CN112316894B - Method for preparing magnetic mesoporous composite adsorbent by using natural mixed clay - Google Patents
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
Abstract
The application provides a method for preparing a magnetic mesoporous composite adsorbent by using natural mixed clay, and belongs to the technical field of deep processing of natural non-metallic ores and preparation of adsorption materials. The method takes low-quality mixed clay as a raw material, converts and recombines mineral components in the clay into a new magnetic mesoporous silicate material through one-step hydrothermal reaction after surface activation and magnetic functionalization modification, and has low cost and wide source of the raw material; the product has stronger magnetism and is easy to carry out magnetic separation; the product has narrow pore size distribution and specific surface area of 513.96m 2 The adsorption reaches 3 to 6 times of the adsorption capacity of the magnetic clay, and the adsorbent is a high-performance adsorbent easy to separate.
Description
Technical Field
The invention relates to a method for preparing a magnetic mesoporous composite adsorbent by using natural mixed clay, belonging to the technical field of deep processing of natural non-metallic ores and preparation of adsorption materials.
Background
The reserves of red clay minerals in autonomous regions of inner Mongolia and Gansu provinces of China are huge, the prospective reserves of the red clay minerals reach as much as 30 hundred million tons, and the potential application values of the reserves are unlimited. The mineral composition analysis result shows that the red clay consists of clay minerals such as attapulgite, illite, chlorite and illite mixed-layer clay and symbiotic or associated minerals such as calcite, dolomite, hematite and quartz. The clay mineral has complex composition, dark color and poor performance, restricts the development of high value-added products, leads to low resource utilization rate and market competitiveness of the products, and restricts the high-efficiency and high-value development and utilization of dominant clay mineral resources in China.
In recent years, with the continuous consumption of high-quality clay mineral resources, the high-efficiency and high-value utilization of clay resources containing co-associated minerals is receiving wide attention, and various methods are adopted to improve the added value of the co-associated clay minerals. Wherein, the purification treatment is the most common method for improving the purity of the clay mineral so as to improve the application value. During the purification process, the carbonate impurities are removed by acid treatment, and then large-particle quartz sand or opal is removed by aging, gravity settling and multiple centrifugal separation, so that the content of clay components is increased. For the clay mineral with higher purity, the purification treatment can effectively reduce the content of miscellaneous minerals, improve the purity of main clay mineral components and further improve the service performance. However, for clay minerals with complex compositions, it is difficult to significantly increase the content of a certain mineral component by purification because different mineral components are symbiotically associated with each other. Even if the content of a certain mineral component can be improved to a certain extent by purifying for many times, the required purification process is complex, the yield is low (only 2-5%), the cost is high, the water and energy are consumed, and the activating agent can cause environmental pollution. Therefore, all components in the mixed clay mineral are synchronously converted and recombined into a new material without any pretreatment, and the method is the most effective way for comprehensive and efficient utilization of the clay mineral.
Disclosure of Invention
The application aims to provide a method for preparing a magnetic mesoporous composite adsorbent by using natural mixed clay, which solves the bottleneck problem of preparing a new material by using low-quality clay while developing a magnetic adsorbent suitable for adsorbing pollutants such as heavy metal ions, dyes, antibiotics and the like, and opens up a new way for high-value and high-efficiency utilization of low-grade clay ores or tailings with abundant reserves in China.
The application provides a method for preparing a magnetic mesoporous composite adsorbent by using natural mixed clay, which comprises the following steps
(1) Performing air plasma ball milling treatment on the natural mixed clay for 1-2 hours, improving the surface activity of clay minerals, and reducing the activation energy of inert Si-O-Si and Si-O-M bonds;
(2) Fully and uniformly mixing clay mineral subjected to air plasma ball milling treatment with ferrous salt and ferric salt solid, and then extruding for 3-5 times by using rollers to obtain a sheet with the thickness of 0.25-1 mm;
(3) Dispersing the slices obtained in the step (2) into water under the action of high-speed shearing at 5000rpm according to a solid-to-liquid ratio of 1;
(4) Adding sodium percarbonate, water-soluble silicate and maleic anhydride into the mixture obtained in the step (3), then adding metal salt, and fully stirring and uniformly mixing;
(5) Transferring the mixture obtained in the step (4) into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, filling nitrogen for protection, reacting for 2 to 12 hours under the conditions of the pressure of 4 to 8MPa and the temperature of 170 to 260 ℃, and naturally cooling to room temperature;
(6) And (3) carrying out solid-liquid separation on the reaction product, and washing, drying and crushing the solid to obtain the magnetic composite adsorbent.
