CN109692651A - A kind of ferroferric oxide nano granules material preparation method and its application as defluorinating agent - Google Patents
A kind of ferroferric oxide nano granules material preparation method and its application as defluorinating agent Download PDFInfo
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- CN109692651A CN109692651A CN201910093745.XA CN201910093745A CN109692651A CN 109692651 A CN109692651 A CN 109692651A CN 201910093745 A CN201910093745 A CN 201910093745A CN 109692651 A CN109692651 A CN 109692651A
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- oxide nano
- ferroferric oxide
- method described
- fluorine ion
- molysite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- Inorganic Chemistry (AREA)
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- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of ferroferric oxide nano granules material preparation method and its as the application of defluorinating agent, belong to nano material and its applied technical field.The present invention has synthesized uniform super-paramagnetic ferriferrous oxide nano granular materials using solvent thermal process that is simple, being easy to get, which is meso-hole structure, and specific surface area reaches 70-100 m2/g.The material shows the removal ability of fluorine ion in excellent water, and when initial concentration is 200mg/L, its adsorption capacity reaches 70.64mg/g at room temperature.Adsorption mechanism is related to hydroxyl exchange and sulfate radical exchange.Present invention process is simple, low in cost, safety and environmental protection, and gained functionalization porous ferroferric oxide nano material has superparamagnetism, is easily recycled, reusable, has higher removal efficiency to the water of fluorine ion pollution, has good application prospect.
Description
Technical field
The invention belongs to the technical fields of environmental protection and processing.
Background technique
Fluorine is a kind of non-metal chemical element, chemical symbol F, and atomic number 9 distributes widely in nature.As dimension
A kind of microelement of function of human body normal operation is held, fluorine plays the role of human health very important.Suitable fluorine can be with
Promote the formation of hard tooth tissue and the deposition of bone calcium, while being also beneficial to absorption of the human body to elements such as calcium, phosphorus, accelerates bone
It is formed, promotes the anti-caries ability of tooth.However, excessive fluorine intake can also bring harm to human body, less serious case influences making for tooth
Glaze function forms den tal fluorosis, and severe one causes whole body fluorosis of bone, so that the element ratios such as fluorine in human bodies, calcium, phosphorus are lacked of proper care, leads to bone
Deformity, arthropathy even cause bone sclerosis, fracture.Therefore, it according to the sanitary standard for drinking water of the World Health Organization, drinks
It is fluorine-containing in water to be not more than 1.5mg/L, and Chinese sanitary standard for drinking water regulation is fluorine-containing should be in 1.0mg/L or less.
Containing excessive fluorine in drinking water is a global problem, and in China, Fluorine Containing Groundwater is widely distributed, is influenced
The drinking water quality of more than 20 a provinces, autonomous region and municipality directly under the Central Government, water problems is drunk in Urbanization Construction seems more prominent.It is high
The improvement of fluorine water can substantially be divided into absorption method and film with topic always popular in recent years, traditional technology of Fluoride Removal is improved
Partition method.Compared to membrane separation process, absorption law technology is more mature, cost is cheaper, operation is simpler, therefore absorption method exists
It is widely used and by the technology as a kind of high-effective defluorination at present.
It is reported that the high volence metal ions such as iron (III), manganese (II, IV), lanthanum (III), aluminium (III), zirconium (IV) or titanium (IV)
In the presence of the adsorption capacity for being remarkably improved fluorine, wherein molysite has the characteristics that low cost.As a kind of common iron oxide material, four
Fe 3 O nano particle is widely used in arsenic in water, fluorine, heavy-metal adsorption material due to its unique and modulated magnetic characteristic
Carrier material.
Summary of the invention
The object of the present invention is to provide the preparation of porous structure ferroferric oxide nano granules material and as defluorinating agent
Using.
Porous structure ferroferric oxide nano granules material of the invention, uses following methods step to obtain:
(1) a certain amount of surfactant PVP K30 and molysite are dissolved in ethylene glycol solution, are then added a certain amount of
Anhydrous sodium acetate, stir 6-8 hours；
(2) (1) resulting homogeneous solution is sealed into polytetrafluoroethyllining lining stainless steel cauldron, is heated to 170-190 DEG C, protected
It is 12-14 hours warm；
(3) solution for standing and obtaining after reaction is taken to be filtered, washed, dry, the ferroso-ferric oxide for obtaining efficient absorption fluorine ion is received
Rice grain material, specific surface area are 70-100 m2/g。
In the reaction, molysite is selected from least one of iron chloride, ferric sulfate, ferric nitrate；
In the reaction, the mass concentration of surfactant PVP K30 is 2-4 g/L；
In the reaction, the molar concentration of molysite is 0.065-0.085 M；
In the reaction, the molar concentration of molysite is 0.35-0.55 M；
In the reaction, the diameter of the ferroferric oxide nano granules material of the efficient absorption fluorine ion of preparation is 70 ~ 80 nm；
In the reaction, the ferroferric oxide nano granules material of the efficient absorption fluorine ion of preparation has superparamagnetic characteristic,
Saturation magnetization is 27 ~ 30 emu/g.
