CN114192119A - Sulfydryl modified magnetic particle dispersion liquid and preparation method and application thereof - Google Patents
Sulfydryl modified magnetic particle dispersion liquid and preparation method and application thereof Download PDFInfo
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- 239000006185 dispersion Substances 0.000 title claims abstract description 84
- 239000006249 magnetic particle Substances 0.000 title claims abstract description 79
- 239000007788 liquid Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 60
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 37
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 24
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 24
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 24
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 19
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007885 magnetic separation Methods 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 23
- 239000002351 wastewater Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 15
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- 238000002474 experimental method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052701 rubidium Inorganic materials 0.000 description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002656 O–Si–O Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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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- 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
-
- 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
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Compounds Of Iron (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a sulfhydryl modified magnetic particle dispersion liquid, a preparation method and application thereof. The preparation method comprises the following steps: s1, dropping the silicate solution into Fe under the condition of stirring and constant temperature3O4Adding hydrochloric acid solution into the dispersion liquid I to adjust the pH, aging, carrying out magnetic separation to remove clear liquid, and washing to obtain Fe3O4@SiO2A dispersion liquid II; s2, stirring and stirring to Fe at constant temperature3O4@SiO2Adding a hydrochloric acid solution into the dispersion liquid II, uniformly mixing, activating, washing, and forming a dispersion liquid III in glycerol; s3, mixingAnd transferring the dispersion liquid III into a reaction container, adding methanol, stirring and keeping constant temperature, dropwise adding the reaction liquid to react, washing and ultrasonically dispersing to obtain a dispersion liquid IV, wherein the magnetic particles in the dispersion liquid IV are sulfhydryl-modified magnetic particles. The functional magnetic particles provided by the invention are porous magnetic particles capable of efficiently removing mercury pollutants in a water body, the effective sites of the porous magnetic particles are distributed on the surfaces of the magnetic particles or in cavities of the magnetic particles in a spider-web shape, and the magnetic particle dispersion liquid can also be used for adsorption removal of mercury in the water body and recycling of mercury resources.
Description
Technical Field
The invention relates to the technical field of environmental science, engineering and materials, in particular to a sulfydryl modified magnetic particle dispersion liquid and a preparation method and application thereof.
Background
The mercury-containing waste water is mainly from non-ferrous metal smelting plants, chemical plants, pesticide plants, paper mills, dye plants, thermal instruments and instrument plants, etc. The main mercury form of the mercury-containing wastewater is inorganic mercury, and methods for removing the inorganic mercury from the wastewater include a sulfide precipitation method, a chemical flocculation method, an activated carbon adsorption method, a metal reduction method and the like. Generally, the alkalescent mercury-containing wastewater is usually treated by a chemical flocculation method or a sulfide precipitation method; the acidic mercury-containing wastewater is treated by a metal reduction method. However, these methods have limitations such as failure to recover the treated mercury and the treated products may cause secondary pollution of the mercury-containing solid waste. These problems greatly limit the recycling of mercury resources and cause a significant loss of the globally limited sulphide resources.
