CN113731378A - Fe for oil-water separation3O4/HA/CSMNPs, preparation method and application - Google Patents
Fe for oil-water separation3O4/HA/CSMNPs, preparation method and application Download PDFInfo
- Publication number
- CN113731378A CN113731378A CN202111094441.9A CN202111094441A CN113731378A CN 113731378 A CN113731378 A CN 113731378A CN 202111094441 A CN202111094441 A CN 202111094441A CN 113731378 A CN113731378 A CN 113731378A
- Authority
- CN
- China
- Prior art keywords
- csmnps
- preparation
- oil
- water
- mnps
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000000926 separation method Methods 0.000 claims abstract description 38
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 13
- DBFFAGQMEMIOQB-UHFFFAOYSA-N hexadecane;hydrate Chemical compound O.CCCCCCCCCCCCCCCC DBFFAGQMEMIOQB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000975 co-precipitation Methods 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 24
- 239000011553 magnetic fluid Substances 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052603 melanterite Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000007908 nanoemulsion Substances 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 abstract description 24
- 239000000839 emulsion Substances 0.000 abstract description 18
- 229920006317 cationic polymer Polymers 0.000 abstract description 13
- 239000003431 cross linking reagent Substances 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 100
- 239000004021 humic acid Substances 0.000 description 100
- 230000000052 comparative effect Effects 0.000 description 17
- 230000000694 effects Effects 0.000 description 13
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000010355 oscillation Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
- 238000000733 zeta-potential measurement Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- 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
- B01J20/26—Synthetic macromolecular compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention belongs to the technical field of functional materials, and particularly relates to Fe for oil-water separation3O4/HA/CSMNPs, preparation method and application thereof, and synthesis of Fe coated by HA and CS through chemical coprecipitation3O4MNPs comprising the steps of: s1 Synthesis of HA-coated Fe3O4MNPs; s2, preparing chitosan CS gel B; s3 preparation of Fe3O4the/HA/CS MNPs. Preparation of Fe3O4HA/CS MNPs grafting cationic polymers CS to magnetic Fe with HA as linking group3O4The surface avoids using a cross-linking agent, and the preparation method is simple and convenient; it utilizes a cationic polymer chitosanThe amino group makes the surface thereof to be positively charged and generate electrostatic attraction with the negatively charged hexadecane-water emulsion, thereby being capable of completing oil-water separation with high efficiency and low dosage.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to Fe for oil-water separation3O4The preparation method and application of the/HA/CSMNPs.
Background
The Magnetic Nano (MNPs) materials are widely applied to the field of sewage treatment due to the advantages of easy recovery, reusability and the like, and meanwhile, the small-sized nano materials have high specific surface area and high surface energy, so that the chemical activity and the capacity of adsorbing various pollutants by the magnetic nano materials are increased. Humic Acid (HA) is a macromolecular organic substance widely existing in nature, and is a macromolecular aromatic compound containing multiple functional groups such as phenolic hydroxyl, carboxyl, alcoholic hydroxyl, methoxyl and the like according to chemical structure analysis, and HA is used as an intermediate bridge to coat a cationic polymer, so that the synthesized magnetic nano material HAs positive charges and is attracted with positive and negative charges of emulsion to achieve the oil-water separation effect.
At present, most of magnetic adsorbents are prepared by cross-linking reaction by using chemical agents such as cross-linking agent, and the environment is polluted by using organic solvent in the process3O4A surface. The cross-linking agent is avoided, so that the preparation process is simple, convenient, economic, green and environment-friendly; the surface of the cationic polymer chitosan is positively charged by using amino of the cationic polymer chitosan, and electrostatic attraction is generated between the cationic polymer chitosan and negatively charged hexadecane-water emulsion, so that the oil-water separation can be efficiently completed with low use amount.
Disclosure of Invention
The present invention is directed to the above problems of the prior art magnetic adsorbents made by grafting a cationic polymer CS to magnetic Fe via an HA linking group3O4The surface of the cationic polymer CS is positively charged by using the amino group of the cationic polymer CS and is electrostatically attracted with the negatively charged hexadecane-water emulsion, so that the oil-water separation can be efficiently completed with low use amount.