In one possible embodiment, the natural mixed clay comprises a plurality of minerals including attapulgite, illite, chlorite, illite clay, quartz, calcite, amorphous hematite, feldspar.
In one possible embodiment, the discharge voltage of the air plasma ball milling treatment is 8-12 kV, the power of a discharge power supply is 1.0-2.5 KW, and the rotating speed is 950-1400 rpm.
In one possible embodiment, the ferrous salt is at least one of ferrous sulfate, ferrous ammonium sulfate and ferrous chloride; the ferric salt is at least one of ferric sulfate, ferric chloride, ferric nitrate, ferric acetate and ferric citrate.
In a possible embodiment, the molar ratio of the ferric iron salt to the ferrous iron salt is 2.
In a possible embodiment, the organic base is at least one of diethylamine, triethylamine and diisopropylethylamine, and the water-soluble silicate is at least one of sodium metasilicate, sodium silicate and potassium silicate.
In one possible embodiment, the molar ratio of the ammonia water to the organic base is 3.
In one possible embodiment, the metal salt is at least two of cerium nitrate, cerium chloride, cerium sulfate, magnesium peroxide, magnesium hydroxide, magnesium oxide, magnesium sulfate, magnesium chloride, calcium nitrate, calcium acetate, manganese sulfate, manganese chloride, and manganese nitrate.
In one possible embodiment, the total molar amount of the metal salt is 30 to 80% of the molar amount of the water-soluble silicate.
In a possible embodiment, the mass of the sodium percarbonate is 3-6% of the mass of the magnetic clay, the amount of the water-soluble silicate is 150-500% of the mass of the magnetic clay, and the amount of the maleic anhydride is 2-5% of the mass of the magnetic clay.
The application provides a method for preparing a magnetic mesoporous composite adsorbent by using natural mixed clay, which has the following beneficial effects:
(1) According to the invention, low-quality mixed clay is used as a raw material, after surface activation and magnetic functionalization modification, mineral components in the clay are converted and recombined into a new magnetic mesoporous silicate material through one-step hydrothermal reaction, and the raw material has low cost and wide source; the product has stronger magnetism and is easy to carry out magnetic separation; the product has narrow pore size distribution and specific surface area of 513.96m 2 The adsorption is 3-6 times of the adsorption capacity of the magnetic clay, and the magnetic clay adsorbent is a high-performance adsorbent easy to separate.
(2) The preparation method disclosed by the invention is simple in process and easy to control in process, can be used for conversion of low-quality clay and conversion and recombination of other silicate minerals or tailings, and is favorable for realizing high-value utilization of the clay or tailings with abundant reserves in China.
(3) The product has stable quality and strong universality, shows excellent adsorption performance on various pollutants such as rare earth, heavy metal, dye, antibiotic, mycotoxin and the like, and has wide application prospect in various fields such as precious metal adsorption separation, environmental remediation, wastewater treatment and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments are briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive efforts and also belong to the protection scope of the present application.
FIG. 1 is a digital photograph of (a) a natural mixed clay and (b) a magnetic adsorbent MMPA-1, (c) a magnetic adsorbent MMPA-2, (d) a magnetic adsorbent MMPA-3, (e) a magnetic adsorbent MMPA-4, and (f) a magnetic adsorbent MMPA-5;
FIG. 2 is a digital photograph of the dispersion of the adsorbent in solution (a) and the magnetic separation of the magnetic adsorbent in solution (b);
FIG. 3 is a hysteresis curve of a natural mixed clay and a magnetic adsorbent MMPA-2;
FIG. 4 is an SEM image of a natural mixed clay and a magnetic adsorbent MMPA-2;
FIG. 5 is an XRD pattern of natural mixed clay and magnetic adsorbent;
FIG. 6 is a pore size distribution curve of the magnetic adsorbent MMPA-2.
Detailed Description
The technical solution of the invention is further illustrated below with reference to examples, which are not to be construed as limiting the technical solution.
