CN109364883A - A kind of humic acid modified Nano Fe2O3Material preparation method and the application for removing estradiol - Google Patents

A kind of humic acid modified Nano Fe2O3Material preparation method and the application for removing estradiol Download PDF

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Publication number
CN109364883A
CN109364883A CN201811286067.0A CN201811286067A CN109364883A CN 109364883 A CN109364883 A CN 109364883A CN 201811286067 A CN201811286067 A CN 201811286067A CN 109364883 A CN109364883 A CN 109364883A
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humic acid
modified nano
acid modified
solution
preparation
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CN109364883B (en
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李艳霞
童心
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Beijing Normal University
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Beijing Normal University
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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
    • 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
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Water Treatment By Sorption (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention discloses a kind of humic acid modified Nano Fe for belonging to technical field of environment function material preparation2O3Material preparation method and the application for removing estradiol.This method is by by Fe (NO3)3.9H2O is dissolved in deionized water, then adds KOH solution, NaHCO3Solution, precipitation and separation after insulation reaction, then solid and humic acid are mixed, pH is adjusted, is centrifugally separating to obtain after isothermal vibration.It is prepared to obtain humic acid modified Nano Fe2O3Material has large specific surface area, and surface has a variety of functional groups, and adsorption site is more, and adsorption capacity is stronger.

