CN117225388A - Prussian blue-nano zero-valent iron composite material and preparation method and application thereof - Google Patents
Prussian blue-nano zero-valent iron composite material and preparation method and application thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002351 wastewater Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 23
- 230000035484 reaction time Effects 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052716 thallium Inorganic materials 0.000 abstract description 13
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 abstract description 13
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 abstract description 6
- 229960003351 prussian blue Drugs 0.000 abstract description 6
- 239000013225 prussian blue Substances 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract description 2
- 239000012279 sodium borohydride Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000000729 antidote Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 ca 2+ Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 208000026015 thallium poisoning Diseases 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a Prussian blue-nano zero-valent iron composite material, and a preparation method and application thereof, and belongs to the field of nano materials and thallium removal. The method synthesizes Prussian Blue (PB) -nano zero-valent iron (nZVI) composite material (PB@nZVI) at room temperature by using a sodium borohydride reduction method. Compared with single Prussian blue and nano zero-valent iron, the prepared PB@nZVI has high removal rate and high selectivity on Tl (I). Can be used as an effective water Tl (I) pollution adsorbent to be applied to the field of water heavy metal pollution treatment.
Description
Technical Field
The invention belongs to the field of nano materials and thallium removal, and particularly relates to a Prussian blue-nano zero-valent iron composite material (PB@nZVI) and a preparation method and application thereof.
Background
Thallium (Tl) is a heavy metal element with extremely high toxicity, and the toxic effect on mammals is far greater than that of conventional heavy metals such as mercury, arsenic, cadmium, lead, antimony and the like. Thallium has lithophilic and thiophilic properties, often associated with minerals such as pyrite, lead zinc ores, and the like. The thallium resource of China is rich, and the reserves are the first in the world. Thallium content in natural water is generally low, lake is 0.001-0.41 mug/L, river is 0.013-1.35 mug/L, groundwater is 0.001-0.55 mug/L, but thallium content in surface water and groundwater is obviously increased around mining and smelting plants and the like. With the development of the smelting industry in China, thallium pollution happens sometimes. The national and Guangdong provinces have successively established strict industrial wastewater thallium pollutant emission standards.
Thallium exists in the aqueous environment mainly in the forms of Tl (I) and Tl (III). Most Tl in natural water bodies and industrial wastewater exists in the form of Tl (I). Tl (I) has very high solubility, stability and fluidity in water, is difficult to adsorb and is difficult to form hydroxide, and is more difficult to process than Tl (III). Along with the continuous expansion of the influence of thallium pollution on the environment and human health hazards, the search for an efficient and economical technical method for treating thallium pollution of wastewater is urgent. Currently, the treatment of Tl (I) mainly includes chemical precipitation, ion exchange, solvent extraction, adsorption, and the like. However, chemical precipitation, solvent extraction and ion exchange methods have drawbacks such as low selectivity in the presence of competing ions and susceptibility to secondary pollution. Therefore, a solid-phase adsorption material that removes Tl (I) by adsorption using a carbon material and Al, ti, fe or Mn groups has been attracting attention because of its advantages of convenience, easy operation, high efficiency, stability, and low cost. Among these adsorbents, titanium peroxide and nano manganese dioxide (nMOS) 2 ) Nano zero valent iron (nZVI) and ferro-manganese complex oxides exhibit excellent removal performance in laboratory tests for Tl in water with low co-existing ion levels.
The nZVI has high specific surface area and high reactivity, has magnetism and is easy to separate, and can be widely applied to the treatment of heavy metals. However, the defects of easy agglomeration and easy oxidation and inactivation limit the application. Furthermore, in an actual water/wastewater environment, coexisting ions (e.g., ca 2+ 、Mg 2+ 、K + ) Is of (1)The degree is usually hundreds or even thousands of times the Tl concentration, and the removal effect of the adsorption material such as nZVI on Tl (I) is poor, which indicates that the selectivity is low. Therefore, developing an adsorption material with high selectivity and large adsorption capacity has important significance for treating Tl polluted wastewater.
Prussian blue (PB, fe) 4 [Fe(CN)) 6 ] 3 ) Has been recognized as an antidote to eliminate thallium poisoning in animals and humans, indicating its safety, high selectivity and effectiveness. Studies have shown that the use of PB and its analogues (PBAs) is considered a viable method for the selective removal of Tl (I) from wastewater containing coexisting ions. However, in the large scale treatment of Tl (I) -containing wastewater, systems involving PB or PBAs nano/micro particles present challenges in separating and recovering from the treated wastewater, and the residual PB or PBAs in the water body present a risk of secondary pollution.
