CN113398897A - Preparation method of magnetic chromium ion chelating agent, obtained product and application - Google Patents
Preparation method of magnetic chromium ion chelating agent, obtained product and application Download PDFInfo
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- 229910001430 chromium ion Inorganic materials 0.000 title claims abstract description 48
- 239000002738 chelating agent Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 239000004005 microsphere Substances 0.000 claims description 57
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 229920000877 Melamine resin Polymers 0.000 claims description 34
- 229960005070 ascorbic acid Drugs 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 22
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 235000010323 ascorbic acid Nutrition 0.000 claims description 18
- 239000011668 ascorbic acid Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- GWQWBFBJCRDINE-UHFFFAOYSA-M sodium;carbamodithioate Chemical compound [Na+].NC([S-])=S GWQWBFBJCRDINE-UHFFFAOYSA-M 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 239000000243 solution Substances 0.000 description 20
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon disulfide Substances S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 ascorbic acid modified Fe3O4 Chemical class 0.000 description 2
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 2
- 239000010840 domestic wastewater Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 208000025865 Ulcer Diseases 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 231100000397 ulcer Toxicity 0.000 description 1
- 239000010887 waste solvent Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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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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- 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
- B01J20/28014—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 form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a preparation method of a magnetic chromium ion chelating agent, an obtained product and application thereof. The material has magnetic and strong adsorption chelating sites, high adsorption capacity, convenient operation and good chromium ion separation effect, realizes the rapid treatment of the hexavalent chromium ion pollution field, and has great application potential.
Description
Technical Field
The invention relates to a preparation method of a magnetic chromium ion chelating agent, in particular to a preparation method of a magnetic chromium ion chelating agent with a melamine formaldehyde shell and an obtained product, and also relates to application of the magnetic chromium ion chelating agent in removing hexavalent chromium ions in sewage.
Background
The gap amount of fresh water in China at present reaches 400 billion cubic meters, farmland drought of 260 million square kilometers is caused by insufficient water resource supply every year, direct grain yield loss can even reach 200 million kilograms, direct GDP loss can reach 2000 million yuan, and 7000 million population possibly faces the danger of no water drinking. Especially, with the implementation of industrial strategy and the high speed of urbanization, the amount of wastewater exponentially increases into our environment, more and more heavy metal substances are accumulated in the whole water system, the environment of the system continuously deteriorates, heavy metal pollutants are discharged into the environment, can only be changed into various forms or transferred into other systems, or continuously diluted and accumulated in the system without being decomposed, and even very low concentrations can accumulate pollution and are accumulated in human bodies through food chains.
The chromium-containing wastewater mainly comes from the industries of ore processing, building material processing, electroplating, leather making, metal and steel smelting, fire-resistant production and the like, the harm of the chromium-containing wastewater is related to the valence state of chromium ions, the wastewater mainly has two valence states of trivalent and hexavalent chromium, the toxicity of the hexavalent chromium is the highest, the toxicity of the hexavalent chromium is 100 times that of the trivalent chromium, ulcers or perforation in the nose can be caused by a small amount of contact, and various diseases and lung cancer can be easily caused by long-term contact.
At present, the chromium ion wastewater treatment methods of various countries in the world mainly comprise: physical adsorption, chemical adsorption, and redox precipitation, with physical adsorption being the most widely used.
For the magnetic heavy metal capture agent at the present stage, the silane coupling agent is mainly used for coupling Fe3O4Modifying the surface of the powder and then modifying SiO2Shell layer of SiO2Surface modification of the chelating sites. By SiO2Shell layer to increase Fe content in core material3O4Stability, but in modifying SiO2A large amount of solvent is required for the shell layer to ensure the particle size of the microcapsule. The reaction can generate a large amount of waste solvent, and the practical synthesis significance is not great. Therefore, research and development of the magnetic chromium ion chelating agent with simple synthesis, good stability, large adsorption capacity and convenient application becomes a key point of research.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a magnetic chromium ion chelating agent and the obtained magnetic chromium ion chelating agent6+Large adsorption capacity and good application prospect.
The specific technical scheme of the invention is as follows:
a preparation method of a magnetic chromium ion chelating agent comprises the following steps:
(1) modifying Ascorbic Acid (AA) on the surface of the ferroferric oxide microspheres to obtain Fe3O4@ AA microsphere;
(2) in Fe3O4Coating melamine formaldehyde resin layer (MF) on the surface of the @ AA microsphere to obtain Fe3O4@ AAMF microspheres;
(3) in Fe3O4Modifying sodium dithiocarbamate on the surface of the @ AAMF microsphere to obtain the magnetic chromium ion chelating agent. The reaction equation is as follows:
furthermore, the ferroferric oxide microspheres are used as the base material, have magnetism, are convenient to recover in the subsequent use process, and are convenient to operate. The particle size of the ferroferric oxide microspheres is 10-100 um, preferably 10-200nm, and in the range, the microspheres have a good specific surface area, are convenient to modify and have good adsorption performance.
