CN112897627A - Method for removing heavy metal wastewater - Google Patents
Method for removing heavy metal wastewater Download PDFInfo
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- CN112897627A CN112897627A CN202110153009.6A CN202110153009A CN112897627A CN 112897627 A CN112897627 A CN 112897627A CN 202110153009 A CN202110153009 A CN 202110153009A CN 112897627 A CN112897627 A CN 112897627A
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002351 wastewater Substances 0.000 title claims abstract description 25
- 239000004005 microsphere Substances 0.000 claims abstract description 62
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003463 adsorbent Substances 0.000 claims abstract description 43
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000002500 ions Chemical class 0.000 claims abstract description 27
- 229960003638 dopamine Drugs 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 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 39
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 229960005070 ascorbic acid Drugs 0.000 claims description 22
- 235000010323 ascorbic acid Nutrition 0.000 claims description 22
- 239000011668 ascorbic acid Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 13
- 239000007853 buffer solution Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000009920 chelation Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011162 core material Substances 0.000 abstract description 2
- 239000012990 dithiocarbamate Substances 0.000 abstract description 2
- 239000011258 core-shell material Substances 0.000 abstract 2
- 229920000642 polymer Polymers 0.000 abstract 2
- 239000000178 monomer Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 25
- 229910021641 deionized water Inorganic materials 0.000 description 25
- 238000005406 washing Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000002953 phosphate buffered saline Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 229920001690 polydopamine Polymers 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
- GWQWBFBJCRDINE-UHFFFAOYSA-M sodium;carbamodithioate Chemical compound [Na+].NC([S-])=S GWQWBFBJCRDINE-UHFFFAOYSA-M 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- -1 ascorbic acid modified Fe3O4 Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- DXHPZXWIPWDXHJ-UHFFFAOYSA-N carbon monosulfide Chemical compound [S+]#[C-] DXHPZXWIPWDXHJ-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000011133 lead 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
- 244000005700 microbiome Species 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229940083608 sodium hydroxide Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000010887 waste solvent Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for removing heavy metal wastewater, which adopts an adsorbent to adsorb and remove heavy metal ions in the wastewater. The adsorbent takes magnetic ferroferric oxide microspheres as core materials, a polymer core-shell structure is formed by surface modification and dopamine monomer polymerization, and dithiocarbamate with strong heavy metal ion adsorption chelation performance is introduced to the magnetic core-shell microsphere polymer, so that the adsorbent has magnetic and strong adsorption chelation sites, high adsorption capacity, good acid/alkali resistance, convenient operation and good heavy metal ion separation effect, can realize rapid treatment of the heavy metal ion pollution field, and has great application potential.
Description
Technical Field
The invention relates to a method for removing heavy metal wastewater, in particular to a method for rapidly removing heavy metal ions in wastewater by adopting an adsorbent, and belongs to the technical field of wastewater treatment.
Background
Heavy metal wastewater mainly comes from the industries of ore processing, building material processing, electroplating, mechanical manufacturing, metal and steel smelting, some chemical production and the like, generally contains copper, lead, nickel, mercury and the like, and the removal of heavy metals is particularly important.
At present, the treatment methods of heavy metal wastewater in various countries in the world mainly comprise three types: the first type is that heavy metal ions in the wastewater are removed by chemical reaction, and comprises a neutralization precipitation method, a sulfide precipitation method, a ferrite coprecipitation method, a chemical reduction method, an electrochemical reduction method, a high-molecular heavy metal trapping agent method and the like. The chemical method is a water treatment method which is widely applied and mature in technology at present, but is suitable for treating high-concentration heavy metal wastewater and is easy to generate a large amount of sludge. The second type is a method of adsorbing, concentrating and separating heavy metals in wastewater under the condition of not changing the chemical form of the heavy metals. The third type is to remove heavy metals in the wastewater by the flocculation, absorption, accumulation, enrichment and other actions of microorganisms or plants.
