, regeneration performance and structural defects during the preparation process, resulting in high costs and difficulty in recycling materials.
By mixing iron trioxide with dolomite, ball milling, washing, drying and high-temperature sintering, an iron trioxide modified dolomite composite material with high efficiency adsorption performance was prepared.
It has achieved efficient adsorption of difficult-to-degrade macromolecular dyes such as Congo red solution, with an adsorption rate of 95%, and has good recycling and regeneration characteristics, reducing production costs and environmental burden.
Smart Images
Figure CN119406392A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of environmental pollution control, and in particular to a ferric oxide modified dolomite composite material and a preparation method and application thereof. Background Art
[0002] Dolomite (CaMg(CO 3 ) 2 ) is a mineral material widely used in water treatment and material modification, mainly used to remove heavy metal ions and certain harmful pollutants in water, such as phosphorus, arsenic, chromium, etc. It has a certain adsorption capacity, but due to the small specific surface area and limited adsorption sites of dolomite, its adsorption performance is weak when treating complex dye wastewater. In order to enhance the adsorption performance of dolomite, modification techniques are often used, such as the preparation of composite materials, the introduction of metal oxides, etc.
[0003] In recent years, dolomite has been widely used in many fields due to its unique physical and chemical properties, such as surface adsorption, provision of magnesium and calcium sources, high refractoriness, large specific surface area, good thermal insulation and heat preservation effects, etc. In terms of modification research, the adsorption of dolomite can be improved by a variety of methods, such as calcination, chemical modification, co-calcination with urea, steam gasification, etc. However, these methods have problems such as fragility of dolomite, carbon deposition deactivation, regeneration performance and structural defects, as well as high energy consumption and high cost. What's more, the preparation of dolomite and modified materials adopts simple mixing or low-temperature treatment, resulting in incomplete material modification.
[0004] Secondly, many existing adsorption materials are difficult to be efficiently recycled after use. For example, although the layered double hydroxide (LDH) synthesized from calcined dolomite and aluminum salt performs well in carmine adsorption, the recovery and regeneration performance of the material after use is limited, which increases the cost and complexity of sewage treatment and is not conducive to sustainable wastewater treatment. Therefore, there is an urgent need for a method for modifying dolomite composite materials to improve the adsorption performance of dolomite, reduce costs, and enable the composite adsorption material to be recycled and regenerated. Summary of the invention
[0005] To solve the above technical problems, the present invention provides a ferric oxide modified dolomite composite material and its preparation method and application. By modifying the surface of dolomite with ferric oxide, a composite material with high-efficiency adsorption performance is prepared, which is used to treat industrial wastewater containing organic dyes such as Congo red solution, thereby achieving the removal of dye pollutants. At the same time, the ferric oxide modified dolomite composite material of the present invention also has the interdisciplinary application characteristics of material surface modification and water pollution control, and is suitable for multiple related fields such as sewage treatment, environmental protection, and new material development.
[0006] To achieve the above purpose, the technical solution provided by the present invention is as follows:
[0007] A ferric oxide modified dolomite composite material is a powdery material obtained by mixing dolomite and ferric oxide, and then subjecting the mixture to ball milling, washing, drying and high-temperature sintering. The ferric oxide modified dolomite composite material is a layered structure, and iron element is doped in the composite material.
[0008] The method for preparing the ferric oxide modified dolomite composite material as described above comprises the following steps:
[0009] (1) mixing dolomite and ferric oxide in a mass ratio of dolomite: ferric oxide = 100: 1-30, and then ball milling to make the ferric oxide evenly distributed on the surface of the dolomite;
[0010] (2) washing and filtering the mixture obtained after ball milling in step (1) to remove impurities and unreacted substances, and drying the solid matter obtained after filtration;
[0011] (3) The material obtained after drying in step (2) is calcined at 500-600° C. for 4-6 hours to obtain a ferric oxide-modified dolomite composite material.
[0012] Preferably, in step (1), dolomite and ferric oxide are mixed in a mass ratio of dolomite: ferric oxide = 100:1, and then ball milled for 4 hours.
[0013] Preferably, the washing in step (2) is washing with anhydrous ethanol for 3-4 times, and the filtration is filtration under reduced pressure.
[0014] Preferably, the drying in step (2) is performed at 60° C. to dry the anhydrous ethanol contained in the solid matter obtained after filtration.
[0015] Preferably, in step (3), the material obtained after drying in step (2) is calcined at 500°C for 4 hours.
[0016] As mentioned above, the iron oxide modified dolomite composite material is used as an adsorption material in the adsorption of dyes.
[0017] As described above, 0.5 mg of the iron oxide-modified dolomite composite material was added for every 1 mL of dye for adsorption.
[0018] Preferably, the adsorption conditions are to adjust the pH value of the dye to 3-11, preferably 5-7, with acid or alkali, the adsorption temperature is 35-45°C, and the adsorption is for 100 minutes; the acid is 1 mol / L hydrochloric acid solution, and the alkali is 1 mol / L sodium hydroxide solution.