The high-performance porous silicate material has the advantages of excellent adsorption performance, low cost, strong adaptability, good stability, environmental friendliness and the like, so that the high-performance porous silicate material serving as a carrier material of an excellent adsorption material or an active substance has strong market demands in the fields of environmental protection, chemical engineering, catalysis, antibiosis, energy, life health, medicine and the like. Therefore, the novel porous silicate material synthesized by using the natural low-quality clay mineral with abundant reserves, low price and environmental protection as the raw material has very wide application prospect. The inventor takes different types of clay minerals as raw materials in the early stage, respectively utilizes low-grade attapulgite clay to prepare a silicate adsorbent, utilizes low-grade attapulgite clay tailings to prepare a spherical analcime mesoporous material, and utilizes red attapulgite clay to prepare a micro-nano hybrid mesoporous adsorption microsphere through a hydrothermal reaction process, and proves that the porous materials have large specific surface area and rich pores, and simultaneously have various metal adsorption sites of Al, mg, fe and Ca, so that the porous materials show excellent adsorption performance. However, when these porous adsorbents are used for adsorbing and removing pollutants in water, separation from water after adsorption is difficult, sludge which is difficult to treat is easily formed, and application in water body purification is restricted. Therefore, on the basis of a great deal of research and technical inventions in the prior period, the natural mixed clay mineral is used as a raw material to synthesize the novel high-efficiency adsorbent which is easy to separate, and the novel high-efficiency adsorbent has a wide application prospect.
The magnetic porous adsorbent has the advantages of high adsorption capacity, high adsorption rate, easy magnetic separation and the like. The structure of the magnetic adsorbent mainly comprises several types of magnetic nano particle organic modification, magnetic nano particle deposition on biomass or carbon materials, magnetic nano particle deposition directly on the surface of inorganic matrix (such as clay, carbon nano tube, magnesium hydroxide, diatomite, graphite, attapulgite, illite clay, silicon dioxide, zeolite and the like), core-shell structure and the like.
According to the invention, by regulating and controlling reaction conditions and a formula, magnetic ferroferric oxide nano particles are firstly deposited on the surface of low-quality mixed clay after activation of a plasma ball mill, and then all mineral components in the clay are subjected to lattice recombination under a hydrothermal condition, so that the high-performance composite adsorbent with magnetism, a mesoporous structure, multi-metal adsorption centers (Mg, al, fe, ca and the like) and negative surface charges is prepared.
The following is a further explanation in conjunction with the technical solution of the present invention.
A method for preparing a magnetic mesoporous composite adsorbent by using natural mixed clay mainly comprises the following steps:
(1) And (3) carrying out air plasma ball milling treatment on the natural mixed clay for 1-2 h, improving the surface activity of the clay mineral, and reducing the activation energy of inert Si-O-Si and Si-O-M bonds.
In a specific embodiment, the natural mixed clay contains a plurality of minerals, including attapulgite (mass fraction is 21.2-36.1%), illite (mass fraction is 20.6-29.1%), chlorite (mass fraction is 5.4-6.1%), illite clay (mass fraction is 4.0-6.3%), quartz (mass fraction is 11.6-19.7%), calcite (mass fraction is 12.1-15.2%), amorphous hematite (mass fraction is 3-6%), and feldspar (mass fraction is 2-5.5%).
(2) The clay mineral subjected to air plasma ball milling treatment is fully and uniformly mixed with ferrous salt and ferric salt solids, and then the mixture is subjected to roller extrusion treatment for 3-5 times to obtain a sheet with the thickness of 0.25-1 mm.
In a specific embodiment, the discharge voltage during the air plasma ball milling treatment is 8-12 kV, the power of a discharge power supply is 1.0-2.5 KW, and the rotating speed is 950-1400 rpm.
Optionally, the ferrous salt is at least one of ferrous sulfate, ferrous ammonium sulfate and ferrous chloride; the ferric iron salt is at least one of ferric sulfate, ferric chloride, ferric nitrate, ferric acetate and ferric citrate.
Optionally, the molar ratio of the ferric iron salt to the ferrous iron salt is 2.
(3) Dispersing the slices obtained in the step (2) into water under the action of high-speed shearing at 5000rpm according to a solid-liquid ratio of 1.
In a specific embodiment, the organic base is at least one of diethylamine, triethylamine, diisopropylethylamine.
Alternatively, the molar ratio of the ammonia water to the organic base is 3.
(4) And (4) adding sodium percarbonate, water-soluble silicate and maleic anhydride into the mixture obtained in the step (3), then adding metal salt, and fully stirring and uniformly mixing.
In a specific embodiment, the water-soluble silicate is at least one of sodium metasilicate, sodium silicate, and potassium silicate.
