CN117899809A - Zeolite-like adsorption material for deeply removing low-concentration fluorine-containing wastewater and preparation method thereof - Google Patents
Zeolite-like adsorption material for deeply removing low-concentration fluorine-containing wastewater and preparation method thereof Download PDFInfo
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- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
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Abstract
The invention discloses a zeolite-like adsorption material for deeply removing low-concentration fluorine-containing wastewater and a preparation method thereof, belonging to the technical fields of solid waste resource utilization and sewage treatment, wherein the method comprises the following steps: (1) Grinding and sieving the dried red mud to obtain 100-mesh powder material; immersing the powder material into dilute sulfuric acid for acid washing and partial dealkalization, and then drying to obtain a partial dealkalized red mud material; (2) Immersing a part of dealkalized red mud material into MnCl 2 solution, performing metal salt activation treatment, and drying at 105 ℃ to obtain an activated red mud material; the activated red mud material is put into a muffle furnace for full roasting and activation at 500-800 ℃, and the zeolite-like adsorption material is obtained after cooling, so that the activated red mud material has good effect on the treatment of low-concentration fluorine-containing wastewater. The preparation method is simple, has high adsorption capacity, can meet the requirement that the emission concentration of the low-concentration fluorine-containing wastewater at the end section of industrial wastewater treatment reaches the III class standard of GB3838-2002 surface water environment quality standard, namely the fluorine content is lower than 1mg/L, and has low preparation cost.
Description
Technical Field
The invention belongs to the technical field of solid waste resource utilization and sewage treatment, and particularly relates to a zeolite-like adsorption material for deep removal of low-concentration fluorine-containing wastewater and a preparation method thereof.
Background
In recent years, environmental pollution problems caused by fluorine and its compounds have been attracting attention worldwide. In many industrial processes, fluorine-containing wastewater is inevitably produced due to fluorine-containing raw materials or fluorine-containing substances added to the process. Such industries include the exploitation of fluorine minerals, synthesis of fluorides, smelting of rare earth metals and nonferrous metals, aluminum electrorefining, electroplating, coke, thermal power generation, glass, fluorosilicates, pesticides, cement, tile, acid cleaning of stainless steel, fertilizers, fluorochlorohydrocarbons, ceramics, washing of silicon-based electrical parts, petrochemical industry and other conventional industries; modern industries such as organic synthesis chemical industry, electronic integrated circuit industry, atomic energy industry and the like. The fluorine in the fluorine-containing wastewater exists in the forms of fluosilicic acid, hydrofluoric acid and other fluoride salts, and the fluorine content in various wastewater is different. In addition, industrial fluorine-containing wastewater is generally mixed with various pollutants, so that the removal is very difficult, fluoride is an pollutant which can not be naturally degraded and has great harm and lasting property, the pollution of fluoride in water is unavoidable, and in the rapidly-developed industrial field, how to effectively treat the fluorine-containing wastewater becomes a hot spot problem. Along with the increasingly prominent environmental problems, new environmental protection policies are continuously issued, and the execution strength of the environmental protection policies is increasingly enhanced: the maximum allowable emission mass concentration of inorganic compounds of fluorine in industrial wastewater is 10mg/L, such as 'electroplating pollutant emission standard', 'battery industry pollutant emission standard', 'electronic industry pollutant emission standard', and the like, the fluoride limit of the total discharge port of new enterprises is 5mg/L, the fluorine content of wastewater is processed to be less than 2mg/L according to local standard, the fluoride limit of discharged surface water is 1.5mg/L according to 'water pollutant comprehensive discharge standard' of Beijing market landmark, and the fluoride mass concentration of water outlet of coal mine needs to meet 'GB 3838-2002 surface water environment quality standard' III class standard, namely the fluoride mass concentration is less than 1mg/L.
The most main fluorine removal method at home and abroad at present comprises the following steps: chemical precipitation, electrochemical method, coagulation precipitation, ion exchange method, adsorption method, etc. However, when the high-concentration fluorine-containing wastewater is treated by adopting a chemical precipitation method, the concentration of fluorine ions in the effluent is unstable and even difficult to reach the standard, so that the effluent is required to be further treated to reach the emission standard. The electrochemical method has the advantages that the electrode is easy to passivate in the treatment process, the electrode is often required to be replaced, and the fluorine removal process has a plurality of influencing factors. The sludge amount by the coagulating sedimentation method is large, inorganic salt ions can be mixed in the effluent, and fluorine-containing complex still exists in the wastewater after the reaction, so that the fluorine removal effect is not thorough. Ion exchange resins are expensive, costly, and costly to regenerate, and are difficult to apply to industrial processing practice. The adsorption method has the advantages of simple operation, no increase of salinity of the water body, excellent effect and the like. The research of removing fluorine by adopting an adsorption method is more, and mainly aims at searching an adsorption material with low raw material price and wide source, and stable effluent quality and excellent performance after the defluorination treatment can be obtained.