Disclosure of Invention
Aiming at the defects of the prior art for treating the Tl (I) polluted water body, the invention provides the Prussian blue-nano zero-valent iron composite material, the preparation method thereof and the method for removing monovalent thallium in the water body with high selectivity. The method has the advantages of low cost and simple process, and the prepared material has high reaction activity, good stability and strong selectivity, and is suitable for industrial production.
The aim of the invention is achieved by the following technical scheme.
The preparation method of the Prussian blue-nanometer zero-valent iron composite material comprises the following steps:
NaBH is carried out 4 Added to K 4 [Fe(CN) 6 ]·3H 2 Forming a mixed solution in the O solution, and then adding the mixed solution into FeCl dropwise 3 And (3) uniformly stirring in the solution to fully react, centrifuging and collecting the precipitate, and washing to obtain the Prussian blue-nanometer zero-valent iron composite material, wherein the PB@nZVI is marked.
PreferablyIn the NaBH 4 With FeCl 3 The molar ratio of (3) to (1) to (3.5) to (1).
Preferably, the FeCl 3 And K is equal to 4 [Fe(CN) 6 ]·3H 2 The molar ratio of O is 4:3-8:3.
Preferably, the NaBH 4 With FeCl 3 The molar ratio of (2) is 3:1, and deionized water used in the synthesis process is introduced with N before use 2 25min to remove dissolved oxygen.
The Prussian blue-nano zero-valent iron composite material prepared by the preparation method of any one of the above.
The application of the Prussian blue-nano zero-valent iron composite material in removing Tl (I) in wastewater comprises the following steps:
adding Prussian blue-nano zero-valent iron composite material into wastewater containing Tl (I), carrying out constant-temperature oscillation, and detecting the concentration of the solution Tl (I) after the reaction.
Preferably, the pH of the Tl (I) -containing wastewater is 3-11, more preferably 3-9.
Preferably, the initial concentration of Tl (I) in the wastewater is in the range of 1-100mg/L, more preferably 1-20mg/L.
Preferably, the additive amount of the Prussian blue-nano zero-valent iron composite material in the Tl (I) -containing wastewater is 0.1-0.5g/L, and more preferably 0.2-0.5g/L.
Preferably, the reaction temperature of the constant-temperature oscillation is 25+/-0.2 ℃, the reaction time is 4 hours, and the rotating speed is 250r/min.
Compared with the prior art, the invention has the following advantages:
the PB@nZVI disclosed by the invention is modified nano zero-valent iron, and compared with a nano zero-valent iron material, the prepared PB@nZVI has higher selectivity, and the efficiency of treating Tl (I) pollution in a water body is increased. The PB@nZVI disclosed by the invention improves the oxidation resistance, stability and selectivity of the nano zero-valent iron particles, has higher removal capability on Tl (I) environmental pollutants, and is suitable for being applied to the field of water environment heavy metal pollution treatment as an adsorption material.
Drawings
FIG. 1 shows X-ray powder diffractometer (XRD) analysis patterns of PB@nZVI, nZVI and PB.
FIG. 2 is a Scanning Electron Microscope (SEM) analysis of PB@nZVI.
FIG. 3 is a graph showing the comparison of PB@nZVI, nZVI, PB versus Tl (I).
FIGS. 4, 5 and 6 are diagrams showing degradation of Tl (I) by PB@nZVI.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1
PB@nZVI was prepared by sodium borohydride reduction, and 0.6446g NaBH was added 4 K added to 50mL of 42.6mmol/L 4 [Fe(CN) 6 ]·3H 2 A mixed solution was formed in the O solution, and then added dropwise to 400mL of 14.2mmol/L FeCl 3 And (3) stirring the solution at a rotating speed of 300r/min by using an electric stirring rod, continuously stirring for 10min after the dripping is finished to fully react, centrifuging and collecting to obtain a precipitate, and alternately washing with deionized water and absolute ethyl alcohol for 2 times to obtain PB@nZVI, wherein an analysis chart of an X-ray powder diffractometer (XRD) and an analysis chart of a Scanning Electron Microscope (SEM) are respectively shown in the figures 1 and 2. The washed materials are sealed by absolute ethyl alcohol and stored in a refrigerator at the temperature of 4 ℃ for standby.
