CN114939402A - Method for preparing magnetic zeolite by wet-process ball-milling method - Google Patents
Method for preparing magnetic zeolite by wet-process ball-milling method Download PDFInfo
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000010457 zeolite Substances 0.000 title claims abstract description 53
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 51
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000000498 ball milling Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 14
- 239000011707 mineral Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 11
- 238000007885 magnetic separation Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000006249 magnetic particle Substances 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000005294 ferromagnetic effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000005415 magnetization Effects 0.000 abstract description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000005431 greenhouse gas Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3021—Milling, crushing or grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- 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
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- 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
- B01J20/28009—Magnetic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- 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
- B01J20/28088—Pore-size distribution
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
- B02C23/08—Separating or sorting of material, associated with crushing or disintegrating
- B02C23/10—Separating or sorting of material, associated with crushing or disintegrating with separator arranged in discharge path of crushing or disintegrating zone
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a method for preparing modified magnetic zeolite by a wet-process ball-milling method, belonging to the field of new materials. The method comprises the steps of mixing zeolite and magnetic mineral powder particles, adding a proper amount of ball-milling auxiliary agent, carrying out wet co-ball milling according to a certain ball-milling system, carrying out magnetic separation on a magnetic product, and then cleaning and drying to obtain the modified magnetic zeolite particles. The invention can modify zeolite to realize zeolite magnetization, so that the zeolite can be magnetically separated with high efficiency, and the magnetic separation efficiency is more than 98 percent, thereby being recycled. The method has the advantages of mild conditions, simple and easily-controlled process, low preparation cost, low industrial production threshold, easy industrial popularization and wide application potential in the fields of environmental protection, chemical industry, catalytic synthesis, greenhouse gas conversion and the like.
Description
One, the technical field
The invention relates to a method for preparing magnetic zeolite by a wet-process ball-milling method, in particular to a magnetic zeolite material and a preparation method and application thereof, belonging to the technical field of magnetic composite materials and water treatment.
Second, background Art
Zeolite is an aqueous aluminosilicate with porous framework structure, belonging to clay mineral, and its framework structure is made up by using silicon oxygen and aluminium oxygen ([ AlO) 4 ] 5 And [ SiO ] 4 ] 4 -) three-dimensional space crystal composed of tetrahedron, ions for balancing charge such as alkali metal or alkaline earth metal in the structure, and cavities and channels with certain apertures in the zeolite framework determine the properties of adsorption, ion exchange, catalysis, good thermal stability and the like. The zeolite can be divided into natural zeolite and artificial zeolite, the natural zeolite is used as a raw material, and the high-performance and multifunctional modified zeolite is prepared by activation and modification treatment, so that the process is simplified, the production cost and the energy consumption are reduced, and the modified zeolite is applied to water treatment engineering, environmental engineering and other aspects as an improved adsorption material. The magnetic carrier technology is to uniformly introduce dispersed ferromagnetic substances into nonmagnetic particles so as to enhance the magnetism of a matrix material, thereby being capable of being rapidly separated by a magnetic separation technology. The combination of the inorganic material and the mineral material not only can change the interlaminar structure of the mineral material, but also can recycle the mineral material for reuse. Currently, magnetic zeolite materials have been prepared by combining magnetic support technology with zeolites. For example, CN102057901A discloses a preparation method of magnetic antibacterial zeolite for treating bacteria-containing wastewaterThe method comprises the following steps: the magnetic zeolite is prepared by using zeolite as a carrier and attaching magnetic particles (hydrochloride, nitrate or sulfate containing divalent metal ions and ferric ions) to the surface of the zeolite by adopting a chemical coprecipitation method. However, it has disadvantages that the magnetic property is not strong, and the binding between zeolite and magnetic fine particles is not strong enough. Shandong science and technology university, application number: CN201310077351.8 name: an active carbon/zeolite composite material for removing simple substance mercury in coal-fired flue gas and a preparation method thereof. Although the method is applicable to wastes, the synthesis period is long, the process is complicated, and the adsorption range is narrow. The zeolite has the characteristics of uniform porous material channels and cavities, high specific surface area, good thermal stability, strong ion exchange performance and the like, and is widely used in various heterogeneous catalytic processes and adsorption processes in industrial production and environmental protection industries. However, inorganic composite materials such as zeolite adsorbents and catalysts are generally used under liquid conditions in industrial production, and since the particle size is small, solid-liquid separation is difficult, which seriously affects the recycling of zeolite, and if zeolite is magnetized, efficient solid-liquid separation can be achieved by a magnetic separation technique. In addition, the problems of complex process, large generation amount of required medicament and waste liquid, difficult industrial production and the like exist in the preparation process of the composite material.