Further, in the step (1), the ferroferric oxide microspheres and ascorbic acid are heated and refluxed in water for 3-5 hours, and the stabilizer ascorbic acid is modified on the surfaces of the ferroferric oxide microspheres to obtain Fe3O4@ AA microspheres. Fe3O4And ascorbic acid in a mass ratio of 1: 0.5-1, and the amount of water is preferably 40-100 times of the mass of the ferroferric oxide microspheres.
Further, in the step (2), formaldehyde, melamine and water are mixed, the pH value is adjusted to 10-11, and the mixture is heated and stirred until the mixture is clear, so that a melamine formaldehyde prepolymer solution is obtained; mixing Fe3O4Dispersing the @ AA microspheres into water, adding a melamine formaldehyde prepolymer solution, adjusting the pH to 1-2, reacting to obtain Fe3O4@ AAMF microspheres.
Further, in the step (2), the mol ratio of melamine to formaldehyde is 1: 2-2.3, Fe3O4The mass ratio of the @ AA microspheres to the melamine formaldehyde prepolymer is 1: 0.2 to 4.
Further, in the step (2), the mass concentration of the melamine formaldehyde prepolymer solution is 15-32%. Fe3O4The @ AA microspheres were dispersed in water at 200-220 times the mass.
Further, in the step (2), heating and stirring are carried out at 70-75 ℃ to obtain the melamine formaldehyde prepolymer solution. Fe3O4The reaction of the @ AA microspheres and the melamine formaldehyde prepolymer was carried out at room temperature until the reaction was complete.
Further, in the step (3), Fe3O4The @ AAMF microspheres are dispersed into NaOH solution, and then CS is dripped2And (3) carrying out reaction, and separating the microspheres after the reaction to obtain the magnetic chromium ion chelating agent. Wherein CS2With Fe3O4The mass ratio of the @ AAMF microspheres is 1: 1-2, CS2With NaOH in the theoretical molar amount, or with NaOH in excess, typically CS2The molar ratio to NaOH is 1: 1-3.
Further, in the step (3), carbon disulfide is slowly dripped at room temperature, and the temperature is kept for continuous reaction for 2-5 hours after dripping.
Further, the concentration of the sodium hydroxide solution may be selected arbitrarily, for example, 1 to 5 mol/L.
The structural formula of the magnetic chromium ion chelating agent is shown as follows:
the magnetic chromium ion chelating agent takes magnetic ferroferric oxide as a base material, is convenient for adsorption and separation operation, and uses ascorbic acid to stabilize Fe3O4The surface modification is carried out by using melamine formaldehyde resin and sodium dithiocarbamate, so that the chelating agent is rich in chelating sites, and the adsorption capacity of the chelating agent is increased. The chelating agent can realize the adsorption removal of hexavalent chromium ions, has simple and easy separation operation and large adsorption capacity, is a high-performance adsorption material with convenient adsorption operation, and is also within the protection scope of the invention.
The invention also provides the application of the magnetic chromium ion chelating agent in removing Cr by adsorption6+The use of (1). Specifically, the magnetic chromium ion chelating agent can be used as an adsorbent for adsorbing Cr in water6+Physical adsorption is carried out. The water body can be various Cr-containing bodies6+Of water, e.g. Cr6+Aqueous solutions, surface water, groundwater, domestic wastewater, industrial wastewater, and the like.
The invention has the following beneficial effects:
1. the magnetic chromium ion chelating agent is obtained by reacting ferroferric oxide, ascorbic acid, melamine formaldehyde resin, sodium hydroxide and carbon disulfide, and has the advantages of easily obtained raw materials, simple synthesis process, simple operation and high practicability in practical application.
2. The magnetic chromium ion chelating agent takes magnetic ferroferric oxide as a base material, and through surface modification, melamine formaldehyde resin and sodium dithiocarbamate with strong adsorption chelating property are introduced to the surface of a magnetic microsphere, and the melamine formaldehyde resin has a plurality of chelating sites, so that more dithio can be introducedSodium carbamate, by reacting sodium dithiocarbamate with Cr6+And (4) coordinating and chelating to remove hexavalent chromium ions in the water body. The magnetic chromium ion chelating agent has high adsorption efficiency, can realize adsorption removal of most hexavalent chromium ions, and can adsorb Cr6+The post-separation operation is simple and easy to implement, and the high-performance adsorbing material is a high-performance adsorbing material with convenient and fast adsorption operation.