One of the objects of the present invention is to provide Fe for oil-water separation3O4/HA/CSMNPs(Fe3O4Magnetic nanoparticles of HA/CS) by chemical coprecipitation3O4MNPs comprising the steps of:
s1 Synthesis of HA-coated Fe3O4MNPs: FeSO (ferric oxide) is added4·7H2O and FeCl3·6H2Dissolving O in water, and vacuumizingEmpty and heat; then dissolving 25% ammonium hydroxide solution and HA in water, adding into a reaction system, stirring at 90 ℃, and cooling to room temperature to obtain Fe3O4The magnetic fluid A is obtained by ultrasonic treatment after the pH value is adjusted to 4.9;
s2, preparation of CS gel B: dissolving CS in an acetic acid solution with the mass fraction of 1%, and stirring to obtain CS gel B;
s3 preparation of Fe3O4[ HA/CSMNPs: dropwise adding the CS gel B obtained in the step S2 into the magnetic fluid A obtained in the step S1 under the ultrasonic condition, stirring after ultrasonic treatment, centrifugally washing with distilled water to obtain a precipitate, and drying the precipitate to obtain Fe3O4/HA/CSMNPs。
Preferably, in S1, the FeSO4·7H2O and FeCl3·6H2The mass ratio of O is 1: 2.
Preferably, in S1, the heating temperature is 60-120 ℃.
Preferably, in S1, the FeSO4·7H2The mass-volume ratio of the O to the HA and ammonium hydroxide solution is 2.78g to 0.77g to 5-10 mL.
Preferably, in S1, the stirring time is 30-150 min, and the ultrasonic time is 10-15 min.
Preferably, in S2, the mass-to-volume ratio of CS to acetic acid solution is 0.2-0.9 g: 50 mL.
Preferably, in S2, the stirring time is 25-35 min.
Preferably, in S3, the ultrasonic time is 15-25 min, and the stirring time is 50-80 min.
Another object of the present invention is to provide Fe for oil-water separation3O4Fe prepared by preparation method of/HA/CSMNPs3O4/HA/CSMNPs。
It is another object of the present invention to provide Fe3O4the/HA/CSNPs are applied to the separation of the hexadecane-water nanoemulsion oil and water.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention is realized by chemical copolymerizationPrecipitation method for grafting cationic polymer CS to magnetic Fe by taking humic acid as connecting group3O4Surface formation of Fe3O4The preparation process of the/HA/CSMNPs avoids using a cross-linking agent, is green and environment-friendly, and HAs a simple preparation method.
2. The invention takes HA as an intermediate bridge to coat the cationic polymer, so that the synthesized Fe3O4the/HA/CS MNPs material HAs positive charges, and the surface of the cationic polymer CS is positively charged by utilizing the amino group of the cationic polymer CS and generates electrostatic attraction with negatively charged hexadecane-water emulsion, so that the oil-water separation can be efficiently and quickly completed.
Drawings
FIG. 1 shows Fe prepared in the present invention3O4A process flow diagram for/HA/CSMNPs;
FIG. 2 shows Fe prepared in the present invention3O4X-ray powder diffractometry of/HA/CSMNPs;
FIG. 3 shows Fe prepared in the present invention3O4Fourier infrared spectrometer plot of/HA/CSMNPs;
FIG. 4 shows Fe prepared in the present invention3O4Zeta potential map of/HA/CSMNPs;
FIG. 5 shows Fe prepared by the present invention3O4Particle size plot of/HA/CSMNPs;
FIG. 6 shows Fe prepared by the present invention3O4Transmission electron microscopy of/HA/CSMNPs;
FIG. 7 shows Fe prepared by the present invention3O4Scanning electron microscopy images of/HA/CSMNPs;
FIG. 8 shows the oscillation time vs. Fe in the present invention3O4Influence graph of oil-water separation effect of/HA/CSMNPs;
FIG. 9 shows Fe of the present invention3O4Graph showing the effect of the addition amount of/HA/CSNPs on the oil-water separation effect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the present invention, Fe3O4For ferroferric oxide, HA is humic acid and CS is chitosan, the terminology used in the present invention is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention, unless otherwise specifically indicated, and the various materials, reagents, equipment and devices used in the following examples of the present invention are commercially available or may be prepared by conventional methods.