Third, the invention
The invention provides a simple and efficient process method for preparing the magnetic zeolite to avoid the defects of the modification application of the zeolite. According to the method, a wet-process co-ball milling method is adopted to energize the coal gangue, so that the modification efficiency is improved; the magnetic mineral powder is added into the ball milling raw material, so that the composition of the magnetic particles and the modified zeolite can be realized simultaneously. The magnetic zeolite prepared by the method has safer and firmer structure; in addition, the magnetic separation can be conveniently utilized for carrying out solid-liquid separation and recovery, so that the recycling performance of the zeolite medicament can be greatly improved.
A method for preparing magnetic zeolite by utilizing a wet-process co-ball milling method comprises the following process steps:
step 1: grinding natural zeolite or artificial zeolite, and then sieving to obtain 100-300-mesh zeolite particles; crushing and screening the magnetic mineral powder to obtain magnetic mineral powder particles with the particle size of 10-75 mu m.
Step 2: putting zeolite particles, magnetic mineral powder particles and a ball-milling assistant into a ball mill or a pebble mill, wherein the ball-material ratio is (3-10): 1, ball milling for 2-12h by a wet method at the speed of 150-.
And step 3: and separating the magnetic particles in the ball-milled product by using a magnetic separation technology, and drying after washing with water or ethanol to obtain the modified magnetic zeolite particles.
Preferably, the magnetic mineral powder refers to powder of magnetite, fly ash magnetic beads or other ferromagnetic ferrite materials;
preferably, the ball milling aid refers to ethanol, water or a mixture of the ethanol and the water, and the mass ratio of the dry materials to the ball milling aid is 1: (1.5-3.5).
Technical effects
Compared with the prior art, the technical method has the following advantages:
1. the wet ball milling is completed in one step, and the process is simple. Compared with the prior art, the method does not need to repeatedly adopt a magnetizer to impregnate the coal gangue, does not need to additionally add a catalyst and other activators, reduces the consumption of chemical reagents and environmental pollution, has low energy consumption, saves the production cost, and is easy for industrial production.
2. The wet ball milling process is a physical energizing method, and the prepared magnetic zeolite has safer and firmer structure and stronger magnetism, and is convenient for solid-liquid separation.
3. The product is nano-scale magnetic zeolite particles with the particle size distribution of 100-800nm, has large specific surface area and is beneficial to the application of the magnetic zeolite in the fields of catalysis, adsorption and the like.
Description of the drawings
The invention is further illustrated by the following examples in conjunction with the drawings.
FIG. 1 is a scanning electron micrograph and an EDS energy spectrum profile scan of a magnetic zeolite.
Fig. 2 is a room temperature magnetic hysteresis chart of the magnetic zeolite.
FIG. 3 is a graph of pH-adsorption data for phosphorus adsorption on magnetic zeolite.
Fifth, detailed description of the invention
The invention is described in further detail below with reference to the figures and examples.