Batch experiments were performed using 50ml centrifuge tubes as the reactor, into which 25ml of 20mg/L Tl (I) solution was introduced, followed by 5min N 2 Removing dissolved oxygen, adding 0.005g PB@nZVI, nZVI and PB, sealing, and performing the reaction in a shaking table at normal temperature (25+ -0.2 ℃) and 250r/min. After 4h of reaction, the solution was filtered in a 10mL centrifuge tube using a 0.22 μm pinhole filter, and the concentration of Tl (I) in the solution was determined using an inductively coupled plasma emission spectrometer (ICP-OES), and all experimental samples were in triplicate, and the results were averaged. The reaction is carried out by centrifuging a centrifuge tube for 5 minutes at 8000r/min to obtain a reaction product, washing the reaction product twice with deionized water and absolute ethyl alcohol respectively, and drying the solid product in vacuum for 24 hours.
As can be seen from FIG. 3, PB@nZVI has a much higher removal rate for Tl (I) than nZVI and PB. When the adding amount is 0.1g/L, the removal rate of PB@nZVI to Tl (I) is more than 90%, and the removal rates of nZVI and PB are about 40% and 64%, and after the adding amount reaches 0.2g/L, the removal rate of PB@nZVI reaches 99%.
Example 2
A50 ml centrifuge tube was used as a reactor, and the treatment object was 1mg/L Tl (I). Measuring 25mL of wastewater containing Tl (I), and adjusting the pH value of the water body to 7.0 by using 0.1mol/L nitric acid and 0.1mol/L sodium hydroxide; introducing 5min N 2 Dissolved oxygen was removed, 0.005g PB@nZVI was added and the reactor was placed on a constant temperature shaking table at 25.+ -. 0.2 ℃ at a speed of 250r/min for a reaction time of 4h. The concentration of Tl (I) in the solution was determined by ICP-OES.
Example 3
A50 ml centrifuge tube was used as a reactor, and the treatment object was 5mg/L Tl (I). Measuring 25mL of wastewater containing Tl (I), and adjusting the pH value of the water body to 7.0 by using 0.1mol/L nitric acid and 0.1mol/L sodium hydroxide; introducing 5min N 2 Dissolved oxygen was removed, 0.005g PB@nZVI was added and the reactor was placed on a constant temperature shaking table at 25.+ -. 0.2 ℃ at a speed of 250r/min for a reaction time of 4h. The concentration of Tl (I) in the solution was determined by ICP-OES.
Example 4
A50 ml centrifuge tube was used as a reactor, and the treatment object was 10mg/L Tl (I). Measuring 25mL of wastewater containing Tl (I), and adjusting the pH value of the water body to 7.0 by using 0.1mol/L nitric acid and 0.1mol/L sodium hydroxide; introducing 5min N 2 Dissolved oxygen was removed, 0.005g PB@nZVI was added and the reactor was placed on a constant temperature shaking table at 25.+ -. 0.2 ℃ at a speed of 250r/min for a reaction time of 4h. The concentration of Tl (I) in the solution was determined by ICP-OES.
Example 5
A50 ml centrifuge tube was used as a reactor, and the treatment object was Tl (I) at a concentration of 20mg/L. Measuring 25mL of wastewater containing Tl (I), and adjusting the pH value of the water body to 7.0 by using 0.1mol/L nitric acid and 0.1mol/L sodium hydroxide; introducing 5min N 2 Dissolved oxygen was removed, 0.005g PB@nZVI was added and the reactor was placed on a constant temperature shaking table at 25.+ -. 0.2 ℃ at a speed of 250r/min for a reaction time of 4h. Filtration and determination of the solution by ICP-OESTl (I) concentration in the sample.
Example 6
A50 ml centrifuge tube was used as a reactor, and the treatment object was 100mg/L Tl (I). Measuring 25mL of wastewater containing Tl (I), and adjusting the pH value of the water body to 7.0 by using 0.1mol/L nitric acid and 0.1mol/L sodium hydroxide; introducing 5min N 2 Dissolved oxygen was removed, 0.005g PB@nZVI was added and the reactor was placed on a constant temperature shaking table at 25.+ -. 0.2 ℃ at a speed of 250r/min for a reaction time of 4h. The concentration of Tl (I) in the solution was determined by ICP-OES.
The specific results are shown in Table 1 and FIG. 4.
TABLE 1 removal Rate of five initial concentrations Tl (I)
As can be seen from table 1 and fig. 4, the removal rate of Tl (I) increases and then decreases with increasing initial concentration.