Example 1
Fe for oil-water separation3O4Preparation method of/HA/CSMNPs, synthesis of Fe coated with HA and CS by chemical coprecipitation3O4MNPs comprising the steps of:
s1 Synthesis of HA-coated Fe3O4MNPs: 2.78g of FeSO4·7H2O and 5.56g FeCl3·6H2Dissolving O in 100mL of water, vacuumizing and heating to 90 ℃; then 10mL of 25% ammonium hydroxide solution and 0.77g of HA were dissolved in 50mL of water and added to the reaction system, stirred at 90 ℃ for 30min, and then cooled to room temperature to obtain Fe3O4Performing ultrasonic treatment for 15min after adjusting the pH value to 4.9 to obtain magnetic fluid A;
s2, preparing chitosan CS gel B: dissolving 0.9g of CS in 50mL of 1% acetic acid solution, and stirring for 30min to obtain chitosan CS gel B;
s3 preparation of Fe3O4[ HA/CSMNPs: dropwise adding the chitosan CS gel B obtained in the step S2 into the magnetic fluid A obtained in the step S1 under the ultrasonic condition, carrying out ultrasonic treatment for 20min, stirring for 60min, carrying out centrifugal washing for 3 times by using distilled water to obtain precipitates, and drying for 12h in a vacuum drying oven at the temperature of 50 ℃ to obtain Fe3O4/HA/CS MNPs。
Example 2
Fe for oil-water separation3O4Preparation method of/HA/CSMNPs by chemical coprecipitationCo-coated Fe to HA and CS3O4MNPs comprising the steps of:
s1 Synthesis of HA-coated Fe3O4MNPs: 2.78g of FeSO4·7H2O and 5.56g FeCl3·6H2Dissolving O in 100mL of water, vacuumizing and heating to 90 ℃; then 5mL of 25% ammonium hydroxide solution and 0.77g of HA were dissolved in 50mL of water and added to the reaction system, stirred at 90 ℃ for 150min, and then cooled to room temperature to obtain Fe3O4Performing ultrasonic treatment for 15min after adjusting the pH value to 4.9 to obtain magnetic fluid A;
s2, preparing chitosan CS gel B: dissolving 0.2g of CS in 50mL of 1% acetic acid solution, and stirring for 25min to obtain chitosan CS gel B;
s3 preparation of Fe3O4[ HA/CSMNPs: dropwise adding the chitosan CS gel B obtained in the step S2 into the magnetic fluid A obtained in the step S1 under the ultrasonic condition, carrying out ultrasonic treatment for 10min, stirring for 80min, centrifugally washing for 5 times by using distilled water to obtain precipitates, and drying for 15h in a vacuum drying oven at the temperature of 55 ℃ to obtain Fe3O4/HA/CS MNPs。
Example 3
Fe for oil-water separation3O4Preparation method of/HA/CSMNPs, synthesis of Fe coated with HA and CS by chemical coprecipitation3O4MNPs comprising the steps of:
s1 Synthesis of HA-coated Fe3O4MNPs: 2.78g of FeSO4·7H2O and 5.56g FeCl3·6H2Dissolving O in 100mL of water, vacuumizing and heating to 90 ℃; then 8mL of 25% ammonium hydroxide solution and 0.77g of HA were dissolved in 50mL of water and added to the reaction system, stirred at 90 ℃ for 90min, and then cooled to room temperature to obtain Fe3O4Performing ultrasonic treatment for 12min after adjusting the pH value to 4.9 to obtain magnetic fluid A;
s2, preparing chitosan CS gel B: dissolving 0.5g of CS in 50mL of 1% acetic acid solution, and stirring for 35min to obtain chitosan CS gel B;
s3 preparation of Fe3O4[ HA/CSMNPs: obtained in S2Adding chitosan CS gel B into the magnetic fluid A obtained in S1 dropwise under the ultrasonic condition, carrying out ultrasonic treatment for 25min, stirring for 50min, carrying out centrifugal washing for 4 times with distilled water to obtain precipitate, and drying in a vacuum drying oven at 60 ℃ for 10h to obtain Fe3O4/HA/CS MNPs。