Red mud is solid waste generated in the aluminum industrial production process, the red mud stockpiling amount in China is about 6 hundred million t at present, the annual new production amount is still more than 7 000 ten thousand t, and the comprehensive utilization rate is only 5%. The increasingly growing red mud discharge brings serious disposal and environmental protection problems, and the recycling of the red mud is an urgent worldwide problem. The red mud is rich in metal minerals, has good dispersibility of particles, has a high specific surface area and rich lattice defects and adsorption sites, and can play an effective role in wastewater treatment. However, for fluoride ion-containing industrial wastewater, the powdery red mud has the problems of low adsorption capacity, high environmental sensitivity, poor material stability, difficult solid-liquid separation, low recovery rate and the like.
Therefore, how to fully utilize the red mud and deeply treat fluoride ions in wastewater is a technical problem which needs to be solved by the technicians in the field.
Disclosure of Invention
In order to solve the technical problems, the invention provides the zeolite-like adsorption material for deeply removing the low-concentration fluorine-containing wastewater and the preparation method thereof, and the zeolite-like adsorption material has good environmental, economic and social benefits and wide application prospects.
In order to achieve the above purpose, the present invention provides the following technical solutions:
The preparation method of the zeolite-like adsorption material for deeply removing the low-concentration fluorine-containing wastewater comprises the following steps:
(1) Grinding the dried red mud into particles, and sieving to obtain red mud powder material;
(2) Mixing the red mud powder material with dilute sulfuric acid in a certain solid-to-liquid ratio, performing partial dealkalization treatment, and then drying to obtain a partial dealkalized red mud material;
(3) Mixing the partially dealkalized red mud material with MnCl 2 solution according to a certain solid-to-liquid ratio, performing metal salt impregnation and activation treatment, and then drying to obtain an activated red mud material;
(4) And (3) roasting the activated red mud material fully, and cooling to obtain the composite adsorption material.
As a further explanation of the present invention, in step (4), the parameters of the firing are set as follows: the roasting temperature is 500-800 ℃, the heating rate is 5-10 ℃/min, the roasting time is 1-2 h, and the heat preservation time is 1.5h.
As a further explanation of the present invention, in the step (2), the certain solid-to-liquid ratio is 0.1 to 1.0g/mL, and the duration of the sulfuric acid dip modification treatment is 2 to 5 hours.
As a further explanation of the present invention, in the step (3), the certain solid-to-liquid ratio is 0.1 to 1.0g/mL, and the duration of the metal salt impregnation activation treatment is 2 to 5 hours.
As a further illustration of the present invention, in both steps (2) and (3), the temperature of the drying was 105 ℃.
As a further illustration of the present invention, in step 1, the mesh number of the screen is 100 mesh.
The invention also provides a zeolite-like adsorption material for deeply removing the low-concentration fluorine-containing wastewater, which is prepared by the preparation method.
The invention further discloses a zeolite-like adsorption material for deeply removing the low-concentration fluorine-containing wastewater, which adopts the following raw materials: the red mud is red mud with the average content of ferric oxide of 30-40%; the concentration of the dilute sulfuric acid is 0.1-0.2 mol/L; the concentration of the MnCl 2 solution is 0.5-1.0 mol/L.
The zeolite-like adsorption material for deeply removing the low-concentration fluorine-containing wastewater has better adsorption effect when being applied to treating the low-concentration fluorine-containing wastewater, is stable, can be repeatedly applied after regeneration, and does not cause secondary pollution.
In the invention, a large amount of solid waste red mud is taken as a base material, the average content of ferric oxide in the red mud is about 30-40%, and the red mud also contains a large amount of metal oxides such as aluminum oxide, calcium oxide and the like, and active hydroxyl sites can be generated by activating the metal oxides, so that the physical and chemical adsorption of fluoride ions can be realized; dilute sulfuric acid is used as an alkali removing agent, and can react with strong alkaline substances in the raw red mud to change the pH of the red mud and enable the surface of the red mud to generate a pore structure; the manganese chloride metal salt is used as an activator, can be combined with metal oxide in red mud to generate manganese-aluminum-iron minerals containing active hydroxyl after high-temperature roasting, and forms porous zeolite-like adsorption materials, and the adsorption materials have better treatment effect on low-concentration fluorine-containing wastewater.