Optionally, the metal salt is at least two of cerium nitrate, cerium chloride, cerium sulfate, magnesium peroxide, magnesium hydroxide, magnesium oxide, magnesium sulfate, magnesium chloride, calcium nitrate, calcium acetate, manganese sulfate, manganese chloride, manganese nitrate.
Optionally, the total molar amount of the metal salt is 30 to 80% of the molar amount of the water-soluble silicate.
Optionally, the mass of the sodium percarbonate is 3-6% of the mass of the magnetic clay, the dosage of the water-soluble silicate is 150-500% of the mass of the magnetic clay, and the dosage of the maleic anhydride is 2-5% of the mass of the magnetic clay.
(5) And (5) transferring the mixture obtained in the step (4) into a hydrothermal reaction kettle, sealing, introducing nitrogen for protection, reacting for 2-12 h under the conditions of pressure of 4-8 MPa and temperature of 170-260 ℃, and naturally cooling to room temperature.
(6) And (3) carrying out solid-liquid separation on the reaction product, and washing, drying and crushing the solid to obtain the magnetic composite adsorbent. And the liquid is recycled after ion concentration measurement.
According to the method for preparing the magnetic mesoporous composite adsorbent by using the natural mixed clay, the natural mixed clay mineral containing one-dimensional and two-dimensional clay minerals and impurities such as quartz, calcite and dolomite is subjected to magnetic modification, and all components in the clay are synchronously converted into the mesoporous silicate adsorbent containing a plurality of active metal centers through hydroxyl radical assisted hydrothermal structure evolution. The method comprises the following specific steps: (1) Performing air plasma ball milling treatment on the natural mixed clay mineral for 1-2 hours, reducing the activation energy of inert Si-O-Si and Si-O-M bonds, and improving the surface activity of the clay mineral; (2) Fully and uniformly mixing the clay mineral subjected to the plasma ball milling treatment with a ferrous salt solid and a ferric salt solid, and then extruding the mixture for 3-5 times by using rollers to obtain a sheet with the thickness of 0.25-1 mm; (3) Dispersing the slices into water under the action of high-speed shearing according to a solid-to-liquid ratio of 1; (4) Adding sodium percarbonate, water-soluble silicate and maleic anhydride into the mixture obtained in the step (3), then adding metal salt, and fully stirring and uniformly mixing; (5) Transferring the mixture obtained in the step (4) into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, introducing nitrogen for protection, reacting for 2 to 12 hours under the conditions of the pressure of 4 to 8MPa and the temperature of 170 to 260 ℃, and naturally cooling to room temperature; (6) And (3) carrying out solid-liquid separation on the reaction product, and washing, drying and crushing the solid to obtain the magnetic composite adsorbent. And the liquid is recycled after ion concentration measurement. According to the invention, after the low-quality clay with rich reserves and complex components is treated by the process, the magnetic mesoporous silicate adsorption material is prepared, the product has a large specific surface area and uniform pore size distribution, is easy to recover through a magnetic field, and can be used for adsorption enrichment/separation of rare earth and rare noble metals or adsorption removal of pollutants such as heavy metal ions, antibiotics, mycotoxins and dyes.
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1:
10kg of natural mixed clay is subjected to air plasma ball milling treatment for 1 hour under the conditions of 8KV of discharge voltage, 1KW of discharge power supply and 1400rpm of rotation speed, so that the reaction activity of clay minerals is improved. Then, the clay mineral subjected to the plasma ball milling treatment is fully and uniformly mixed with 5.48kg of ferrous chloride tetrahydrate and 23.35kg of ferric chloride hexahydrate solid, and then the mixture is subjected to roller extrusion treatment for 5 times to obtain a sheet with the thickness of 1 mm. The flakes were dispersed in water at a solid-to-liquid ratio of 1. To the mixture were added 0.6kg of sodium percarbonate, 30kg of sodium metasilicate nonahydrate and 0.4kg of maleic anhydride, and then 0.9234kg of magnesium hydroxide and 1.76kg of calcium chloride, followed by thorough mixing and stirring. And then transferring the obtained mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, filling nitrogen for protection, reacting for 2 hours under the conditions of the pressure of 8MPa and the temperature of 260 ℃, and naturally cooling to room temperature. And finally, carrying out solid-liquid separation on the reaction product, and washing, drying and crushing the solid to obtain the magnetic composite adsorbent. The resulting sample was labeled MMPA-1.