Description

A kind of humic acid modified Nano Fe2O3Material preparation method and the application for removing estradiol
Technical field
The invention belongs to technical field of environment function material preparation, in particular to a kind of humic acid modified Nano Fe2O3Material Preparation method and the application for removing estradiol.
Background technique
Nanometer Fe2O3It is a kind of nanometer materials, there is nano-scale particle to constitute, rough surface, hole is abundant, compares table Area is huge, has stronger adsorption capacity to inorganic ions.However, the absorption due to the property of itself, to organic pollutant Often be limited, solve the problems, such as this method be exactly it is carried out it is organically-modified, improve its lipophilicity.In the past about the organic of mineral Modified to use the organically-modified methods such as surfactant or coupling agent, at high cost, complex steps easily cause secondary pollution.This hair It is bright to explore a kind of humic acid modified Nano Fe2O3The preparation of composite material, method is simple, to the removal effect of 17 beta estradiols Significantly.
Summary of the invention
The purpose of the present invention is to provide a kind of humic acid modified Nano Fe2O3Material preparation method and removal estradiol Using, which is characterized in that specific step is as follows:
(1) Fe (NO of 40-50g is weighed3)3·9H2O is dissolved in 500mL and is preheated in 90 DEG C of deionized water, and preheating is added To 90 DEG C of 1mol/L KOH solutions, it is preheated to 90 DEG C of 1mol/L NaHCO3Solution is kept the temperature in water bath in 90 DEG C of cappings 36-48h；
(2) topple over supernatant, precipitation and separation removes extra OH-And NO3 -, drying at room temperature；
(3) it weighs obtained solid to be placed in beaker, the mixing of 500mL Humic Acid Solution is added, with the NaOH of 0.1mol/L Or it is 8.0 that HCl, which adjusts solution ph, in 25 DEG C of constant temperature oscillation 36-48h, is then centrifuged 15min with 4 000r/min.
(4) topple over supernatant, with deionized water by solid be centrifuged repeatedly rinsing until organic concentration of carbon in supernatant not There is significant change again, grinding obtains humic acid modified Nano Fe after freeze-drying2O3Material.
Wherein step (1) Fe (NO3)3·9H2The aqueous solution mass concentration of O is 8-10wt%.
The wherein KOH solution and Fe (NO of step (1) described addition3)3·9H2O aqueous solution volume ratio is (3-4): 5, NaHCO3Solution and Fe (NO3)3·9H2O aqueous solution volume ratio is (1-2): 10.
Wherein the solid-to-liquid ratio of step (3) solid and Humic Acid Solution is 1:20-25.
Wherein the temperature of step (4) described lyophilization is -45 DEG C, and the time of processing is 48-72h.
The humic acid modified Nano Fe2O3Material is applied to enhancing to the removal ability of 17 beta estradiols.
The invention has the benefit that humic acid modified Nano Fe proposed by the present invention2O3Material preparation method is quickly simple Instrument and equipment single, without complexity, prepared material have the characteristics that nontoxic, large specific surface area, surface functional group are more, It is high to the removal efficiency of 17 beta estradiols.
Detailed description of the invention
Fig. 1 is humic acid modified Nano Fe in embodiment 12O3The scanning electron microscope structure chart of material；
Fig. 2 is the LC-MS measurement result figure of reaction solution concentration in embodiment 3；
Fig. 3 is the LC-MS measurement result figure of reaction solution concentration in embodiment 4.
Specific embodiment
The present invention provides a kind of humic acid modified Nano Fe2O3Material preparation method and the application for removing estradiol, below The present invention is described further in conjunction with the accompanying drawings and embodiments.
Embodiment 1:
Humic acid modified Nano Fe2O3Material specific the preparation method is as follows:
(1) Fe (NO of 40g is weighed3)3·9H2O is dissolved in 500mL and is preheated in 90 DEG C of deionized water, and it is pre- that 300mL is added The 1mol/L NaHCO that 50mL is preheated to 90 DEG C is added in the 1mol/L KOH solution of heat to 90 DEG C3, add in water bath in 90 DEG C Lid keeps 48h.
(2) topple over supernatant, precipitation and separation removes extra OH-And NO3 -, dry.
(3) it weighs the solid that 25g is obtained to be placed in beaker, the mixing of 500mL Humic Acid Solution is added, solid-to-liquid ratio 1: 20, pH value is transferred to 8.0 with the NaOH solution of 0.1mol/L or HCl solution, in 25 DEG C of constant temperature oscillation 48h, then with 4 000r/ Min is centrifuged 15min.
(4) topple over supernatant, with deionized water by solid be centrifuged repeatedly rinsing until organic concentration of carbon in supernatant not There is significant change again, grinding obtains humic acid modified Nano Fe after solid to be freeze-dried to 48h at -45 DEG C2O3Material.
Humic acid modified Nano Fe obtained above2O3Material appearance is rufous, by the humic acid modified Nano of preparation Fe2O3Material is placed under scanning electron microscope and observes, and surface texture is as shown in Figure 1, be observed that the material surface is coarse by Fig. 1 Without type, there is pore structure abundant.
Embodiment 2:
Humic acid modified Nano Fe prepared by embodiment 12O3Material is applied to 17 beta estradiols of removal, and specific method is such as Under:
(1) compound concentration gradient is the 17 beta estradiol solution of 0.025-1mg/L.
(2) the humic acid modified Nano Fe of 0.05g is weighed2O3It is above-mentioned not to be separately added into 10mL into Brown Glass Brown glass bottles and jars only for material With 17 beta estradiol solution of concentration, constant temperature oscillation 48h at 25 DEG C.
(3) it takes suspension to be centrifuged after adsorption equilibrium, is added in 1mL sample bottle, adopts after crossing 0.22 μm of glass filters With solution concentration after LC-MS measurement reaction.The results are shown in Table 1:
Table 1: the adsorbance under different 17 beta estradiol primary condition
Initial concentration (mg/L) Adsorbance (mg/kg)
1 23.26
0.6 21.89
0.4 17.61
0.2 10.58
0.1 5.98
0.05 1.73
0.025 1.13
As shown in Table 1, humic acid modified Nano Fe2O3Material to 17 beta estradiols adsorption capacity with higher, and with Initial concentration increase, adsorption capacity enhancing.
Embodiment 3:
Humic acid modified Nano Fe prepared by embodiment 12O3Material is applied to 17 beta estradiols of removal, and specific method is such as Under:
(1) the humic acid modified Nano Fe of 0.05g is weighed2O3Material is as the 0.1mg/L that 100mL in conical flask, is added 17 beta estradiol solution, in 25 DEG C of constant temperature oscillation 48h.
(2) it takes suspension to be centrifuged in the different interval time point of 0-250min, then crosses 0.22 μm of glass filters It is added in 1mL sample bottle afterwards, with the levels of solution after LC-MS measurement reaction.
Adsorbance result under different time is as shown in Fig. 2, as shown in Figure 2, humic acid modified Nano Fe2O3Material pair The adsorbance of 17 beta estradiols is continuously increased as time increases.Between 0-120min, adsorbance is quicklyd increase, Saturation is progressivelyed reach after 120min.
Embodiment 4:
Humic acid modified Nano Fe prepared by embodiment 12O3Material is applied to 17 beta estradiols of removal, and specific method is such as Under:
(1) the humic acid modified Nano Fe of 5 parts of 0.05g is weighed2O3Material is separately added into 10mL's into Brown Glass Brown glass bottles and jars only The 17 beta estradiol solution of 0.1mg/L, while adjusting pH value with the NaOH or HCl of 0.1mol/L is 3,5,7,9,11, at 25 DEG C Constant temperature oscillation 48h.
(2) it takes suspension to be centrifuged after adsorption equilibrium, is added in 1mL sample bottle, uses after crossing 0.22 μm of glass filters Solution concentration after LC-MS measurement reaction.
Adsorbance result under different pH value is as shown in figure 3, from the figure 3, it may be seen that the adsorption effect of material is influenced by pH value, pH It is unfavorable for removal of the adsorbent to 17 beta estradiols when value is higher, as pH is increased, adsorbance is gradually reduced.
The above is only the preferred embodiment for the present invention, the scope of the present invention is not limited merely to above-described embodiment, with this Various process programs of the inventive concept without substantial differences are in protection scope of the present invention.