Example 1:
1. preparation and pretreatment of modified zeolite and magnetic mineral powder
(1) And preparing NaA zeolite by using gangue. Calcining 250-mesh coal gangue at 700 ℃ for 1h, mixing with NaOH, grinding uniformly, calcining at 500 ℃ for 1h, and adding a certain amount of sodium silicate or sodium aluminate to adjust the silica-alumina ratio. The hydrothermal reaction was carried out at 110 ℃ for 12 hours. Separating the solid product, washing and drying to obtain the NaA zeolite. Grinding NaA zeolite, and sealing for later use.
(2) Grinding magnetite powder (with magnetic material content > 98%) to 10-75 μm, and sealing for use.
2. Preparation of magnetically modified zeolites
Mixing the prepared Na-A zeolite and magnetite powder (Fe) 3 O 4 ) Mixing and preparing into mixed materials. Placing the mixed material in a ball milling tank, mixing the material with a certain mass with 30mL of absolute ethyl alcohol under the condition that the ball material ratio is 12:1, and then carrying out ball milling for 24 hours at 200r/min by a wet co-ball milling method.
3. Drying and post-treatment
Separating out the magnetic particles in the product by using a magnet, washing the product for 2 times by using deionized water, and drying the product for 5 hours in vacuum at 100 ℃ to obtain the magnetic nano-scale zeolite particles.
Referring to fig. 1-2, fig. 1 is a scanning electron micrograph and EDS power plane scan of a magnetic zeolite. As can be seen from the figure, the particle size of the magnetic zeolite particles is in the range of 60-600nm, and the doped Fe 3 O 4 Uniformly distributed in the zeolite particles.
FIG. 2 shows the hysteresis loop at room temperature of the magnetic zeolite, which is known to have a strong magnetic property as high as 28.4emu/g in specific magnetization, and thus to realize efficient solid-liquid separation in a magnetic field. ,
example 2:
PO for laboratory deployment using magnetically modified zeolites 4 3- And simulating sewage to carry out an adsorption treatment experiment. The results showed that PO was adsorbed by rapid stirring for 10min with the amount of the modified zeolite added being 5% by mass 4 3- The specific adsorption capacity of the ions is 42.15mg/g, and the magnetic separation efficiency is high>98% PO adsorbed in Zeolite 4 3- The ion desorption ratio is more than 95 percent. After 5 times of cyclic utilization, the specific adsorption capacity of the magnetic modified zeolite is still more than 40.11mg/g, which shows that the structure and the performance of the magnetic modified zeolite are very stable.
Fig. 3 is a table of pH-adsorbate data for magnetic zeolite phosphorus adsorption, including linear data for a thermodynamic adsorption model. It can be seen from the figure that the phosphorus adsorption performance of the magnetic zeolite is best, and the specific adsorption capacity can reach more than 8 times of that of the zeolite particles.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (3)
1. A method for preparing magnetic zeolite by utilizing a wet-process co-ball milling method is characterized by comprising the following process steps:
step 1: grinding natural zeolite or artificial zeolite, and sieving to obtain 100-300 mesh zeolite particles; crushing and screening the magnetic mineral powder to obtain magnetic mineral powder particles with the particle size of 10-75 mu m;
step 2: putting zeolite particles, magnetic mineral powder particles and a ball-milling assistant into a ball mill or a pebble mill, wherein the ball-material ratio is (3-10): 1, ball milling for 2-12h by a wet method at the speed of 150-;
and step 3: and separating the magnetic particles in the ball-milled product by using a magnetic separation technology, and drying after washing with water or ethanol to obtain the modified magnetic zeolite particles.
2. The method of claim 1, wherein:
the magnetic mineral powder is powder of magnetite, fly ash magnetic beads or other ferromagnetic ferrite materials.
3. The method of claim 1, wherein:
the ball milling auxiliary agent is ethanol, water or a mixture of the ethanol and the water, and the mass ratio of the dry material to the ball milling auxiliary agent is 1: (1.5-3.5).
Priority Applications (1)
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