For the present-stage adsorbent, the coupling agent is mainly used for 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, it is necessary to develop a method for removing heavy metal ions, which is rapid, convenient to use and good in effect.
Disclosure of Invention
The invention aims to provide a method for removing heavy metal wastewater, which removes heavy metal ions in the wastewater by adopting an adsorbent, is simple to operate and convenient to use, can quickly remove various heavy metal ions, and has great application potential.
The specific technical scheme of the invention is as follows:
a method for removing heavy metal wastewater comprises the following steps: the method comprises the following steps of (1) adsorbing and removing heavy metal ions in the wastewater by using an adsorbent, wherein the adsorbent is prepared by the following method:
(1) modifying ascorbic acid on the surface of ferroferric oxide microspheres to obtain Fe3O4@ AA microsphere;
(2) with dopamine on Fe3O4Surface modification of @ AA microsphere to obtain Fe3O4@ AAPDA microspheres;
(3) mixing Fe3O4And dispersing the @ AAPDA microspheres into a sodium hydroxide aqueous solution, dropwise adding carbon disulfide for reaction, and separating the microspheres after the reaction to obtain the adsorbent. The equation for the synthesis reaction of the adsorbent is shown below:
furthermore, the adsorbent provided by the invention takes ferroferric oxide microspheres as a base material, and the ferroferric oxide microspheres have magnetism, are convenient to recover in the subsequent use process, and are convenient and fast to operate. The particle size of the ferroferric oxide microspheres is 10 nm-50 um. Preferably, the particle size of the ferroferric oxide microspheres is 10-100nm, 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 mass ratio of the ferroferric oxide microspheres to the ascorbic acid is 1: (0.5 to 1).
Further, in the step (1), the ferroferric oxide microspheres and ascorbic acid are subjected to reflux reaction in a solvent, and a stabilizer ascorbic acid is modified on the surfaces of the ferroferric oxide microspheres to obtain Fe3O4@ AA microspheres. The time of the reflux reaction is generally 3 to 5 hours. The solvent used in the reaction is water, and the amount of the water is 40-100 times of the weight of the ferroferric oxide microspheres.
Further, in the step (2), Fe3O4The mass ratio of the @ AA microspheres to the dopamine is 1: (0.2-2).
Further, in the step (2), Fe3O4Mixing the @ AA microsphere, dopamine and solvent uniformly, and adding PBS buffer solution to ensure thatThe system is alkalescent and fully reacts to obtain Fe3O4@ AAPDA microspheres. Fe3O4The @ AA microsphere, the dopamine and the solvent can be dispersed and mixed under ultrasound. After adding PBS buffer solution, reaction is carried out for 3-4 h. The solvent used for the reaction was water, and the PBS buffer solution used was phosphate buffered saline, which had a pH of 7.4. The dosage of the solvent is Fe3O4@ AA 1000-1500 times of the mass of the microsphere, and the mass ratio of the PBS buffer solution to the solvent is 1:0.9-1.1, preferably 1: 1.
Further, in the step (3), Fe3O4NH on the @ AAPDA microspheres reacts with NaOH and carbon disulfide to form sodium dithiocarbamate, CS2With Fe3O4The mass ratio of the @ AAPDA microspheres is 1:1 to 2, CS2Added in theoretical molar amount with NaOH, or CS2Excess addition of NaOH with CS2Is preferably 1: 1-2.
Further, in the step (3), carbon disulfide is dropwise added at room temperature, and the temperature is kept for continuous reaction for 2-5 hours after the carbon disulfide is dropwise added. The concentration of NaOH solution used in the reaction is 1-5 mol/L.