[0019] Preferably, the dye is a Congo red solution; the concentration of the Congo red solution is 50-1000 mg / L, and the pH value is 5.5.
[0020] Preferably, the concentration of the Congo red solution is 50-400 mg / L
[0021] Compared with the prior art, the present invention has the following beneficial effects:
[0022] The ferric oxide and dolomite used in the present invention are both cheap and readily available natural resources. No expensive or difficult-to-obtain chemical reagents are required in the preparation process, which reduces the production cost, reduces the burden on the environment, and conforms to the technical development direction of green environmental protection. Furthermore, the ferric oxide-modified dolomite composite material prepared by the present invention has a high adsorption efficiency as an adsorption material, and can reach an adsorption rate of 95% in 100 minutes, especially in low-concentration dye wastewater, it still shows an excellent adsorption effect, and can effectively remove Congo red solution and other difficult-to-degrade macromolecular dyes. Finally, the composite material of the present invention has a recycling and regeneration characteristic, and maintains a stable adsorption efficiency after repeated use. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 The removal rate of different materials in the process of adsorbing Congo red solution varies with time; 2 O 3 / CaMg(CO 3 ) 2 The iron oxide modified dolomite composite material prepared in Example 1, CaMg(CO 3 ) 2 For dolomite.
[0024] Figure 2 This is a photo of the iron oxide modified dolomite composite material prepared in Example 1.
[0025] Figure 3 This is a graph showing the variation of the removal rate of the iron oxide modified dolomite composite material prepared in Example 1 with the number of cycles during the adsorption of the dye Congo red solution.
[0026] Figure 4 The left picture is a transmission electron microscope (TEM) image of the iron oxide modified dolomite composite material prepared in Example 1, and the right picture is a mapping image of the left picture.
[0027] Figure 5 This is a transmission electron microscope (TEM) image of dolomite. DETAILED DESCRIPTION
[0028] The following is a detailed description of the specific embodiments in conjunction with the accompanying drawings, but it should be understood that the scope of protection of the present invention is not limited by the specific embodiments. The raw materials and reagents used in the embodiments are all commercially available unless otherwise specified. The dolomite and ferric oxide used in the embodiments are all commercially available, and the transmission electron microscope image of dolomite is shown in Figure 5. The Congo red solution in the embodiment is obtained by dissolving the commercially available Congo red solid in deionized water, and the pH value of the obtained Congo red solution is about 5.5.
[0029] Example 1
[0030] A method for preparing a ferric oxide modified dolomite composite material, the operating steps are as follows:
[0031] (1) 2000 mg of dolomite and 20 mg of ferric oxide were mixed and then ball-milled for 4 hours to make the ferric oxide evenly distributed on the surface of the dolomite;
[0032] (2) washing the mixture obtained after ball milling in step (1) with anhydrous ethanol three times, filtering under reduced pressure to remove impurities and unreacted substances, and drying the solid matter obtained after filtration at a drying temperature of 60° C. until the anhydrous ethanol contained in the solid matter obtained after filtration is dried;
[0033] (3) The material obtained after drying in step (2) was calcined at 500° C. for 4 hours to obtain a ferric oxide modified dolomite composite material (α-Fe 2 O 3 / CaMg(CO 3 ) 2 ),like Figure 2 The obtained iron oxide modified dolomite composite material was subjected to transmission electron microscopy scanning, and the results were as follows Figure 4 As shown, from Figure 4 The iron element can be clearly seen, and the composite material prepared by the present invention has a layered structure.
[0034] Example 2
[0035] A method for preparing a ferric oxide modified dolomite composite material, the operating steps are as follows:
[0036] (1) 2000 mg of dolomite and 40 mg of ferric oxide were mixed, and then ball-milled for 4 hours to make the ferric oxide evenly distributed on the surface of the dolomite;
[0037] (2) washing the mixture obtained after ball milling in step (1) with anhydrous ethanol for 4 times, filtering under reduced pressure to remove impurities and unreacted substances, and drying the solid matter obtained after filtration at a drying temperature of 60° C. until the anhydrous ethanol contained in the solid matter obtained after filtration is dried;
[0038] (3) The material obtained after drying in step (2) is calcined at 550° C. for 6 hours to obtain a ferric oxide-modified dolomite composite material.
[0039] Example 3
[0040] A method for preparing a ferric oxide modified dolomite composite material, the operating steps are as follows:
[0041] (1) 2000 mg of dolomite and 600 mg of ferric oxide were mixed and then ball-milled for 4 hours to make the ferric oxide evenly distributed on the surface of the dolomite;
[0042] (2) washing the mixture obtained after ball milling in step (1) with anhydrous ethanol three times, filtering under reduced pressure to remove impurities and unreacted substances, and drying the solid matter obtained after filtration at a drying temperature of 60° C. until the anhydrous ethanol contained in the solid matter obtained after filtration is dried;
[0043] (3) The material obtained after drying in step (2) is calcined at 600° C. for 5 hours to obtain a ferric oxide-modified dolomite composite material.