Example 2:
10kg of natural mixed clay is subjected to air plasma ball milling treatment for 2 hours under the conditions of 12KV discharge voltage, 2.5KW discharge power supply power and 950rpm rotation speed, so that the reaction activity of clay minerals is improved. Then, the clay mineral subjected to the plasma ball milling treatment was sufficiently and uniformly mixed with 3.60kg of ferrous sulfate heptahydrate and 10.47kg of ferric nitrate nonahydrate solid, and then subjected to the roll extrusion treatment for 3 times to obtain a sheet having a thickness of 0.25 mm. The flakes were dispersed in water at a solid-to-liquid ratio of 1. To the mixture were added 0.78kg of sodium percarbonate, 65kg of potassium silicate and 0.65kg of maleic anhydride, followed by 13.52kg of magnesium oxide and 13.825kg of calcium nitrate, followed by thorough mixing. And then transferring the obtained mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, filling nitrogen for protection, reacting for 12 hours under the conditions of 4MPa of pressure and 170 ℃, and naturally cooling to room temperature. And finally, carrying out solid-liquid separation on the reaction product, and washing, drying and crushing the solid to obtain the magnetic composite adsorbent. The resulting sample was labeled MMPA-2.
Example 3:
carrying out air plasma ball milling treatment on 10kg of natural mixed clay for 2 hours under the conditions of 10KV of discharge voltage, 2.0KW of discharge power supply and 120rpm of rotation speed, and improving the reaction activity of clay minerals. Then, the clay mineral subjected to the plasma ball milling treatment is fully and uniformly mixed with 2.74kg of ferrous chloride tetrahydrate and 10.06kg of ferric acetate solid, and then the mixture is subjected to roller extrusion treatment for 5 times to obtain a sheet with the thickness of 0.5 mm. The flakes were dispersed in water at a solid-to-liquid ratio of 1. To the mixture were added 0.70kg of sodium percarbonate, 35kg of sodium silicate nonahydrate and 0.5kg of maleic anhydride, and then 7.59kg of magnesium sulfate heptahydrate, 2.53kg of calcium nitrate and 2.605kg of manganese sulfate monohydrate, followed by thorough mixing. And then transferring the obtained mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, filling nitrogen for protection, reacting for 8 hours under the conditions of 6MPa of pressure and 200 ℃, and naturally cooling to room temperature. And finally, carrying out solid-liquid separation on the reaction product, and washing, drying and crushing the solid to obtain the magnetic composite adsorbent. The resulting sample was labeled MMPA-3.
Example 4:
10kg of natural mixed clay is subjected to air plasma ball milling treatment for 1.5h under the conditions of 12KV of discharge voltage, 1.5KW of discharge power supply and 1200rpm of rotation speed, so that the reactivity of clay minerals is improved. Then, the clay mineral subjected to the plasma ball milling treatment is fully and uniformly mixed with 4.80kg of ferrous sulfate heptahydrate and 9.34kg of ferric chloride hexahydrate solid, and then the mixture is subjected to roller extrusion treatment for 4 times to obtain a sheet with the thickness of 1 mm. The flakes were dispersed in water at a solid-to-liquid ratio of 1. To the mixture were added 0.6kg of sodium percarbonate, 42kg of sodium metasilicate nonahydrate and 0.54kg of maleic anhydride, and then 2.08kg of magnesium peroxide, 6.76kg of magnesium chloride hexahydrate and 1.604kg of cerium nitrate hexahydrate were added, and sufficiently stirred and mixed uniformly. And then transferring the obtained mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, filling nitrogen for protection, reacting for 12 hours under the conditions of 5MPa of pressure and 180 ℃, and naturally cooling to room temperature. And finally, carrying out solid-liquid separation on the reaction product, and washing, drying and crushing the solid to obtain the magnetic composite adsorbent. The resulting sample was labeled MMPA-4.