Disclosure of Invention
The invention solves the problems in the prior art, and aims to provide the sulfydryl modified magnetic particle dispersion liquid and the preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of sulfhydryl modified magnetic particle dispersion liquid comprises the following steps:
s1 preparation of superparamagnetic nano Fe by chemical coprecipitation method3O4Stirring the dispersion liquid I, and dripping a silicate solution into Fe under the condition of keeping the constant temperature of 40-100 DEG C3O4Adding a hydrochloric acid solution into the dispersion liquid I to adjust the pH value to 5.5-7.0, stopping stirring, aging, carrying out magnetic separation to remove clear liquid, and washing the obtained magnetic substance to obtain Fe3O4@SiO2A dispersion liquid II;
s2, stirring and keeping the temperature of the mixture constant at 40-100 ℃, and adding Fe3O4@SiO2Dropwise adding a hydrochloric acid solution into the dispersion liquid II, uniformly mixing, activating for 16-24 hours, washing to be neutral, washing for a plurality of times by using methanol, and dispersing the magnetic particles in glycerol to form a dispersion liquid III;
s3, transferring the dispersion liquid III into a reaction container, adding methanol, stirring and keeping the temperature of the dispersion liquid at 40-100 ℃, dropwise adding the reaction liquid for reaction, wherein the reaction liquid is formed by mixing strong ammonia water, methanol and 3-mercaptopropyltrimethoxysilane, stopping stirring after the reaction is finished, washing and ultrasonically dispersing to obtain a dispersion liquid IV, and the magnetic particles in the dispersion liquid IV are mercapto-modified magnetic particles (functional magnetic particles Fe with mercapto as an end group)3O4@SiO2@R-SH)。
Preferably, in step S1, the superparamagnetic nano-Fe is prepared by a chemical coprecipitation method3O4The procedure for dispersion I was: with Fe2+And Fe3+Preparing magnetic core Fe by chemical coprecipitation method as precursor3O4Magnetically separating to obtain Fe as black magnetic substance3O4，Fe3O4Dispersing the washed solution in ultrapure water to prepare superparamagnetic nano Fe3O4And (3) a dispersion liquid I. The magnetic separation is specifically performed by using a strong magnet, and the strong magnet is a permanent magnet of iron, rubidium and boron.
Further preferably, in step S1, a chemical coprecipitation method is used to prepare superparamagnetic nano-Fe3O4The specific steps of the dispersion I are as follows:taking FeCl2And FeCl3Dissolving in HCl solution to obtain Fe2+And Fe3+Precursor solution of Fe2+And Fe3+In a molar ratio of 1:2, Fe2+The molar ratio of HCl to HCl is 1: 1; stirring NaOH solution under anaerobic condition, heating to 80 ℃, and adding Fe2+And Fe3+Precursor solution, reacting for 30 min; magnetic separation is carried out by a strong magnet, and the separated black magnetic substance is Fe3O4Washing the black magnetic substance to be neutral, and then dispersing the black magnetic substance in deionized water to prepare the superparamagnetic nano Fe3O4And (3) a dispersion liquid I.
Preferably, Fe in step S13O4The ratio of the solid content of the dispersion liquid I to the solid content of the silicate solution is 1: 6-1: 2.
Further preferably, the silicate in step S1 is sodium silicate.
Preferably, the concentration of the hydrochloric acid solution in the step S1 is 1.5-2.5 mol/L, the dripping duration of the hydrochloric acid solution is 10-120 min, and the aging time is 3-6 h; in the step S2, the concentration of the hydrochloric acid solution is 0.5-1.5 mol/L, and the volume ratio of the hydrochloric acid solution to the dispersion liquid II is 1: and 10, dropwise adding the hydrochloric acid solution for 10-120 min.
Preferably, the specific steps of transferring the dispersion liquid III into a reaction vessel, adding methanol, stirring and slowly dripping the reaction liquid to react under the condition of keeping the constant temperature of 40-100 ℃ are as follows: and transferring the dispersion liquid III into a reaction container, adding methanol to enable the volume ratio of the methanol to reach 25%, slowly dropwise adding the reaction liquid under the conditions of stirring and keeping the constant temperature of 80 ℃, and then reacting for 4-6 hours.
Preferably, the volume ratio of concentrated ammonia water, methanol and 3-mercaptopropyltrimethoxysilane in the reaction liquid is 3:80:20, and the dropping time of the reaction liquid is 1 hour.
The second object of the present invention is to protect the thiol-modified magnetic particle dispersion prepared by the above-mentioned preparation method.
The invention also protects the application of the sulfhydryl modified magnetic particle dispersion liquid in the treatment of mercury-containing wastewater.
Compared with the prior art, the invention has the beneficial effects that: the sulfhydryl modified magnetic particle dispersion liquid provided by the invention can efficiently remove mercury in a water body, has an effect superior to that of adsorbents such as activated carbon, iron oxide and the like, increases the equilibrium adsorption capacity by nearly one hundred times compared with activated carbon and iron oxide, and has a wide application prospect in the field of industrial mercury removal.