[0044] Application Example 1
[0045] The iron oxide modified dolomite composite material prepared in Example 1 was used as an adsorption material in the adsorption of dyes: 1 mol of hydrochloric acid solution was added to adjust the pH value of the Congo red solution to 5, and the temperature of the Congo red solution was adjusted to 45°C for standby use; 50 mg of the iron oxide modified dolomite composite material prepared in Example 1 was weighed and placed in 100 mL of the above-mentioned standby Congo red solution with a concentration of 100 mg / L for adsorption, with dolomite as a control. When the adsorption time was 20 min, 40 min, 60 min, 80 min, 100 min, and 120 min, respectively, UV-visible spectrophotometry was used for detection, and the results were as follows: Figure 1 The removal rate of Congo red solution by the iron oxide modified dolomite composite material prepared in Example 1 of the present invention after adsorption for 100 minutes was 95%.
[0046] Desorption of adsorbent material :The system after 120min adsorption in the above application example 1 was filtered, the filtrate was removed, and the solid matter was taken. For the iron oxide modified dolomite composite material after 120min adsorption, a hydrochloric acid solution with a concentration of 1mol / L was added to the iron oxide modified dolomite composite material, heated, maintained at 45°C, and the stirring speed was 500r / min for desorption for 2 hours. After centrifugal filtration, it was dried at 90°C for 6 hours. The obtained iron oxide modified dolomite composite material can be reused. The iron oxide modified dolomite composite material obtained after desorption was repeated in the application example 1 operation and continued to be used for adsorption. The removal rate of Congo red solution after adsorption for 100min was 85%.
[0047] Continue to repeat the above adsorption material desorption process and application process for a total of 3 cycles. The removal rate of the dye Congo red solution is as follows: Figure 3 As shown, the removal efficiency of Congo red solution in the second cycle of adsorption for 100 minutes is 73%, and the removal efficiency of Congo red solution in the third cycle of adsorption for 100 minutes is 61%.
[0048] The foregoing description of specific exemplary embodiments of the present invention is for the purpose of illustration and demonstration. These descriptions are not intended to limit the present invention to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can realize and utilize various different exemplary embodiments of the present invention and various different selections and changes. The scope of the present invention is intended to be limited by the claims and their equivalents.
Claims
1. A ferric oxide modified dolomite composite material, characterized in that: The powder material is obtained by mixing dolomite and ferric oxide and then subjecting them to ball milling, washing, drying and high-temperature sintering. The ferric oxide-modified dolomite composite material is a layered structure, and iron is doped in the composite material.
2. The method for preparing the ferric oxide modified dolomite composite material according to claim 1, characterized in that: The following steps are included: (1) mixing dolomite and ferric oxide in a mass ratio of dolomite: ferric oxide = 100: 1-30, and then ball milling; (2) washing, filtering and drying the mixture obtained after ball milling in step (1); (3) The material obtained after drying in step (2) is calcined at 500-600° C. for 4-6 hours to obtain a ferric oxide-modified dolomite composite material.
3. The method for preparing the ferric oxide modified dolomite composite material according to claim 1, characterized in that: In step (1), dolomite and ferric oxide are mixed in a mass ratio of dolomite: ferric oxide = 100:1, and then ball milled for 4 hours.
4. The method for preparing the ferric oxide modified dolomite composite material according to claim 1, characterized in that: The washing in step (2) is washing with anhydrous ethanol for 3-4 times, and the filtration is vacuum filtration; the drying in step (2) is drying the anhydrous ethanol contained in the solid matter obtained after filtration at 60°C.
5. The method for preparing the ferric oxide modified dolomite composite material according to claim 1, characterized in that: In step (3), the material obtained after drying in step (2) is calcined at 500° C. for 4 hours.
6. Use of the iron oxide modified dolomite composite material as claimed in any one of claims 1 to 5 as an adsorption material in adsorbing dyes.
7. The use of the iron oxide modified dolomite composite material as an adsorption material in adsorbing dyes according to claim 6, characterized in that: When used, 0.5 mg of the ferric oxide-modified dolomite composite material is added to every 1 mL of dye for adsorption.
8. The use of the iron oxide modified dolomite composite material as an adsorption material in adsorbing dyes according to claim 6, characterized in that: The adsorption conditions are: adjusting the pH value of the dye to 3-11 with acid or alkali, the adsorption temperature to 35-45° C., and the adsorption for 100 minutes; the acid is 1 mol / L hydrochloric acid solution, and the alkali is 1 mol / L sodium hydroxide solution.
9. The use of the iron oxide modified dolomite composite material as an adsorption material in adsorbing dyes according to claim 6, characterized in that: The dye is Congo red solution; the concentration of the Congo red solution is 50-1000 mg / L.
10. The use of the iron oxide modified dolomite composite material as an adsorption material in adsorbing dyes according to claim 6, characterized in that: The concentration of the Congo red solution is 50-400 mg / L.