Example 4
Fe for oil-water separation3O4Preparation method of/HA/CSMNPs, synthesis of Fe coated with HA and CS by chemical coprecipitation3O4MNPs comprising the steps of:
s1 Synthesis of HA-coated Fe3O4MNPs: 2.78g of FeSO4·7H2O and 5.56g FeCl3·6H2Dissolving O in 100mL of water, vacuumizing and heating to 90 ℃; then 10mL of 25% ammonium hydroxide solution and 0.77g of HA were dissolved in 50mL of water and added to the reaction system, stirred at 90 ℃ for 120min, and then cooled to room temperature to obtain Fe3O4Performing ultrasonic treatment for 15min after adjusting the pH value to 4.9 to obtain magnetic fluid A;
s2, preparing chitosan CS gel B: dissolving 0.7g of CS in 50mL of 1% acetic acid solution, and stirring for 25min to obtain chitosan CS gel B;
s3 preparation of Fe3O4[ HA/CSMNPs: dropwise adding the chitosan CS gel B obtained in the step S2 into the magnetic fluid A obtained in the step S1 under the ultrasonic condition, carrying out ultrasonic treatment for 15min, stirring for 65min, carrying out centrifugal washing for 4 times by using distilled water to obtain precipitates, and drying for 12h in a vacuum drying oven at the temperature of 65 ℃ to obtain Fe3O4/HA/CS MNPs。
Example 5
Fe for oil-water separation3O4Preparation method of/HA/CSMNPs, synthesis of Fe coated with HA and CS by chemical coprecipitation3O4MNPs comprising the steps of:
s1 Synthesis of HA-coated Fe3O4MNPs: 2.78g of FeSO4·7H2O and 5.56g FeCl3·6H2Dissolving O in 100mL of water, vacuumizing and heating to 90 ℃; 10mL of 25% ammonium hydroxide solution and 0.77g of HA were then dissolved in 50mL of waterAdding into a reaction system, stirring at 90 ℃ for 30min, and cooling to room temperature to obtain Fe3O4A HA magnetic fluid A;
s2, preparing chitosan CS gel B: dissolving 0.5g of CS in 50mL of 1% acetic acid solution, and stirring for 30min to obtain chitosan CS gel B;
s3 preparation of Fe3O4[ HA/CSMNPs: dropwise adding the chitosan CS gel B obtained in the step S2 into the magnetic fluid A obtained in the step S1 under the ultrasonic condition to adjust the pH value to 4.9, carrying out ultrasonic treatment for 25min, then stirring for 60min, carrying out centrifugal washing for 5 times by using distilled water to obtain precipitates, drying for 10h in a vacuum drying oven at the temperature of 60 ℃ to obtain Fe3O4/HA/CSMNPs。
Comparative example 1 Synthesis of Fe3O4/HAMNPs：
Synthesis of HA-coated Fe by chemical coprecipitation3O4MNPs, 2.78g of FeSO4·7H2O and 5.56g FeCl3·6H2Dissolving O in 100mL of distilled water, vacuumizing and heating to 90 ℃; then 10mL of ammonium hydroxide (25%) solution and 0.77g of HA were dissolved in 50mL of water and added to the reaction system quickly; the mixture was stirred at 90 ℃ for 30 minutes and then cooled to 25 ℃; finally, the black precipitate was collected by centrifugation, washed with distilled water and dried in a vacuum oven at 65 ℃.
Comparative example 2 Synthesis of Fe3O4/CSMNPs：
0.5g of chitosan was dissolved in 50mL of acetic acid solution (1%, v/v), followed by addition of 2.0g of Fe3O4And (3) after mechanical stirring for 30min, dropwise adding 100mL of 1M NaOH solution, stirring for 1h, washing with absolute ethyl alcohol and distilled water for multiple times, and separating the product under the action of a magnet.