Drawings
FIG. 1 shows the synthesis of functional magnetic particle Fe with mercapto group as terminal group3O4@SiO2The technical scheme of @ R-SH;
FIG. 2 shows functional magnetic Fe particles synthesized by the method of example 1 and example 23O4@SiO2An infrared spectrum of @ R-SH (A and B-D, respectively);
FIG. 3 shows thiol-terminated functional magnetic particles Fe obtained in example 23O4@SiO2Infrared spectrogram before/after absorbing mercury of @ R-SH;
FIG. 4 shows thiol-terminated functional magnetic particles Fe obtained in example 23O4@SiO2SEM morphology photograph before (left)/after (right) of @ R-SH adsorbing mercury;
FIG. 5 shows thiol-terminated functional magnetic particles Fe obtained in example 23O4@SiO2The curve of the adsorption kinetics of @ R-SH to the simulated mercury-containing sewage;
FIG. 6 shows mercapto-terminated functional magnetic particles Fe obtained in examples 1 to 23O4@SiO2The adsorption isotherm of the @ R-SH on the simulated mercury-containing sewage.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof. The equipment used in the present invention is a conventional commercial product in the art unless otherwise specified.
Example 1
As shown in figure 1, a functional magnetic particle Fe with mercapto as a terminal group3O4@SiO2@ R-SH, FIG. 2 magnetic particles A and their dispersions were prepared as follows:
s1 preparation of superparamagnetism Fe by chemical coprecipitation method3O4The dispersion liquid I comprises the following specific steps:
2g of FeCl is taken2·4H2O and 5.2g FeCl3·6H2Dissolving O in 25mL0.4 mol/L HCl solution to prepare solution A; adding 250mL of 1.6mol/L NaOH solution into a flask, introducing nitrogen, rapidly stirring, heating to 80 ℃, rapidly pouring the solution A into the flask, reacting for 30min, stopping stirring, performing magnetic separation by using a permanent magnet of iron, rubidium and boron, wherein the separated black magnetic substance is magnetic core Fe3O4Discarding clear liquid, washing with deionized water until no impurities exist and the pH value is neutral, dispersing the collected magnetic particles in 200mL of deionized water to prepare the superparamagnetic Fe3O4And (3) storing the dispersion liquid I at normal temperature, wherein the main component of the dispersion liquid I is superparamagnetic Fe3O4And (4) magnetic particles.
S2 ultrasonic treating the whole dispersion I obtained in the step S1 for 30min, transferring into a flask, introducing nitrogen, rapidly stirring, heating to 80 ℃, and adding 40mL of 0.02mol/L Na dropwise in 30min2SiO3·5H2Slowly adjusting pH of the O solution to 6.0 by using 20mL of 2mol/L HCl solution, continuously dripping the HCl solution for 30min, and aging for 3h under the conditions of stirring and keeping constant temperature of 80 ℃ to enable the silicon dioxide to wrap magnetic core Fe3O4Performing magnetic separation on the surface by using a permanent magnet of iron, rubidium and boron, washing the surface by using methanol and deionized water until no impurities exist and the pH value is neutral to obtain a dispersion liquid II, wherein the dispersion liquid II is Fe3O4@SiO2The dispersion is stored at 0-35 ℃.
S3, under the conditions of stirring and keeping the constant temperature of 80 ℃, dropwise adding 20mL of 1.0mol/L HCl solution into the dispersion liquid II, dropwise adding for 60min, uniformly mixing, activating for 20h, washing with water to be neutral, washing with methanol for 3 times, dispersing the magnetic particles into 150mL of glycerol, and performing ultrasonic treatment for a moment to form a dispersion liquid III.
S4, transferring the dispersion liquid III into a reaction container, adding 50mL of methanol to enable the volume ratio of the methanol to reach 25%, slowly dropwise adding the reaction liquid under the conditions of stirring and keeping the constant temperature of 80 ℃, wherein the reaction liquid is formed by mixing 1.5mL of concentrated ammonia water, 40mL of methanol and 10mL of 3-mercaptopropyltrimethoxysilane, and the dropwise adding of the reaction liquid is kept for keepingThe duration is 1 hour, the reaction is carried out for 5 hours again, the stirring is stopped, methanol is used for washing for 3 times, ultrapure water is used for washing for 3 times, and the dispersion liquid IV is prepared after ultrasonic dispersion, wherein the magnetic particles in the dispersion liquid IV are functional magnetic particles Fe taking sulfydryl as end groups3O4@SiO2@ R-SH, which is the magnetic particle A in FIG. 2.