Claims (6)

1. a kind of humic acid modified Nano Fe2O3Material preparation method and the application for removing estradiol, which is characterized in that specific step It is rapid as follows:
(1) Fe (NO of 40-50g is weighed3)3.9H2O is dissolved in 500mL and is preheated in 90 DEG C of deionized water, and addition is preheated to 90 DEG C 1mol/L KOH solution, be preheated to 90 DEG C of 1mol/L NaHCO3Solution keeps the temperature 36- in 90 DEG C of cappings in water bath 48h；
(2) topple over supernatant, precipitation and separation removes extra OH-And NO3 -, drying at room temperature；
(3) it weighs obtained solid to be placed in beaker, the mixing of 500mL Humic Acid Solution is added, with the NaOH or HCl of 0.1mol/L Adjusting solution ph is 8.0, in 25 DEG C of constant temperature oscillation 36-48h, is then centrifuged 15min with 4 000r/min；
(4) topple over supernatant, with deionized water by solid be centrifuged repeatedly rinsing until organic concentration of carbon in supernatant there is no Significant change, grinding obtains humic acid modified Nano Fe after solid is freeze-dried2O3Material.
2. a kind of humic acid modified Nano Fe according to claim 12O3The preparation method of material, which is characterized in that step (1) Fe (NO3)3.9H2The aqueous solution mass concentration of O is 8-10wt%.
3. a kind of humic acid modified Nano Fe according to claim 12O3The preparation method of material, which is characterized in that step (1) KOH solution of the addition and Fe (NO3)3.9H2O aqueous solution volume ratio is (3-4): 5, NaHCO3Solution and Fe (NO3)3.9H2O aqueous solution volume ratio is (1-2): 10.
4. a kind of humic acid modified Nano Fe according to claim 12O3The preparation method of material, which is characterized in that step (3) solid-to-liquid ratio of the solid and Humic Acid Solution is 1:20-25.
5. a kind of humic acid modified Nano Fe according to claim 12O3The preparation method of material, which is characterized in that step (4) temperature of the lyophilization is -45 DEG C, and the time of processing is 48-72h.
6. humic acid modified Nano Fe described in claim 1-5 any claim2O3Material, which is characterized in that the humic acid Modified Nano Fe2O3Material is applied to enhancing to the removal ability of 17 beta estradiols.
CN201811286067.0A 2018-10-31 2018-10-31 Humic acid modified nano Fe2O3Preparation method of material and application of material in removal of estradiol Active CN109364883B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1119664A (en) * 1997-07-04 1999-01-26 Kazuyoshi Matsunaga Decomposition of hardly biologically decomposable organic matter and removing method of phosphorus by zirconium oxide/ferric salt/hydrogen peroxide/ ultraviolet rays system
CN101209868A (en) * 2007-12-21 2008-07-02 中国科学院广州地球化学研究所 Method for inhibiting offensive odor of riverway water body and bottom mud
CN201648182U (en) * 2010-03-05 2010-11-24 天津创业环保集团股份有限公司 Sewage treatment device without odor generation
CN102874888A (en) * 2011-07-13 2013-01-16 北京师范大学 Method for fixing heavy metal ions via microwave irradiation activated carbon by using humic acid as additive
CN102872816A (en) * 2012-08-28 2013-01-16 常州大学 Composite adsorption material for removing manganese ions from natural water and preparation method for adsorption material
CN108328718A (en) * 2018-04-24 2018-07-27 南京林业大学 A kind of generating means of fulvic acid chelated iron ion

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1119664A (en) * 1997-07-04 1999-01-26 Kazuyoshi Matsunaga Decomposition of hardly biologically decomposable organic matter and removing method of phosphorus by zirconium oxide/ferric salt/hydrogen peroxide/ ultraviolet rays system
CN101209868A (en) * 2007-12-21 2008-07-02 中国科学院广州地球化学研究所 Method for inhibiting offensive odor of riverway water body and bottom mud
CN201648182U (en) * 2010-03-05 2010-11-24 天津创业环保集团股份有限公司 Sewage treatment device without odor generation
CN102874888A (en) * 2011-07-13 2013-01-16 北京师范大学 Method for fixing heavy metal ions via microwave irradiation activated carbon by using humic acid as additive
CN102872816A (en) * 2012-08-28 2013-01-16 常州大学 Composite adsorption material for removing manganese ions from natural water and preparation method for adsorption material
CN108328718A (en) * 2018-04-24 2018-07-27 南京林业大学 A kind of generating means of fulvic acid chelated iron ion

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