The adsorbent prepared by the invention has magnetism, good adsorption effect on various heavy metal ions, good stability, large adsorption capacity, simple adsorption operation and convenient recovery. The structural formula is as follows:
the adsorbent is a novel magnetic heavy metal trapping material, takes magnetic ferroferric oxide as a base material, is convenient for adsorption and separation operation, and uses ascorbic acid to stabilize Fe3O4Surface modification with polydopamine and sodium Dithiocarbamate (DTC) to provide Fe3O4The surface of the adsorbent is rich in stabilizer ascorbic acid and polydopamine, and the surface of the polydopamine is rich in chelating sites, so that the adsorption capacity of the adsorbent is increased. The adsorbent can realize the adsorption removal of most heavy metal ions, the separation operation is simple and easy to implement, and the adsorption operation is convenientThe high-performance adsorbing material.
The adsorbent can adsorb various heavy metal ions with large adsorption capacity, and the heavy metal ions can be Cu2+,Cd2+,Ni2+,Pb2+,Hg2+And the like.
Furthermore, the heavy metal wastewater of the invention can be various wastewater containing heavy metal ions, mainly industrial wastewater, such as wastewater produced in the industries of ore processing, building material processing, electroplating, mechanical manufacturing, metal and steel smelting, chemical production and the like.
The invention has the following beneficial effects:
1. according to the invention, the adsorbent is used for treating the wastewater containing noble metal ions, the adsorbent is obtained by reacting ferroferric oxide, ascorbic acid, dopamine, sodium hydroxide and carbon disulfide, the raw materials are easy to obtain, the synthesis process is simple, the operation is simple, a large amount of wastewater is not generated in the synthesis process, the environmental protection property is higher, and the practicability is high in practical application.
2. The adsorbent is prepared by using magnetic ferroferric oxide as a base material, modifying ascorbic acid and polydopamine serving as stabilizing agents on the surface of a magnetic microsphere, introducing sodium dithiocarbamate with strong adsorption chelation performance, and coordinating and chelating the sodium dithiocarbamate with heavy metal ions, so that the heavy metal ions in the wastewater are removed. The adsorbent has high adsorption efficiency, can realize adsorption and removal of most heavy metal ions, and is simple and easy to operate after heavy ions are adsorbed.
3. The adsorbent has magnetic property and chelating sites with strong adsorption effect, has good acid/alkali resistance, can be conveniently operated and can be used for adsorbing heavy metal ions Cu in a short time2+,Cd2+,Ni2+,Pb2+,Hg2+The adsorption separation is realized, the waste water containing heavy metal ions can be quickly treated, the recovery is convenient, the operation is convenient and quick, and the method has huge application potential.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to be limiting and whose scope is indicated in the claims.
Example 1
1.1 g of ferroferric oxide microspheres with the particle size of 500 nm are dispersed in 100 mL of deionized water, 0.5 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 microspheres.
2. 1g of Fe prepared as described above3O4@ AA @ 100 g of dopamine is uniformly dispersed in 1000 mL of deionized water. 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@ AAPDA microspheres.
3. Mixing 1g of Fe3O4The @ AAPDA microsphere is dispersed in 10mL of 1 mol/L NaOH aqueous solution, 1g of carbon disulfide is slowly dripped, after dripping, the mixture is stirred and reacted for 3 hours at room temperature, then the product is separated by strong magnet, and after 20 mL of deionized water is washed for three times, the mixture is dried in vacuum, thus obtaining the adsorbent.
Example 2
1. 2 g of ferroferric oxide microspheres with the particle size of 100nm are uniformly dispersed in 150 mL of deionized water, 1.5 g of ascorbic acid is added, and heating reflux is carried out for 5 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. 1g of Fe prepared as described above3O4@ AA @ microsphere is uniformly dispersed in 1100 mL of deionized water, 1g of dopamine is added, ultrasonic dispersion is carried out for 1 h, and 1100 mL of PBS buffer solution (pH7.4) is added for reaction for 3 h. 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@ AAPDA microspheres.
3. Mixing 1g of Fe3O4@ AAPDA microspheres are dispersed in 5 mL of 2 mol/L NaOH aqueous solution, 1g of carbon disulfide is slowly dripped, the mixture is stirred and reacted for 3 hours at room temperature after dripping, and then strong magnet is used for feeding the productAnd (5) separating, washing with 10mL of deionized water for three times, and drying in vacuum to obtain the adsorbent.