Example 2
As shown in fig. 1, all the preparation steps were the same as in example 1 except that: in step S2, the pH was slowly adjusted to 6.0 using 20mL of 2mol/L HCl solution, and the continuous dropwise addition time of the HCl solution was 60 min. Parallel experiments were performed 3 times according to the preparation procedure of example 2, magnetic particles B, C and D, respectively.
10 μ L of the functional magnetic particle dispersion prepared in example 1-2 was dried in vacuum, the dried powder was homogenized, and a small amount of the powder was tabletted with potassium bromide and tested in an infrared spectrometer, the results of which are shown in FIG. 2. From FIG. 2, it can be seen that the distance is at 577cm-1A stretching vibration peak of Fe-O appears at 690cm-1Is of Si-CH2Characteristic absorption Peak, 802cm-1Is located at 1116cm of Si-O stretching vibration peak-1A strong absorption peak appears, which is an antisymmetric stretching vibration peak of O-Si-O, and is 2931cm-1Is at occurrence of-CH3and-CH2The stretching vibration peak of-SH is weaker and appears at 2551cm-1Here, these functional groups confirmed successful grafting of thiol groups onto the silica surface, and FIG. 2 shows 4 different batches of synthesized functional magnetic particles Fe3O4@SiO2@ R-SH are highly compatible in terms of the kind and number of groups, etc. Example 1 and example 2 prepared functional magnetic particles Fe by measuring thiol groups by three-dimensional fluorescence3O4@SiO2The content of-SH in @ R-SH is about 0.318mmol/g, and the yield of sulfhydryl is about 12.7%.
Example 3
The same as example 1, except that: in step S2, the constant temperature is 40 ℃, Fe3O4The ratio of the solid content of the dispersion liquid I to the solid content of the silicate solution is 1:2, the concentration of the hydrochloric acid solution is 1.5mol/L,adding a hydrochloric acid solution, adjusting the pH value to 5.5, and aging for 3 hours; in the step S3, the constant temperature is 40 ℃, the concentration of the hydrochloric acid solution is 1.5mol/L, the dripping duration of the hydrochloric acid solution is 10min, and the mixture is activated for 16h after being uniformly mixed; in step S4, the temperature was maintained at 40 ℃ and the duration of dropwise addition of the reaction solution was 1 hour, followed by 9 hours of reaction.
Example 4
The same as example 1, except that: in step S2, the constant temperature is 100 ℃, Fe3O4The ratio of the solid content of the dispersion liquid I to the solid content of the silicate solution is 1:6, the concentration of the hydrochloric acid solution is 2.5mol/L, the hydrochloric acid solution is added, the pH value is adjusted to 7.0, and the mixture is aged for 6 hours; in the step S3, the constant temperature is 100 ℃, the concentration of the hydrochloric acid solution is 0.5mol/L, the dripping duration of the hydrochloric acid solution is 120min, and the mixture is activated for 24h after being uniformly mixed; in step S4, the temperature is maintained at 100 ℃, the duration of dropwise addition of the reaction solution is 1 hour, and the reaction is carried out for 3 hours.
Examples of the experiments
Functional magnetic particle Fe prepared in example 13O4@SiO2@ R-SH Dispersion No. #3MNPs and #4MNPs, and Fe functional magnetic particles prepared in example 23O4@SiO2The following experiments were carried out with @ R-SH dispersions, numbered #1MNPs and #2 MNPs:
preparing a magnetic particle dispersion liquid: functional magnetic particle Fe prepared by means of calculation through a decrement method3O4@SiO2@ R-SH solid content of the dispersion, and diluting it to a magnetic particle dispersion having a solid content of 1 mg/mL.