FIG. 2 is an XRD pattern of MNPs synthesized in example 1 and comparative examples 1-2 of the present invention, as shown in standard card (PDF #19-0629), Fe3O4The (220), (311), (400), (511), and (440) crystal planes of the crystal should correspond to six sets of characteristic absorption peaks, i.e., 2 θ equal to 29.8 °, 35.2 °, 43.2 °, 57.0 °, and 62.8 °; the MNPs synthesized in example 1 and comparative examples 1-2 all have the same diffraction peak, indicating that the MNPs are synthesizedFe3O4Example 1 and comparative examples 1 to 2 synthesized three types of Fe3O4The MNPs all had a cubic spinel magnetite structure, indicating that the HA and CS coatings did not alter Fe3O4Crystal structure of (a).
FIG. 3 is an infrared chart of MNPs synthesized in example 1 of the present invention and comparative examples 1-2, as shown in FIG. 3, at 587cm-1The absorption peak appears as pure Fe3O4The tensile vibration of Fe-O in the medium is 1071cm-1 Peak 1 is C-OH stretching vibration; 931cm-1And 2866cm-1The absorption peak is CH on chitosan2And CH3C-H strong stretching vibration absorption peak of 1382cm-1Is a deformation vibration of N-H, 1625cm-1And 1540cm-1Absorption peak is-NH3+and-COO–The existence of humic acid indicates that the humic acid and the chitosan have electrostatic interaction; 3400cm-1The absorption peak is due to-NH2and-OH, indicating that the synthetic magnetic chitosan surface contains a large number of amino and carboxyl groups 1625cm-1The characteristic peak is caused by C ≡ N, which indicates that CS is modified in Fe3O4The surface of/HA.
FIG. 4 shows the synthesis of Fe in example 1 of the present invention3O4Zeta potential diagram of/HA/CSMNPs, it is clear from the zeta potential analysis of FIG. 4 that Fe is contained in large amounts in the HA surface due to the carboxyl and phenolic hydroxyl groups3O4The potential of the/HA nanoparticles was-31.8 (. + -. 1.1) m. And the potential at pH 7.0 after CS modification was 15.6 mV. Fe3O4The isoelectric point of the/HA/CSMNPs is 8.69, and the Fe is lower than the pH value of 8.693O4the/HA/CSmNPs are positively charged on the surface and electrostatically attracted to a negatively charged hexadecane-water emulsion, and Fe at a pH of greater than 8.693O4the/HA/CSNPs surface is negatively charged and electrostatically repels the negatively charged hexadecane-water emulsion.
TABLE 1 contact angles of MNPs of example 1 and comparative examples 1-2
| Contact angle (°) | |
| Example 1 | 43.078° |
| Comparative example 1 | 24.462 |
| Pure Fe3O4 | 20° |
Inventive example 1 Synthesis of Fe3O4the/HA/CSMNPs were measured by Water Contact Angle (WCA) and as shown in Table 1, pure Fe was modified3O4Contact angle (. theta.w) of 20 DEG, Fe3O4The contact angle of HA is 24.462 degrees, and the contact angle is increased by 4.629 degrees after HA modification; and Fe3O4The contact angle of/HA/CSMNPs was 43.078 deg., which indicates Fe3O4After HA and CS are modified on the surface, the contact angle is changed, and the hydrophobicity of the CS is increased by the surface modification; thus, Fe3O4the/HA/CSMNPs have great potential for attaching emulsified oil droplets.
FIG. 5 shows the synthesis of Fe in example 1 of the present invention3O4Dynamic light Scattering of/HA/CSMNPs, as can be seen from the analysis of FIG. 5, Fe3O4The hydrodynamic diameter of the/HA nanoparticles was 30.6 (+ -12.4) nm, 487.94 (+ -30.5) nm after CS modification. These results indicate CS modification of Fe3O4the/HA/CSMNPs are positively charged on the surface and increase in particle size.
FIGS. 6 and 7 are views for synthesizing Fe according to example 1 of the present invention3O4TEM and SEM images of/HA/CSMNPs from the TEM of FIG. 6, nanoscale particles were successfully prepared, and Fe was prepared3O4the/HA/CSMNPs particles are basically monodisperse, and after modification by using HA and CS, the surfaces of the particles are agglomerated to different degrees, so that the particles are not uniform; from SEM in FIG. 7, it can be seen that Fe was grafted3O4The surface of the/HA/CSMNPs is rough, and the loose porous structure of CS provides more adsorption sites for oil-water separation.