Porous structure prepared by the present invention adsorb fluorine ion ferroferric oxide nano granules material absorption water in fluorine from
Overabundance of amniotic fluid foot pseudo-second order kinetic model, isothermal adsorption meet Freundlich model, and adsorption mechanism is the sulfuric acid of material surface
Root and hydroxyl exchange.
Detailed description of the invention
Fig. 1 be ferroferric oxide nano granules material (a) X ray diffracting spectrum, (b) Raman spectrum, (c) XPS map and
(d) Fe 2p peak figure is composed.
Fig. 2 is ferroferric oxide nano granules material (a) low range TEM figure, (b) high magnification TEM figure.
Fig. 3 is ferroferric oxide nano granules material (a) nitrogen Adsorption and desorption isotherms, (b) pore size distribution curve.
Fig. 4 is ferroferric oxide nano granules material magnetic curves.
Fig. 5 is ferroferric oxide nano granules material (a) curve of adsorption kinetics, the matched curve of (b) pseudo-second order kinetic.
Fig. 6 is ferroferric oxide nano granules material (a) adsorption isothermal curve, (b) isothermal adsorption Freundlich model
Matched curve.
Fig. 7 is that ferroferric oxide nano granules material adsorbs fluorine ion pH value influence in water.
Fig. 8 is that ferroferric oxide nano granules material adsorbs Zeta electric potential curve in water.
Fig. 9 is the infrared spectrum spectrogram in ferroferric oxide nano granules material absorption water before and after fluorine ion.
Specific embodiment
Under the present invention is further elaborated combined with specific embodiments below, but substantive content of the invention is not limited in
It states described in embodiment.The method is conventional method unless otherwise instructed, and the material unless otherwise instructed can be from disclosure
Commercial sources obtain, and the technical staff in the domain of ability should know any simple transformation based on substantive content of the present invention or replace
In generation, belongs to protection scope of the presently claimed invention.
In following embodiments, adsorbent pattern is characterized using 200 type scanning electron microscope (SEM) of FEI-Quanta,
The infrared transform spectrometer of NEXUS-870 type Fourier (FT-IR) analyzes sample, uses Micromeritics ASAP
2020 M carry out nitrogen adsorption desorption specific surface area analysis and partial size to composite metal oxide adsorbent and pore-size distribution is analyzed, and adopt
With fluorinion concentration in E-201-C type pH combination electrode and PXS-270 type ionometer detection water.
Embodiment 1
Step 1:0.3g surfactant PVP K30 and molysite are dissolved in 100ml ethylene glycol solution, are then added
3.69g anhydrous sodium acetate stirs 6 hours；
Step 2: resulting homogeneous solution is sealed into polytetrafluoroethyllining lining stainless steel cauldron, is heated to 180 DEG C, heat preservation 12 is small
When；
Step 3: taking the solution for standing and obtaining after reaction to be filtered, washed, dry, obtain ferroferric oxide nano granules material fluorine removal
Agent.
Above-mentioned ferroferric oxide nano granules material defluorinating agent can through the characterization such as XRD, Raman spectrum, infrared spectroscopy (Fig. 1)
To determine the material as ferriferrous oxide material, its pattern (Fig. 2 a, 2b) is characterized through scanning electron microscope and projection Electronic Speculum, it can
To be seen to be porous structure, defluorinating agent is measured in adsorption desorption in nitrogen using 2020 M analyzer of Micromeritics ASAP
Specific surface area is 70.24 m2/g (300 ℃).Adsorption desorption curve and pore size distribution curve such as Fig. 3 a, 3b.
The resulting ferroferric oxide nano granules material defluorinating agent of this example is applied to the absorption of fluorine ion in water: claiming respectively
Taking 300 mg of ferroferric oxide nano granules material for implementing the preparation in 1 to be added to 0.3 L fluorinion concentration is 2.5 mg/L
Water sample in adsorbed under the conditions of 25 DEG C, 35 DEG C, 45 DEG C, fullyd shake in shaking table make its absorption 12 hours then
Filtering detects its fluorine ion adsorbance (Fig. 6), which meets Freundlich model to the isothermal adsorption of fluorine ion, have
Excellent adsorption capacity, adsorption capacity can reach 70.64 mg/g.
Embodiment 2
Step 1:0.2g surfactant PVP K30 and molysite are dissolved in 100ml ethylene glycol solution, and 4g is then added
Anhydrous sodium acetate stirs 8 hours；
Step 2: resulting homogeneous solution is sealed into polytetrafluoroethyllining lining stainless steel cauldron, is heated to 190 DEG C, heat preservation 14 is small
When；
Step 3: taking the solution for standing and obtaining after reaction to be filtered, washed, dry, obtain ferroferric oxide nano granules material fluorine removal
Agent.