1. The experiment on the adsorption kinetics of the simulated mercury-containing sewage comprises the following steps: 200 mu L (or 400 mu L) of magnetic particle dispersion liquid with solid content of 1mg/mL (namely 0.2 or 0.4mg of magnetic particles) is dripped into 20mL of simulated mercury-containing sewage (the absolute content of Hg (II) in the solution is 10 mu g or 0.4 mu g), the solution to be tested is taken out at a set moment by oscillating on a reciprocating oscillator for 4 hours at the rotating speed of 200r/min, and the total mercury content in the solution to be tested is determined, and the result is shown in figures 3-5. Magnetic particle Fe3O4@SiO2The infrared spectrum before/after adsorption of mercury in the @ R-SH dispersion is shown in FIG. 3, and the scanning electron micrograph is shown in FIG. 4.
As shown in fig. 3, the groups of the magnetic particles were changed before and after the adsorption of mercury, and the peak difference (transmittance) of the-SH characteristic absorption peak was reduced from 2.2 to 0.3 after the experiment of adsorbing Hg, indicating a decrease in the number of mercapto groups. Fe can be seen from the scanning electron micrograph (FIG. 4)3O4@SiO2The removal of mercury by @ R-SH is mainly caused by that mercury is adsorbed on the surfaces of magnetic particles and in cavities of the magnetic particles, and the surfaces of sites where the adsorption occurs are changed from smooth to rough before and after the adsorption.
As shown in fig. 5, the difference of the adsorption effect of the same magnetic particle on different systems hg (ii) is very large, and the same system is selective for different magnetic particles, which suggests that in the actual use process, the bidirectional selection of the magnetic particle on the system needs to be taken into consideration, and manufacturers should combine with the actual application site to prepare the optimized magnetic particles, such as #4MNPs and the reaction system thereof of the present invention.
2. The magnetic particle pair simulates an isothermal adsorption experiment of the mercury-containing sewage: 200 mu L of magnetic particle dispersion liquid with the solid content of 1mg/mL (namely 0.2mg of magnetic particles) is dripped into 20mL of simulated mercury-containing sewage with different initial concentrations, the magnetic particle dispersion liquid is oscillated on a reciprocating oscillator for 4 hours at the rotating speed of 200r/min, the liquid to be detected is taken out at the set moment, and the total mercury content in the liquid to be detected is determined. The results are shown in FIG. 6.
From FIG. 6, it is found that isothermal adsorption of magnetic particles on simulated mercury-containing wastewater follows the Lamgmuir model, which suggests Fe in the magnetic particle dispersion of the present invention3O4@SiO2The maximum adsorption amount of @ R-SH to Hg (II) is more than 400mg Hg/g MNPs.
3. And (3) removing free mercury in the wastewater by the magnetic particles: 200. mu.L of magnetic particle dispersion with a solid content of 1mg/mL (i.e., 0.2mg of magnetic particles) was added dropwise to 20mL of wastewater, and the mixture was shaken on a reciprocal shaker at a rotation speed of 200r/min for 4 hours to measure the total mercury content in the solution before and after adsorption.
Through batch experiments, the removal of mercury in 3 types of alkaline wastewater and 1 type of acidic wastewater is examined under room temperature and oscillating experimental conditions by comparing the use of magnetic particles with the absence of magnetic particles, and the comparison of the removal effect of mercury in wastewater by using magnetic particles with the absence of magnetic particles is shown in table 1:
TABLE 1 comparison of the removal of mercury from wastewater with and without magnetic particles
Table 1 illustrates that the removal rate of mercury-containing wastewater using the magnetic particle experimental group of the present invention can be as high as 99% compared to that without the magnetic particle experimental group.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. A preparation method of sulfhydryl modified magnetic particle dispersion liquid is characterized by comprising the following steps:
s1 preparation of superparamagnetic nano Fe by chemical coprecipitation method3O4Stirring the dispersion liquid I, and dripping a silicate solution into Fe under the condition of keeping the constant temperature of 40-100 DEG C3O4Adding a hydrochloric acid solution into the dispersion liquid I to adjust the pH value to 5.5-7.0, stopping stirring, aging, carrying out magnetic separation to remove clear liquid, washing the obtained magnetic substance to obtain Fe3O4@SiO2A dispersion liquid II;
s2, stirring and keeping the temperature of the mixture constant at 40-100 ℃, and adding Fe3O4@SiO2Dropwise adding a hydrochloric acid solution into the dispersion liquid II, uniformly mixing, activating, washing to be neutral, washing for a plurality of times by using methanol, and dispersing the magnetic particles into glycerol to form a dispersion liquid III;
s3, transferring the dispersion liquid III to a reaction container, adding methanol, stirring, keeping the temperature constant at 40-100 ℃, dropwise adding the reaction liquid A for reaction, stopping stirring after the reaction is finished, and washing and ultrasonically dispersing to obtain a dispersion liquid IV, wherein the magnetic particles in the dispersion liquid IV are mercapto-modified magnetic particles.