3. The magnetic chromium ion chelating agent has both magnetism and strong adsorption chelating sites, can be conveniently operated, can realize adsorption separation of hexavalent chromium ions in a short time, can realize quick treatment of various water bodies (surface water, underground water, domestic wastewater and industrial wastewater), is convenient to recover, is convenient and quick to operate, and has great application potential.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be exemplary only and are not intended to be limiting.
In the following examples, unless otherwise specified, the concentrations are mass percent concentrations.
Example 1
1. Dispersing 1g of ferroferric oxide microspheres with the particle size of 100 nm in 100 mL of deionized water, adding 0.5g of ascorbic acid, and heating and refluxing for 3 h. Separating the product by strong magnet after the reaction is finished, washing the product for three times by 20 mL deionized water, and drying the product in vacuum to obtain ascorbic acid modified Fe3O4@ AA microspheres.
2. To a 250 mL beaker were added 6.3 g of melamine, 8.1 g of aqueous formaldehyde (37%), 32.1 g of deionized water, and the pH was adjusted with 0.1M NaOH = 10. Placing the beaker in a water bath and heating to 70 DEGoAnd C, stirring and reacting until a clear and transparent solution is obtained, namely the melamine formaldehyde prepolymer solution.
1g of Fe prepared as described above3O4@ AA microsphere is uniformly dispersed in 200 mL of deionized water, 5g of prepared melamine formaldehyde prepolymer solution is added, the PH is adjusted to 2, and the reaction is carried out for 3h at room temperature. Separating the product with high-strength magnet after the reaction is finished, alternately washing the product with deionized water and ethanol for three times (20 mL/time), and then washing the product with deionized water and ethanol for three timesAir-drying to obtain Fe3O4@ AAMF microspheres.
3. Mixing 1g of Fe3O4The @ AAMF microspheres are dispersed in 20 mL of 1 mol/L NaOH aqueous solution, 1g of carbon disulfide is slowly dripped, the mixture is stirred and reacts for 4 hours at room temperature after dripping, then a product is separated by strong magnet, and after 20 mL of deionized water is washed for three times, the mixture is dried in vacuum, so that the magnetic chromium ion chelating agent is obtained.
Example 2
1. 2 g of ferroferric oxide microspheres with the particle size of 200nm are uniformly dispersed in 100 mL of deionized water, 2 g of ascorbic acid is added, and heating reflux is carried out for 3 hours. Separating the product by strong magnet after the reaction is finished, washing the product for three times by 20 mL deionized water, and drying the product in vacuum to obtain ascorbic acid modified Fe3O4@AA。
2. To a 250 mL beaker were added 6.3 g of melamine, 8.1 g of aqueous formaldehyde (37%), 32.1 g of deionized water, and the pH was adjusted with 0.1M NaOH = 10. Placing the beaker in a water bath and heating to 70 DEGoAnd C, stirring for reaction until a clear and transparent solution is obtained, thus obtaining the melamine formaldehyde prepolymer solution.
1g of Fe prepared as described above3O4@ AA microsphere is uniformly dispersed in 200 mL of deionized water, 6 g of prepared melamine formaldehyde prepolymer solution is added, the PH is adjusted to 2, and the reaction is carried out for 3h at room temperature. Separating the product by using high-strength magnet after the reaction is finished, alternately washing the product for three times (20 mL/time) by using deionized water and ethanol, and drying the product in vacuum to obtain Fe3O4@ AAMF microspheres.
3. Mixing 1g of Fe3O4The @ AAMF microspheres are dispersed in 12 mL of 2 mol/L NaOH aqueous solution, 1g of carbon disulfide is slowly dripped, the mixture is stirred and reacts for 3 hours at room temperature after dripping, then a product is separated by strong magnet, and after being washed by 10 mL of deionized water for three times, the mixture is dried in vacuum, so that the magnetic chromium ion chelating agent is obtained.
Example 3
1. Dispersing 1g of ferroferric oxide microspheres with the particle size of 10 nm in 100 mL of deionized water, adding 1g of ascorbic acid, and heating and refluxing for 3 h. Separating the product with strong magnet after the reaction is finished, washing the product with 20 mL of deionized water for three times, and drying the product in vacuumDrying to obtain ascorbic acid modified Fe3O4@ AA microspheres.