Adding 250mg/L of MNPs synthesized in the embodiment 1 and the comparative examples 1-2 into 20mL of an oil-water emulsion mixture prepared from hexadecane-water, placing the mixture in an oscillator for oscillation, taking a certain amount of emulsion every 30min, placing the emulsion for 15min under the action of an external magnetic field, separating the MNPs synthesized in the embodiment 1 and the comparative examples 1-2 from the emulsion mixture under the action of the external magnetic field, measuring the wavelength of the emulsion at 225nm by using an ultraviolet spectrophotometer, and repeatedly measuring for three times to determine an average value; then, C is obtained according to the standard curve0And Ce, and solving the demulsification efficiency.
The demulsification efficiency formula is as follows:
where Es is the emulsion breaking efficiency, C0(mg/L) is the initial oil concentration of the emulsion mixture, CeIs the oil concentration of the emulsion after addition of the MNPs.
As shown in FIG. 8, the MNPs synthesized in example 1 and comparative examples 1-2 contain Fe at the same concentration3O4/HA/CS、Fe3O4/HA、Fe3O4FIG. 8 shows that the oil-water separation of the MNPs synthesized in example 1 and comparative examples 1-2 is almost balanced by 230min of oscillation, and Fe synthesized in example 1 increases with the oscillation time3O4Es increase for/HA/CSMNPs, Fe3O4The Es of the HA/CS MNPs can reach 69.44% within 30min, and when the oscillation time is 230min, the Es can reach 96.39%; while the Fe synthesized in comparative examples 1-2 is oscillated for 230min3O4/HA and Fe3O4The Es of the CS can reach 18.16 percent and 24.85 percent respectively; without adding any materialThe emulsion mixture of (a) has substantially no oil-water separation effect. Compared with comparative examples 1-2, the Fe synthesized in the example 1 of the invention3O4The oil-water separation efficiency of the/HA/CSMNPs is higher and faster, and due to the fact that the surface amino of the CS is easy to protonate and is positive, HA is used as a bridge and is in contact with Fe3O4Phase-connecting to synthesize positively charged Fe3O4the/HA/CSNPs and the emulsion with negative electricity generate electrostatic attraction, so that the oil-water separation effect is better. While comparative example 2 synthesized Fe3O4CS surface modified chitosan and Fe3O4The interaction force is small, and CS falls off in the oil-water separation process, so that the oil-water separation efficiency is poor; HA HAs abundant functional groups, wherein carboxyl, carbonyl, hydroxyl and phenolic groups make Fe synthesized in comparative example 13O4The surfaces of the HAMNPs are negatively charged and generate electrostatic repulsion with negatively charged emulsion, so that the oil-water separation effect is poor.
FIG. 9 shows the effect of MNPs synthesized in example 1 and comparative examples 1-2 on the emulsion Es at a concentration of 0-250 mg/L, and it can be seen from FIG. 9 that the oil-water separation effect increases with the increase of the addition amount of MNPs, wherein when Fe synthesized in example 13O4When the addition amount of the/HA/CSNPs is 25mg/L, the oil-water separation effect can reach 26.13 percent, and when the addition amount of the/HA/CSNPs is Fe3O4The addition amount of the/HA/CSNPs is 100mg/L, the oil-water separation effect can reach 89.35%, the addition amount is 250mg/L, and the oil-water separation effect can reach 96.38%. Thus, it was found that Fe was synthesized3O4the/HA/CSNPs can rapidly separate oil from water in a short time and with a small addition amount.