2. The method of claim 1, wherein the step S1 of preparing superparamagnetic nanometer Fe particles by chemical coprecipitation method3O4The procedure for dispersion I was: with Fe2+And Fe3+Preparing magnetic core Fe by chemical coprecipitation method as precursor3O4Magnetically separating to obtain Fe as black magnetic substance3O4，Fe3O4Dispersing the washed solution in ultrapure water to prepare superparamagnetic nano Fe3O4And (3) a dispersion liquid I.
3. The method for preparing thiol-modified magnetic particle dispersion of claim 2, wherein the step S1 is performed by chemical co-precipitation to obtain superparamagnetic nano-Fe3O4The specific steps of the dispersion I are as follows: taking FeCl2And FeCl3Dissolving in HCl solution to obtain Fe2+And Fe3+Precursor solution of Fe2+And Fe3+In a molar ratio of 1:2, Fe2+The molar ratio of HCl to HCl is 1: 1; stirring NaOH solution under anaerobic condition, heating to 80 ℃, and adding Fe2+And Fe3+Precursor solution, reacting for 30 min; magnetic separation is carried out by a strong magnet, and the separated black magnetic substance is Fe3O4Washing the black magnetic substance to be neutral, and then dispersing the black magnetic substance in deionized water to prepare the superparamagnetic nano Fe3O4And (3) a dispersion liquid I.
4. The method of claim 1, wherein in step S1, Fe is added3O4The ratio of the solid content of the dispersion liquid I to the solid content of the silicate solution is 1: 6-1: 2.
5. The method of preparing a thiol-modified magnetic particle dispersion of claim 1 or 4, wherein the silicate in step S1 is sodium silicate.
6. The method for preparing a thiol-modified magnetic particle dispersion according to claim 1, wherein the concentration of the hydrochloric acid solution in step S1 is 1.5-2.5 mol/L, the dripping duration of the hydrochloric acid solution is 10-120 min, and the aging time is 3-6 h; in the step S2, the concentration of the hydrochloric acid solution is 0.5-1.5 mol/L, and the volume ratio of the hydrochloric acid solution to the dispersion liquid II is 1: and 10, dropwise adding the hydrochloric acid solution for 10-120 min.
7. The method for preparing the thiol-modified magnetic particle dispersion liquid of claim 1, wherein the specific steps of transferring the dispersion liquid III into a reaction vessel, adding methanol, and slowly dropping the reaction liquid to react under the conditions of stirring and keeping the constant temperature of 40-100 ℃ are as follows: transferring the dispersion liquid III into a reaction container, adding methanol to enable the volume ratio of the methanol to reach 25%, and slowly dropwise adding the reaction liquid to react for 4-6 hours under the conditions of stirring and keeping the constant temperature of 80 ℃.
8. The method of claim 1, wherein the volume ratio of concentrated ammonia water, methanol and 3-mercaptopropyltrimethoxysilane in the reaction solution is 3:80:20, and the dropping time of the reaction solution is 1 hour.
9. The thiol-modified magnetic particle dispersion prepared by the method of claim 1.
10. Use of the thiol-modified magnetic particle dispersion of claim 9 for treating mercury-containing wastewater.
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