The invention has the advantages that:
1. The preparation method provided by the invention has the advantages of simple process, no need of complex technical equipment and high-pressure equipment, low cost and good adsorption performance of the prepared material, and is suitable for industrial popularization and mass production.
2. The material prepared by the invention has high stability, long service life and good regeneration effect.
3. The material prepared by the invention is suitable for treating low-concentration fluorine-containing wastewater at the end of industrial sewage treatment, has good effect, and the effluent can reach the III class standard of GB3838-2002 surface water environment quality standard, namely the fluoride mass concentration is less than 1mg/L.
Drawings
FIG. 1 is a topography of the material of the present application.
Detailed Description
The invention will be further illustrated with reference to specific examples.
The raw materials used in the following examples were: the red mud is from solid waste red mud of large scale industry, the content of ferric oxide is 32%, the content of calcium oxide is 19.4%, the content of aluminum oxide is 18%, and the content of silicon dioxide is 14.6%; both dilute sulfuric acid and manganese chloride employ analytical and pure chemical reagents.
Example 1:
The preparation method of the zeolite-like adsorption material for deeply removing the low-concentration fluorine-containing wastewater comprises the following steps:
(1) Grinding the dried red mud into fine particles, and sieving the fine particles with a 100-mesh sieve to obtain a red mud powder material;
(2) Mixing the red mud powder material with dilute sulfuric acid (0.1 mol/L) at a solid-to-liquid ratio of 0.5g/mL, performing impregnation modification treatment for 3h, and then sending into a 105 ℃ oven for drying to obtain a partially dealkalized red mud material;
(3) Mixing the dealkalized red mud material with MnCl 2 solution (0.5 mol/L) at a solid-to-liquid ratio of 0.5g/mL, performing impregnation and activation treatment for 3h, and then sending into a 105 ℃ oven for drying to obtain an activated red mud material;
(4) And (3) putting the activated red mud material into a muffle furnace for full roasting (the roasting temperature is 600 ℃, the heating rate is 7 ℃/min, the roasting time is 1.5h, the heat preservation time is 1.5 h), taking out and cooling to room temperature to obtain the zeolite-like adsorption material.
Example 2:
The preparation method of the composite adsorbing material for the advanced treatment of the low-concentration fluorine-containing wastewater comprises the following steps:
(1) Grinding the dried red mud into fine particles, and sieving the fine particles with a 100-mesh sieve to obtain an initial red mud raw material;
(2) Mixing the initial red mud raw material with dilute sulfuric acid (0.1 mol/L) at a solid-to-liquid ratio of 1.0g/mL, performing impregnation modification treatment for 2 hours, and then sending into a 105 ℃ oven for drying to obtain a modified red mud material;
(3) Mixing the modified red mud material with MnCl 2 solution (0.5 mol/L) at a solid-to-liquid ratio of 1.0g/mL, performing impregnation and activation treatment for 2.5h, and then sending into a 105 ℃ oven for drying to obtain an activated red mud material;
(4) And (3) placing the activated red mud material into a muffle furnace for full roasting (the roasting temperature is 700 ℃, the heating rate is 5 ℃/min, the roasting time is 1h, the heat preservation time is 1.5 h), and taking out and cooling to room temperature to obtain the zeolite-like adsorption material.
Example 3:
The preparation method of the composite adsorbing material for the advanced treatment of the low-concentration fluorine-containing wastewater comprises the following steps:
(1) Grinding the dried red mud into fine particles, and sieving the fine particles with a 100-mesh sieve to obtain an initial red mud raw material;
(2) Mixing the initial red mud raw material with dilute sulfuric acid (0.2 mol/L) at a solid-to-liquid ratio of 0.5g/mL, performing impregnation modification treatment for 2h, and then sending into a 105 ℃ oven for drying to obtain a modified red mud material;
(3) Mixing the modified red mud material with MnCl 2 solution (1.0 mol/L) at a solid-to-liquid ratio of 0.5g/mL, performing impregnation and activation treatment for 3h, and then sending into a 105 ℃ oven for drying to obtain an activated red mud material;
(4) And (3) placing the activated red mud material into a muffle furnace for full roasting (the roasting temperature is 500 ℃, the heating rate is 10 ℃/min, the roasting time is 3h, the heat preservation time is 1.5 h), and taking out and cooling to room temperature to obtain the zeolite-like adsorption material.
Those skilled in the art will appreciate that the equipment or devices used in the various embodiments described above are for illustration of the embodiments only and not for limitation. Any other available equipment or apparatus may be used in the preparation process according to the invention, with the assurance that the operating steps are satisfactory.