It should be noted that, when the present invention relates to a numerical range, it should be understood that two endpoints of each numerical range and any value between the two endpoints can be selected, and since the steps and methods adopted are the same as those in the embodiment, in order to prevent redundancy, the present invention describes a preferred embodiment. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. Fe for oil-water separation3O4Method for preparing/HA/CSMNPs, characterized in that the synthesis of HA and CS co-coated Fe by chemical co-precipitation3O4MNPs comprising the steps of:
s1 Synthesis of HA-coated Fe3O4MNPs: FeSO (ferric oxide) is added4·7H2O and FeCl3·6H2Dissolving O in water, vacuumizing and heating; then dissolving 25% ammonium hydroxide solution and HA in water, adding into a reaction system, stirring at 90 ℃, and cooling to room temperature to obtain Fe3O4@ HA magnetic fluid, and obtaining magnetic fluid A by ultrasonic after adjusting the pH value to 4.9;
s2, preparation of CS gel B: dissolving CS in an acetic acid solution with the mass fraction of 1%, and stirring to obtain CS gel B;
s3 preparation of Fe3O4[ HA/CSMNPs: dropwise adding the CS gel B obtained in the step S2 into the magnetic fluid A obtained in the step S1 under the ultrasonic condition, stirring after ultrasonic treatment, centrifugally washing with distilled water to obtain a precipitate, and drying the precipitate to obtain Fe3O4/HA/CSMNPs。
2. Fe for oil-water separation according to claim 13O4The preparation method of/HA/CSMNPs is characterized in that in S1, the FeSO4·7H2O and FeCl3·6H2The mass ratio of O is 1: 2.
3. Fe for oil-water separation according to claim 23O4The preparation method of the/HA/CSMNPs is characterized in that in S1, the heating temperature is 60-120℃。
4. Fe for oil-water separation according to claim 33O4The preparation method of/HA/CSMNPs is characterized in that in S1, the FeSO4·7H2The mass-volume ratio of the O to the HA and ammonium hydroxide solution is 2.78g to 0.77g to 5-10 mL.
5. Fe for oil-water separation according to claim 43O4The preparation method of the/HA/CSMNPs is characterized in that in S1, the stirring time is 30-150 min, and the ultrasonic time is 10-15 min.
6. Fe for oil-water separation according to claim 53O4The preparation method of the/HA/CSMNPs is characterized in that in S2, the mass-to-volume ratio of the CS to the acetic acid solution is 0.2-0.9 g: 50 mL.
7. Fe for oil-water separation according to claim 63O4The preparation method of the/HA/CSMNPs is characterized in that in S2, the stirring time is 25-35 min.
8. Fe for oil-water separation according to claim 73O4The preparation method of the/HA/CSMNPs is characterized in that in S3, the ultrasonic time is 15-25 min, and the stirring time is 50-80 min.
9. Fe prepared by the preparation method of claim 13O4/HA/CSMNPs。
10. Fe as claimed in claim 93O4Application of/HA/CSMNPs in separation of oil and water of hexadecane-water nano emulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111094441.9A CN113731378A (en) | 2021-09-17 | 2021-09-17 | Fe for oil-water separation3O4/HA/CSMNPs, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111094441.9A CN113731378A (en) | 2021-09-17 | 2021-09-17 | Fe for oil-water separation3O4/HA/CSMNPs, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113731378A true CN113731378A (en) | 2021-12-03 |
Family
ID=78739725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111094441.9A Pending CN113731378A (en) | 2021-09-17 | 2021-09-17 | Fe for oil-water separation3O4/HA/CSMNPs, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113731378A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013106948A1 (en) * | 2012-01-18 | 2013-07-25 | 芮宝生医股份有限公司 | Method for manufacturing magnetic particle composite |
| CN103962106A (en) * | 2014-06-03 | 2014-08-06 | 湖南大学 | Method for removing lead in wastewater by virtue of chitosan/humic acid-modified magnetic adsorbent |
| CN105367715A (en) * | 2015-12-16 | 2016-03-02 | 杭州电子科技大学 | Preparing method for amphiphilic positive ion and chitosan based magnetic flocculating agent |
| CN105692821A (en) * | 2016-03-10 | 2016-06-22 | 浙江海洋学院 | Method for removing oil in water |
| CN106268680A (en) * | 2016-10-12 | 2017-01-04 | 沈阳航空航天大学 | Magnetic Nano microcapsule adsorbent and its preparation method and application |