2. To a 250 mL beaker were added 6.3 g of melamine, 8.1 g of aqueous formaldehyde (37%), 32.1 g of deionized water, and the pH was adjusted with 0.1M NaOH = 10. Placing the beaker in a water bath and heating to 70 DEGoAnd C, stirring and reacting until a clear and transparent solution is obtained, namely the melamine formaldehyde prepolymer solution.
1g of Fe prepared as described above3O4@ AA microsphere is uniformly dispersed in 200 mL of deionized water, 10 g of prepared melamine formaldehyde prepolymer solution is added, the PH is adjusted to 2, and the reaction is carried out for 3h at room temperature. Separating the product by using high-strength magnet after the reaction is finished, alternately washing the product for three times (20 mL/time) by using deionized water and ethanol, and drying the product in vacuum to obtain Fe3O4@ AAMF microspheres.
3. Mixing 1g of Fe3O4The @ AAMF microspheres are dispersed in 20 mL of 1 mol/L NaOH aqueous solution, 1g of carbon disulfide is slowly dripped, the mixture is stirred and reacts for 3 hours at room temperature after dripping, then a product is separated by strong magnet, and after 20 mL of deionized water is washed for three times, the mixture is dried in vacuum, so that the magnetic chromium ion chelating agent is obtained.
Example 4
1. 1g of ferroferric oxide microspheres with the particle size of 100 um are uniformly dispersed in 100 mL of deionized water, 0.5g of ascorbic acid is added, and heating reflux is carried out for 3 hours. Separating the product by strong magnet after the reaction is finished, washing the product for three times by 20 mL deionized water, and drying the product in vacuum to obtain ascorbic acid modified Fe3O4@AA。
2. To a 250 mL beaker were added 6.3 g of melamine, 8.1 g of aqueous formaldehyde (37%), 32.1 g of deionized water, and the pH was adjusted with 0.1M NaOH = 10. Placing the beaker in a water bath and heating to 70 DEGoAnd C, stirring and reacting until a clear and transparent solution is obtained, namely the melamine formaldehyde prepolymer solution.
1g of Fe prepared as described above3O4@ AA microsphere is uniformly dispersed in 200 mL of deionized water, 1g of prepared melamine formaldehyde prepolymer solution is added, the PH is adjusted to 2, and the reaction is carried out for 3h at room temperature. Separating the product with high-strength magnet after the reaction is finished, and using deionized waterWashing with ethanol for three times (20 mL/time), and vacuum drying to obtain Fe3O4@ AAMF microspheres.
3. Mixing 1g of Fe3O4The @ AAMF microspheres are dispersed in 15 mL of 1 mol/L NaOH aqueous solution, 1g of carbon disulfide is slowly dripped, the mixture is stirred and reacts for 3 hours at room temperature after dripping, then a product is separated by strong magnet, and after washing is carried out for three times by 10 mL of deionized water, vacuum drying is carried out, so as to obtain the magnetic chromium ion chelating agent.
Example 5
A magnetic chromium ion chelating agent was prepared as in example 3, except that: the particle size of the ferroferric oxide microspheres is 1 um.
Example 6
A magnetic chromium ion chelating agent was prepared as in example 3, except that: the particle size of the ferroferric oxide microspheres is 50 um.
Application example
The magnetic chromium ion chelating agent prepared in the above example was tested for its adsorption performance to hexavalent chromium ions by the following method:
preparing a 2 mol/L hexavalent chromium ion standard solution by using potassium dichromate, and measuring the concentration of chromium ions by using an atomic absorption spectrophotometry.
Accurately weighing a certain amount of the magnetic chromium ion chelating agent (m) prepared in the above example, and adding the weighed amount of the magnetic chromium ion chelating agent (m) into a certain volume (V) and a certain concentration (C)0) In solution (pH 5). Fully absorbing in a shaking table at room temperature until the absorption is saturated, and separating the chelating agent by using strong magnet. And measuring the concentration (Ce) of heavy metal ions in the solution after absorption saturation by adopting an atomic absorption spectrophotometry.
Adsorption capacity Q of magnetic chromium ion chelating agent to hexavalent chromium ionseThe calculation is performed as follows:
Qe = （C0-Ce）V/m
wherein, C0 Unit mol/L; ceUnit mol/L; v unit ml; m units g.
The adsorption capacity of the magnetic chromium ion chelating agent for hexavalent chromium ions is shown in table 1 below:
Claims (10)
1. a preparation method of a magnetic chromium ion chelating agent is characterized by comprising the following steps:
(1) modifying ascorbic acid on the surface of ferroferric oxide microspheres to obtain Fe3O4@ AA microsphere;
(2) in Fe3O4Coating melamine formaldehyde resin layer on the surface of the @ AA microsphere to obtain Fe3O4@ AAMF microspheres;
(3) in Fe3O4Modifying sodium dithiocarbamate on the surface of the @ AAMF microsphere to obtain the magnetic chromium ion chelating agent.