Comparative example 1
A method for preparing an adsorption material is different from example 1 in that only MnCl 2 metal salt is used for activation, and sulfuric acid is not used for partial dealkalization.
Comparative example 2
A method for preparing an adsorption material, which is different from example 1 in that only sulfuric acid dealkalized red mud is used, and MnCl 2 metal salt is not used for activation.
And (3) implementation effect analysis:
the materials prepared in examples 1-3 and comparative examples 1-2 were used for the treatment of power plant desulfurization wastewater applications, respectively.
The treatment process comprises the following steps: the initial concentration of fluoride ions in the desulfurization wastewater of the power plant is 16.7mg/L, the initial pH value is adjusted to 4.5, the adsorption is carried out by using a filtering device with the adsorption materials obtained in examples 1-3 and comparative examples 1-2 as adsorbents, then the maximum adsorption quantity of fluoride ions by the zeolite-like adsorption material is measured by using a Langmuir model, and the measurement of the concentration of fluoride ions in the wastewater is referred to the standard HJ 488-2009 fluorine reagent spectrophotometry for measuring water quality fluoride, and the result is shown in Table 1.
Table 1 comparison of the effects of treating fluorine-containing wastewater with Red mud raw materials in examples 1-2
As can be seen from Table 1, the fluoride ion content in the wastewater treated by the material of the invention can meet the optimal conditions
The mass concentration of fluoride is less than 1mg/L, which is a class III standard in GB3838-2002 surface water environment mass standard.
It is to be understood that the above-described embodiments are merely illustrative of the invention and are not intended to limit the practice of the invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art; it is not necessary here nor is it exhaustive of all embodiments; and obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (9)
1. A preparation method of a zeolite-like adsorption material for deeply removing low-concentration fluorine-containing wastewater is characterized by comprising the following steps of: the method comprises the following steps:
(1) Grinding the dried red mud into particles, and sieving to obtain a powder material;
(2) Immersing the powder material into dilute sulfuric acid for acid washing and partial dealkalization, and drying the powder material after partial dealkalization to obtain a partial dealkalized red mud material;
(3) Immersing the partially dealkalized red mud material into MnCl 2 solution for metal salt activation treatment, and then drying to obtain an activated red mud material;
(4) And (3) placing the activated red mud material into a muffle furnace for full roasting, and cooling to obtain the zeolite-like adsorption material.
2. The method for preparing the zeolite-like adsorption material for deep removal of low-concentration fluorine-containing wastewater, which is characterized by comprising the following steps of: in step (4), the parameters of the firing are set as follows: the roasting temperature is 500-800 ℃, the heating rate is 8-12 ℃/min, the roasting time is 1-2 h, and the heat preservation time is 1.5h.
3. The method for preparing the zeolite-like adsorption material for deep removal of low-concentration fluorine-containing wastewater, which is characterized by comprising the following steps of: in the step (2), the solid-to-liquid ratio of the powder material to the dilute sulfuric acid is 0.1-1.0 g/mL, and the duration of the impregnation modification treatment is 2-5 h.
4. The method for preparing the zeolite-like adsorption material for deep removal of low-concentration fluorine-containing wastewater, which is characterized by comprising the following steps of: in the step (3), the solid-to-liquid ratio of the partially dealkalized red mud material to the MnCl 2 solution is 0.1-1.0 g/mL, and the duration of the soaking activation treatment is 2-5 h.
5. The method for preparing the zeolite-like adsorption material for deep removal of low-concentration fluorine-containing wastewater, which is characterized by comprising the following steps of: in the steps (2) and (3), the temperature of the drying is 105-150 ℃.
6. The method for preparing the composite adsorbing material for the advanced treatment of the low-concentration fluorine-containing wastewater, which is characterized by comprising the following steps of: in the step (1), the grinding is dry grinding, and the grinding is carried out until the 100-mesh screen allowance is 1%.
7. A composite adsorbing material for advanced treatment of low-concentration fluorine-containing wastewater, which is prepared by the preparation method according to any one of claims 1 to 6.
8. The composite adsorbing material for the advanced treatment of low-concentration fluorine-containing wastewater, according to claim 7, wherein the red mud is red mud with an average ferric oxide content of 30-40%; the concentration of the dilute sulfuric acid is 0.1-0.2 mol/L; the concentration of the MnCl 2 solution is 0.5-1.0 mol/L.
9. The use of the low-concentration fluorine-containing wastewater advanced treatment composite adsorption material according to claim 7 or 8 for treating low-concentration fluorine-containing wastewater.
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