Example 5: carrying out air plasma ball milling treatment on 10kg of natural mixed clay for 2 hours under the conditions of 10KV of discharge voltage, 2KW of discharge power supply and 1000rpm of rotation speed, and improving the reaction activity of clay minerals. Then, the clay mineral subjected to the plasma ball milling treatment is fully and uniformly mixed with 8.47kg of ammonium ferrous sulfate and 11.674kg of ferric chloride hexahydrate solid, and then the mixture is subjected to roller extrusion treatment for 5 times to obtain a sheet with the thickness of 0.5 mm. The flakes were dispersed in water at a solid-to-liquid ratio of 1. To the mixture were added 0.50kg of sodium percarbonate, 30kg of sodium metasilicate nonahydrate and 0.45kg of maleic anhydride, and then 2.96kg of magnesium hydroxide, 1.60kg of manganese chloride and 1.564kg of cerium trichloride, followed by thoroughly stirring and uniformly mixing. And then transferring the obtained mixture into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, filling nitrogen for protection, reacting for 10 hours under the conditions of 6MPa of pressure and 190 ℃, and naturally cooling to room temperature. And finally, carrying out solid-liquid separation on the reaction product, and washing, drying and crushing the solid to obtain the magnetic composite adsorbent. The resulting sample was labeled MMPA-5.
Table 1 specific surface area of natural mixed clay and magnetic adsorbent, and table 2 saturated adsorption amount (mg/g) of natural mixed clay and magnetic adsorbent to Pb2+ ion, cd2+ ion, tetracycline, methylene blue dye.
TABLE 1 specific surface area of Natural Mixed Clay and magnetic adsorbent
| Sample (I) | S BET (m 2 /g) | S micro (m 2 /g) | S ext (m 2 /g) |
| Natural mixed clay | 64.57 | 7.80 | 56.77 |
| Magnetic adsorbent MMPA-1 | 409.92 | 6.11 | 403.81 |
| Magnetic adsorbent MMPA-2 | 513.96 | 25.66 | 488.30 |
| Magnetic adsorbent MMPA-3 | 489.86 | 9.64 | 480.22 |
| Magnetic adsorbent MMPA-4 | 463.73 | 16.13 | 447.60 |
| Magnetic adsorbent MMPA-5 | 506.70 | 13.24 | 493.46 |
TABLE 2 saturated adsorption capacity of natural mixed clay and magnetic adsorbent for Pb2+, cd2+, tetracycline, methylene blue dye
| Sample(s) | Pb(II) | Cd(II) | Tetracycline compounds | Methylene blue |
| Natural mixed clay | 44.04 | 40.92 | 154.23 | 103.56 |
| Magnetic adsorbent MMPA-1 | 204.66 | 194.36 | 345.24 | 324.61 |
| Magnetic adsorbent MMPA-2 | 221.14 | 202.61 | 388.67 | 386.79 |
| Magnetic adsorbent MMPA-3 | 218.73 | 200.52 | 374.86 | 377.63 |
| Magnetic adsorbent MMPA-4 | 216.65 | 195.32 | 332.47 | 323.23 |
| Magnetic adsorbent MMPA-5 | 202.34 | 190.27 | 337.98 | 354.13 |
The structural characterization and performance of the product of the invention are as follows: the structure and morphology of the adsorption microspheres are confirmed by Scanning Electron Microscopy (SEM) and X-ray powder diffraction (XRD), and the specific surface area and the pore size distribution of the magnetic adsorbent are tested by BET specific surface area analysis. As can be seen from the attached figure 1, the natural clay is red, and the brown-gray adsorbing material is obtained after magnetic functionalization and hydrothermal treatment. As can be seen from the attached figure 2, the magnetic adsorbent has strong magnetism and can be rapidly separated from the solution under the action of a magnet after being dispersed in water. As can be seen from FIG. 3, the magnetic strength of the magnetic adsorbent was 24.63emu/g. As shown in FIG. 4, the natural clay has rod shapeAttapulgite and flaky illite, chlorite, with accompanying granular material. After the treatment by the process, the rod-shaped and flaky crystals disappear, and a uniform adsorbing material with pores on the surface is formed. As can be seen from fig. 5, the natural clay has characteristic diffraction peaks of (110) and (200) crystal planes of attapulgite at 2 θ =8.38 ° and 2 θ =13.85 °, a strong characteristic quartz peak at 2 θ =26.68 °, a characteristic illite peak at 2 θ =8.88 °, and characteristic chlorite peaks at 2 θ =6.19 ° and 12.41 °, indicating that the clay contains multiple minerals. After the treatment by the method, the attapulgite, chlorite and illite characteristic peaks disappear, the characteristic diffraction peak of quartz is obviously weakened, and the characteristic peak of ferroferric oxide (2 theta =35.74 degrees) appears, so that all mineral components in the clay are converted and recombined to form the mesoporous silicate adsorbent, and the ferroferric oxide is loaded on the adsorbent as a magnetic component. The compositions of the magnetic adsorbents obtained in examples 1 to 5 were mainly amorphous