Above-mentioned ferroferric oxide nano granules material defluorinating agent is through Quantum Design MPMSXL-5 superconductive quantum interference
Device can be carried out measurement (Fig. 4) its magnetism, the hysteresis loop measured at 300 K, magnetic field from -60000 Oe to
60000 Oe, it can be seen that the material is superparamagnetic characteristic.
The resulting ferroferric oxide nano granules material defluorinating agent of this example is applied to the absorption of fluorine ion in water: claiming respectively
Taking 300 mg of ferroferric oxide nano granules material for implementing the preparation in 2 to be added to 0.3 L fluorinion concentration is 2.5 mg/L
Water sample in adsorbed under the conditions of 25 DEG C, pH=7.0, fullyd shake in shaking table make its adsorb 3 hours, at this 3 hours
It is interior to detect its fluorine ion adsorbance (Fig. 5) at interval of extracting the filtering of a certain amount of solution for a period of time.The adsorption dynamics adsorption kinetics meets
Pseudo-second order kinetic model, fitting correlation coefficient 0.9994.The defluorinating agent can in 5 minutes to fluorine ion in water removal rate
Reach 80% or more.Influence (as shown in Figure 7) of the pH value in solution to fluorine ion adsorption efficiency is analyzed, it is inhaled in pH=7
Attached efficiency highest.
Claims (7)
1. a kind of ferroferric oxide nano granules material preparation method and its application as defluorinating agent, it is characterised in that:
(1) a certain amount of surfactant PVP K30 and molysite are dissolved in ethylene glycol solution, are then added a certain amount of
Anhydrous sodium acetate, stir 6-8 hours；
(2) (1) resulting homogeneous solution is sealed into polytetrafluoroethyllining lining stainless steel cauldron, is heated to 170-190 DEG C, protected
Temperature 12 hours；
(3) solution for standing and obtaining after reaction is taken to be filtered, washed, dry, the ferroso-ferric oxide for obtaining efficient absorption fluorine ion is received
Rice grain material, specific surface area are 70-100 m2/g。
2. according to the method described in claim 1, it is characterized by: the molysite is in iron chloride, ferric sulfate, ferric nitrate
At least one.
3. according to the method described in claim 1, it is characterized by: the surfactant PVP K30
Mass concentration is 2-4 g/L.
4. according to the method described in claim 1, it is characterized by: the molar concentration of the molysite is 0.065-0.085 M.
5. according to the method described in claim 1, it is characterized by: the molar concentration of the molysite is 0.35-0.55 M.
6. according to the method described in claim 1, it is characterized by: four oxidations three of the efficient absorption fluorine ion of the preparation
The diameter of iron nano-particle material is 70 ~ 80 nm.
7. according to the method described in claim 1, it is characterized by: four oxidations three of the efficient absorption fluorine ion of the preparation
Iron nano-particle material has superparamagnetic characteristic, and saturation magnetization is 27 ~ 30 emu/g.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437345A (en) * | 2014-11-15 | 2015-03-25 | 中国科学院过程工程研究所 | Solvent-thermal preparation method of porous ferroferric oxide adsorption material |
| CN105032422A (en) * | 2015-06-29 | 2015-11-11 | 中国科学院广州能源研究所 | Fe3O4 nanometer catalyst for Fischer-Tropsch synthesis and preparation method of Fe3O4 nanometer catalyst |
| CN107827164A (en) * | 2017-09-30 | 2018-03-23 | 清华大学 | The preparation method of the ferroferric oxide nano granules of the high yield thermal efficiency under a kind of magnetic field |
-
2019
- 2019-01-30 CN CN201910093745.XA patent/CN109692651A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437345A (en) * | 2014-11-15 | 2015-03-25 | 中国科学院过程工程研究所 | Solvent-thermal preparation method of porous ferroferric oxide adsorption material |
| CN105032422A (en) * | 2015-06-29 | 2015-11-11 | 中国科学院广州能源研究所 | Fe3O4 nanometer catalyst for Fischer-Tropsch synthesis and preparation method of Fe3O4 nanometer catalyst |
| CN107827164A (en) * | 2017-09-30 | 2018-03-23 | 清华大学 | The preparation method of the ferroferric oxide nano granules of the high yield thermal efficiency under a kind of magnetic field |
Non-Patent Citations (2)
| Title |
|---|
| MAIYONG ZHU等: "Synthesis of Porous Fe3O4 Nanospheres and Its Application for the Catalytic Degradation of Xylenol Orange", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| 曾宪银等: "氨基化纳米Fe3O4 处理含氟废水的研究", 《黑龙江科技信息》 * |
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Application publication date: 20190430 |