Example 3
1. Dispersing 1g of ferroferric oxide microspheres with the particle size of 50 nm in 100 mL of deionized water, adding 1g of ascorbic acid, and heating and refluxing for 4 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. 1g of Fe prepared as described above3O4@ AA microsphere is uniformly dispersed in 1500 mL deionized water, 1g dopamine is added, ultrasonic dispersion is carried out for 1 h, 1500 mL PBS buffer solution (pH7.4) is added, and reaction is carried out for 3 h. 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@ AAPDA microspheres.
3. Mixing 1g of Fe3O4The @ AAPDA microsphere is dispersed in 8 mL of 1 mol/L NaOH aqueous solution, 1g of carbon disulfide is slowly dripped, after dripping, the mixture is stirred and reacted for 3 hours at room temperature, then the product is separated by strong magnet, and after 20 mL of deionized water is washed for three times, the mixture is dried in vacuum, thus obtaining the adsorbent.
Example 4
1. 2 g of ferroferric oxide microspheres with the particle size of 10 nm are uniformly dispersed in 100 mL of deionized water, 1g of ascorbic acid is added, and heating and refluxing are carried out for 5 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. 1g of Fe prepared as described above3O4@ AA microsphere is uniformly dispersed in 1500 mL deionized water, 2 g dopamine is added, ultrasonic dispersion is carried out for 1 h, 1500 mL PBS buffer solution (pH7.4) is added, and reaction is carried out for 3 h. 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@ AAPDA microspheres.
3. Mixing 1g of Fe3O4@ AAPDA microspheres were dispersed in 10mL of 1 mol/L NaOH aqueous solution, and 1g of bis (methylene bis) was slowly droppedAnd (3) stirring and reacting carbon sulfide at room temperature for 3 hours after dripping, separating a product by using strong magnet, washing the product for three times by using 10mL of deionized water, and drying the product in vacuum to obtain the adsorbent.
Example 5
1. 2 g of ferroferric oxide microspheres with the particle size of 50 um are uniformly dispersed in 80 mL of deionized water, 1g of ascorbic acid is added, and heating and refluxing are carried out for 5 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. 1g of Fe prepared as described above3O4@ AA @ 100 g of dopamine is uniformly dispersed in 1000 mL of deionized water. 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@ AAPDA microspheres.
3. Mixing 1g of Fe3O4The @ AAPDA microsphere is dispersed in 7 mL of 1 mol/L NaOH aqueous solution, 1g of carbon disulfide is slowly dripped, after dripping, the mixture is stirred and reacted for 3 hours at room temperature, then a product is separated by strong magnet, and after washing is carried out for three times by 10mL of deionized water, the product is dried in vacuum, and the adsorbent is obtained.
Application example
The adsorbent prepared in the above example was tested for its adsorption performance on heavy metals by the following method:
a defined amount of the adsorbent (m) prepared in the above example was weighed accurately and added to a defined volume (V) and concentration (C)0) In a solution of heavy metal ions (pH 5). Fully absorbing in a shaking table at room temperature until the absorption is saturated, and separating the adsorbent by using strong magnet. And measuring the concentration (Ce) of heavy metal ions in the solution after saturated absorption by adopting an inductively coupled atomic emission spectrum.
Adsorption capacity Q of the adsorbent to noble metal ionseThe calculation is performed as follows:
Qe = （C0-Ce）V/m
wherein, C0Unit mol/L; ceUnit mol/L; v unit ml; m units g.