| CN107081138A (en) * | 2017-05-19 | 2017-08-22 | 上海工程技术大学 | Magnetic polystyrene base enclosure glycan composite adsorbent and preparation method and application |
-
2021
- 2021-09-17 CN CN202111094441.9A patent/CN113731378A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013106948A1 (en) * | 2012-01-18 | 2013-07-25 | 芮宝生医股份有限公司 | Method for manufacturing magnetic particle composite |
| CN103962106A (en) * | 2014-06-03 | 2014-08-06 | 湖南大学 | Method for removing lead in wastewater by virtue of chitosan/humic acid-modified magnetic adsorbent |
| CN105367715A (en) * | 2015-12-16 | 2016-03-02 | 杭州电子科技大学 | Preparing method for amphiphilic positive ion and chitosan based magnetic flocculating agent |
| CN105692821A (en) * | 2016-03-10 | 2016-06-22 | 浙江海洋学院 | Method for removing oil in water |
| CN106268680A (en) * | 2016-10-12 | 2017-01-04 | 沈阳航空航天大学 | Magnetic Nano microcapsule adsorbent and its preparation method and application |
| CN107081138A (en) * | 2017-05-19 | 2017-08-22 | 上海工程技术大学 | Magnetic polystyrene base enclosure glycan composite adsorbent and preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lü et al. | Treatment of emulsified oil wastewaters by using chitosan grafted magnetic nanoparticles | |
| CN107999037B (en) | Magnetic polymer adsorption material, preparation method and application | |
| CN110961085B (en) | By using CO2Method for preparing amidoxime functionalized hollow porous polymer microspheres for emulsion template | |
| Mahdavinia et al. | Facile and green rout to prepare magnetic and chitosan-crosslinked κ-carrageenan bionanocomposites for removal of methylene blue | |
| Yu et al. | Preparation of a novel chitosan-based magnetic adsorbent CTS@ SnO2@ Fe3O4 for effective treatment of dye wastewater | |
| Ma et al. | Hydrophilic dual‐responsive magnetite/PMAA core/shell microspheres with high magnetic susceptibility and ph sensitivity via distillation‐precipitation polymerization | |
| Pei et al. | Tannin‐immobilized cellulose microspheres as effective adsorbents for removing cationic dye (Methylene Blue) from aqueous solution | |
| Chen et al. | Synthesis of magnetic carboxymethyl cellulose/graphene oxide nanocomposites for adsorption of copper from aqueous solution | |
| CN110938282A (en) | Composite material with covalent organic framework and core-shell structure and preparation method and application thereof | |
| Zeng et al. | Fabrication of chitosan/alginate porous sponges as adsorbents for the removal of acid dyes from aqueous solution | |
| CN109293976B (en) | Preparation method of porous chitosan microspheres | |
| CN110548478A (en) | modified magnetic nano particle and application thereof | |
| Li et al. | Preparation, characterization, adsorption kinetics and thermodynamics of chitosan adsorbent grafted with a hyperbranched polymer designed for Cr (VI) removal | |
| CN112169773B (en) | Enhanced magnetic adsorbent | |
| CN112090406A (en) | Preparation method of polyethyleneimine modified chitosan magnetic composite material | |
| Jia et al. | Water-Insoluble Cyclodextrin-based nanocubes for highly efficient adsorption toward diverse organic and inorganic pollutants | |
| Wang et al. | Preparation and adsorption properties of chitosan–poly (acrylic acid) nanoparticles for the removal of nickel ions | |
| Xu et al. | β-Cyclodextrin functionalized magnetic nanoparticles for the removal of pharmaceutical residues in drinking water | |
| CN113278096A (en) | White carbon black with surface grafted with poly Schiff base ionic liquid and preparation method thereof | |
| Peng et al. | A bowl-shaped biosorbent derived from sugarcane bagasse lignin for cadmium ion adsorption | |
| Si et al. | Preparation of β-cyclodextrin/Fe 3 O 4/polyvinylpyrrolidone composite magnetic microspheres for the adsorption of methyl orange | |
| Heydari et al. | Fabrication and characterization of polymer based magnetic dialdehyde carboxymethyl cellulose/cysteine nanocomposites for methylene blue removal | |
| CN113731378A (en) | Fe for oil-water separation3O4/HA/CSMNPs, preparation method and application | |
| Zhang et al. | Preparation of starch-based adsorbing-flocculating bifunctional material St-A/F and its removal of active, direct and disperse dyes from textile printing and dyeing wastewater | |
| CN110330671B (en) | Preparation method of cyclodextrin microspheres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211203 |
|
| RJ01 | Rejection of invention patent application after publication |