silicates, and only a few characteristic analcime peaks were observed in the XRD pattern of MMPA 2. As can be seen from FIG. 6, the peak at 4.01nm appears on the pore size distribution curve of the magnetic adsorbent, demonstrating that the adsorbent is a mesoporous material. As can be seen from the attached table 1, the specific surface area of the adsorbent can reach 409.92-513.96 m 2 The specific surface area is far higher than that of natural mixed clay. As can be seen from the data in the attached table 2, the saturated adsorption capacity of the magnetic adsorbent to Pb (II) is 4.6-5.02 times of that of the natural mixed clay, the saturated adsorption capacity to Cd (II) is 4.64-4.95 times of that of the natural mixed clay, the saturated adsorption capacity to tetracycline is 2.16-2.52 times of that of the natural mixed clay, and the saturated adsorption capacity to methylene blue is 3.12-3.74 times of that of the natural mixed clay.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Claims (10)
1. A method for preparing a magnetic mesoporous composite adsorbent by using natural mixed clay is characterized by comprising the following steps: comprises the following steps
(1) Performing air plasma ball milling treatment on the natural mixed clay for 1-2 hours, improving the surface activity of clay minerals, and reducing the activation energy of inert Si-O-Si and Si-O-M bonds;
(2) Fully and uniformly mixing clay mineral subjected to air plasma ball milling treatment with ferrous salt and ferric salt solid, and then extruding for 3-5 times by using rollers to obtain a sheet with the thickness of 0.25-1 mm;
(3) Dispersing the slices obtained in the step (2) into water under the action of high-speed shearing at 5000rpm according to a solid-to-liquid ratio of 1;
(4) Adding sodium percarbonate, water-soluble silicate and maleic anhydride into the mixture obtained in the step (3), then adding metal salt, and fully stirring and uniformly mixing;
(5) Transferring the mixture obtained in the step (4) into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, introducing nitrogen for protection, reacting for 2 to 12 hours under the conditions of the pressure of 4 to 8MPa and the temperature of 170 to 260 ℃, and naturally cooling to room temperature;
(6) And (3) carrying out solid-liquid separation on the reaction product, and washing, drying and crushing the solid to obtain the magnetic composite adsorbent.
2. The method of claim 1, wherein the method comprises the steps of: the natural mixed clay contains multiple minerals including attapulgite, illite, chlorite, illite clay, quartz, calcite, amorphous hematite and feldspar.
3. The method of claim 1, wherein the method comprises the steps of: the discharge voltage during the air plasma ball milling treatment is 8-12 kV, the power of a discharge power supply is 1.0-2.5 KW, and the rotating speed is 950-1400 rpm.
4. The method for preparing a magnetic mesoporous composite adsorbent using natural mixed clay as claimed in claim 1, wherein: the ferrous salt is at least one of ferrous sulfate, ammonium ferrous sulfate and ferrous chloride; the ferric iron salt is at least one of ferric sulfate, ferric chloride, ferric nitrate, ferric acetate and ferric citrate.
5. The method for preparing a magnetic mesoporous composite adsorbent using natural mixed clay as claimed in claim 1, wherein: the molar ratio of the ferric iron salt to the ferrous iron salt is 2.
6. The method of claim 1, wherein the method comprises the steps of: the organic base is at least one of diethylamine, triethylamine and diisopropylethylamine, and the water-soluble silicate is at least one of sodium metasilicate, sodium silicate and potassium silicate.
7. The method of claim 1, wherein the method comprises the steps of: the molar ratio of the ammonia water to the organic base is 3.
8. The method of claim 1, wherein the method comprises the steps of: the metal salt is at least two of cerous nitrate, cerous chloride, cerous sulfate, magnesium peroxide, magnesium hydroxide, magnesium oxide, magnesium sulfate, magnesium chloride, calcium nitrate, calcium acetate, manganese sulfate, manganese chloride and manganese nitrate.
9. The method of claim 1, wherein the method comprises the steps of: the total molar weight of the metal salt is 30-80% of the molar weight of the water-soluble silicate.
10. The method of claim 1, wherein the method comprises the steps of: the mass of the sodium percarbonate is 3-6% of that of the magnetic clay, the dosage of the water-soluble silicate is 150-500% of that of the magnetic clay, and the dosage of the maleic anhydride is 2-5% of that of the magnetic clay.
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