The adsorption capacity of each adsorbent for each heavy metal ion is shown in table 1 below:
Claims (10)
1. a method for removing heavy metal wastewater is characterized by comprising the following steps: the method comprises the following steps of (1) adsorbing and removing heavy metal ions in the wastewater by using an adsorbent, wherein the adsorbent is prepared by the following method:
(1) modifying ascorbic acid on the surface of ferroferric oxide microspheres to obtain Fe3O4@ AA microsphere;
(2) with dopamine on Fe3O4Surface modification of @ AA microsphere to obtain Fe3O4@ AAPDA microspheres;
(3) mixing Fe3O4And dispersing the @ AAPDA microspheres into a sodium hydroxide aqueous solution, dropwise adding carbon disulfide for reaction, and separating the microspheres after the reaction to obtain the adsorbent.
2. The removal method as set forth in claim 1, wherein: when the adsorbent is prepared, in the step (1), the particle size of the ferroferric oxide microspheres is 10 nm-50 um, preferably 10-100 nm.
3. The removing method according to claim 1 or 2, wherein: when the adsorbent is prepared, in the step (1), the mass ratio of the ferroferric oxide microspheres to the ascorbic acid is 1: 0.5 to 1; in step (2), Fe3O4The mass ratio of the @ AA microspheres to the dopamine is 1: 0.2 to 2; in step (3), CS2With Fe3O4The mass ratio of the @ AAPDA microspheres is 1: 1-2, NaOH and CS2In a molar ratio of 1: 1-2.
4. The removal method as set forth in claim 1, wherein: in the preparation of the adsorbent, in the step (1)Carrying out reflux reaction on ferroferric oxide microspheres and ascorbic acid in a solvent to obtain Fe3O4@ AA microspheres.
5. The removal method according to claim 4, wherein: when the adsorbent is prepared, in the step (1), the reaction time of the ferroferric oxide microspheres and the ascorbic acid is 3-5 hours; the reaction solvent is water, and the amount of the water is 40-100 times of the weight of the ferroferric oxide microspheres.
6. The removing method according to claim 1 or 2, wherein: in the step (2) of preparing the adsorbent, Fe is added3O4Mixing the @ AA microspheres, the dopamine and the solvent uniformly, adding PBS buffer solution, and fully reacting to obtain Fe3O4@ AAPDA microspheres.
7. The removal method as set forth in claim 6, wherein: when the adsorbent is prepared, in the step (2), the pH of the PBS buffer solution is 7.4, and the solvent is water.
8. The removing method according to claim 6 or 7, wherein: when the adsorbent is prepared, in the step (2), the dosage of the solvent is Fe3O4The mass of the @ AA microsphere is 1000-1500 times, and the mass ratio of the PBS buffer solution to the solvent is 1: 0.9-1.1; adding PBS buffer solution and reacting for 3-4 h.
9. The removing method according to claim 1 or 2, wherein: when the adsorbent is prepared, in the step (3), carbon disulfide is dropwise added at room temperature, and the temperature is kept for continuous reaction for 2-5 hours after the carbon disulfide is dropwise added; the concentration of the NaOH solution is 1-5 mol/L.
10. The removal method as set forth in claim 1, wherein: the heavy metal ions comprise Cu2+,Cd2+,Ni2+,Pb2 +Or Hg2+。
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| CN113274991A (en) * | 2021-06-17 | 2021-08-20 | 山东天玉墙体工程有限公司 | Method for removing hexavalent chromium ions in wastewater |
| CN115055171A (en) * | 2022-06-27 | 2022-09-16 | 湖南国重环境科技有限责任公司 | Composite magnetic adsorption material and preparation method and application thereof |
| CN115055171B (en) * | 2022-06-27 | 2024-04-05 | 湖南国重环境科技有限责任公司 | Composite magnetic adsorption material and preparation method and application thereof |
| CN114890606A (en) * | 2022-07-05 | 2022-08-12 | 湖南国重环境科技有限责任公司 | Treatment system and treatment method for multi-pollutant wastewater |
| CN115155516A (en) * | 2022-09-09 | 2022-10-11 | 淄博正河净水剂有限公司 | Heavy metal wastewater adsorbent and preparation method thereof |
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