2. The method of claim 1, wherein: in the step (1), ferroferric oxide microspheres and ascorbic acid are heated and refluxed in water for 3-5 hours to obtain Fe3O4@ AA microspheres.
3. The method of claim 2, wherein: in step (1), Fe3O4And ascorbic acid in a mass ratio of 1: 0.5-1, and the amount of water is preferably 40-100 times of the mass of the ferroferric oxide microspheres.
4. The method of claim 1, wherein: in the step (2), formaldehyde, melamine and water are mixed, the pH value is adjusted to 10-11, and the mixture is heated and stirred until the mixture is clear, so that a melamine formaldehyde prepolymer solution is obtained; mixing Fe3O4Dispersing the @ AA microspheres into water, adding a melamine formaldehyde prepolymer solution, adjusting the pH to 1-2, reacting to obtain Fe3O4@ AAMF microspheres.
5. The method according to claim 4, wherein: in the step (2), the mol ratio of melamine to formaldehyde is 1: 2-2.3,Fe3O4the mass ratio of the @ AA microspheres to the melamine formaldehyde prepolymer is 1: 0.2 to 4.
6. The method according to claim 4 or 5, wherein: in the step (2), the mass concentration of the melamine formaldehyde prepolymer solution is 15-32%, and Fe is added3O4The @ AA microspheres were dispersed in water at 200-220 times the mass.
7. The method according to claim 4 or 5, wherein: in the step (2), heating and stirring are carried out at the temperature of 70-75 ℃ to obtain the melamine formaldehyde prepolymer solution.
8. The method of claim 1, wherein: in the step (3), Fe3O4The @ AAMF microspheres are dispersed into NaOH solution, and then CS is dripped2Carrying out reaction, and separating the microspheres after the reaction to obtain the magnetic chromium ion chelating agent; preferably, in step (3), CS2With Fe3O4The mass ratio of the @ AAMF microspheres is 1: 1-2, NaOH and CS2In a molar ratio of 1 to 3: 1.
9. the method of claim 1, wherein: the particle size of the ferroferric oxide microspheres is 10 nm-100 um, preferably 10-200 nm.
10. The magnetic chromium ion chelating agent prepared by the method for preparing the same according to any one of claims 1 to 9, and the use thereof for removing Cr by adsorption6+The use of (1).
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|---|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496483A (en) * | 2016-11-09 | 2017-03-15 | 吉林大学 | A kind of magnetic hydrophilic molecules trace resin, preparation method and its application in aqueous medium sample |
| CN111068626A (en) * | 2019-12-31 | 2020-04-28 | 西南石油大学 | Magnetic dithiocarbamic acid modified chitosan microsphere as well as preparation method and application thereof |
-
2021
- 2021-06-17 CN CN202110672227.0A patent/CN113398897A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496483A (en) * | 2016-11-09 | 2017-03-15 | 吉林大学 | A kind of magnetic hydrophilic molecules trace resin, preparation method and its application in aqueous medium sample |
| CN111068626A (en) * | 2019-12-31 | 2020-04-28 | 西南石油大学 | Magnetic dithiocarbamic acid modified chitosan microsphere as well as preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| NASIBEH NIKRAFTAR等: "Adsorption of As(V) Using Modified Magnetic Nanoparticles with Ascorbic Acid: Optimization by Response Surface Methodology", 《WATER AIR SOIL POLLUT》 * |
| SILVIA VILLA等: "Functionalization of Fe3O4 NPs by Silanization: Use of Amine (APTES) and Thiol (MPTMS) Silanes and Their Physical Characterization", 《MATERIALS》 * |
| YANFANG ZHAO等: "Design and preparation of magnetic mesoporous melamine-formaldehyde resin: A novel material for pre-concentration and determination of silver", 《APPLIED ORGANOMETALLIC CHEMISTRY》 * |
| YIMIN DAI等: "Preparation of core-shell magnetic Fe3O4@SiO2-dithiocarbamate nanoparticle and its application for the Ni2+, Cu2+ removal", 《CHINESE CHEMICAL LETTERS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115074084A (en) * | 2022-06-08 | 2022-09-20 | 南京信息工程大学 | Preparation method of ferroferric oxide and carbon core-shell structure composite particles |
| CN115074084B (en) * | 2022-06-08 | 2023-11-17 | 南京信息工程大学 | Preparation method of ferroferric oxide and carbon core-shell structure composite particles |
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