Example 7
A50 ml centrifuge tube was used as a reactor, and the treatment object was Tl (I) at a concentration of 20mg/L. Measuring 25mL of wastewater containing Tl (I), and adjusting the pH value of the water body to 3.0 by using 0.1mol/L nitric acid and 0.1mol/L sodium hydroxide; introducing 5min N 2 Dissolved oxygen was removed, 0.005g PB@nZVI was added and the reactor was placed on a constant temperature shaking table at 25.+ -. 0.2 ℃ at a speed of 250r/min for a reaction time of 4h. The concentration of Tl (I) in the solution was determined by ICP-OES.
Example 8
A50 ml centrifuge tube was used as a reactor, and the treatment object was Tl (I) at a concentration of 20mg/L. Measuring 25mL of wastewater containing Tl (I), and adjusting the pH value of the water body to 5.0 by using 0.1mol/L nitric acid and 0.1mol/L sodium hydroxide; introducing 5min N 2 Dissolved oxygen was removed, 0.005g PB@nZVI was added and the reactor was placed on a constant temperature shaking table at 25.+ -. 0.2 ℃ at a speed of 250r/min for a reaction time of 4h. The concentration of Tl (I) in the solution was determined by ICP-OES.
Example 9
Centrifugation with 50mlThe tube was used as a reactor, and the treatment object was a concentration of 20mg/L Tl (I). Measuring 25mL of wastewater containing Tl (I), and adjusting the pH value of the water body to 9.0 by using 0.1mol/L nitric acid and 0.1mol/L sodium hydroxide; introducing 5min N 2 Dissolved oxygen was removed, 0.005g PB@nZVI was added and the reactor was placed on a constant temperature shaking table at 25.+ -. 0.2 ℃ at a speed of 250r/min for a reaction time of 4h. The concentration of Tl (I) in the solution was determined by ICP-OES.
Example 10
A50 ml centrifuge tube was used as a reactor, and the treatment object was Tl (I) at a concentration of 20mg/L. Measuring 25mL of wastewater containing Tl (I), and adjusting the pH value of the water body to 11.0 by using 0.1mol/L nitric acid and 0.1mol/L sodium hydroxide; introducing 5min N 2 Dissolved oxygen was removed, 0.005g PB@nZVI was added and the reactor was placed on a constant temperature shaking table at 25.+ -. 0.2 ℃ at a speed of 250r/min for a reaction time of 4h. The concentration of Tl (I) in the solution was determined by ICP-OES.
The specific results are shown in Table 2 and FIG. 5.
TABLE 2 removal rates for five pH values Tl (I)
As is clear from Table 2 and FIG. 5, the change in the removal rate of Tl (I) was small and 97% or more of Tl (I) was removed at pH 3-9; at ph=11, 49% of Tl (I) was removed.
Example 11
A50 ml centrifuge tube was used as a reactor, and the treatment object was Tl (I) at a concentration of 20mg/L and coexisting ions (K) + 、Ni 2+ 、Pb 2+ 、Zn 2+ 、Ca 2+ 、Mg 2+ 、Cd 2+ 、Cu 2+ ) Is a mixed solution of (a) and (b). 25mL of a Tl (I) -containing mixed solution was measured and introduced for 5min N 2 Dissolved oxygen was removed, 0.005g PB@nZVI was added and the reactor was placed on a constant temperature shaking table at 25.+ -. 0.2 ℃ at a speed of 250r/min for a reaction time of 4h. The concentration of Tl (I) in the solution was determined by ICP-OES.
Example 12
A50 ml centrifuge tube was used as a reactor, and the treatment object was Tl (I) at a concentration of 20mg/L and coexisting ion (K) at a concentration of 100mg/L + 、Ni 2+ 、Pb 2+ 、Zn 2+ 、Ca 2+ 、Mg 2+ 、Cd 2+ 、Cu 2+ ) Is a mixed solution of (a) and (b). 25mL of a Tl (I) -containing mixed solution was measured and introduced for 5min N 2 Dissolved oxygen was removed, 0.005g PB@nZVI was added and the reactor was placed on a constant temperature shaking table at 25.+ -. 0.2 ℃ at a speed of 250r/min for a reaction time of 4h. The concentration of Tl (I) in the solution was determined by ICP-OES.
Example 13
A50 ml centrifuge tube was used as a reactor, and the treatment object was Tl (I) at a concentration of 20mg/L and 1000mg/L coexisting ions (K + 、Ni 2+ 、Pb 2+ 、Zn 2+ 、Ca 2+ 、Mg 2+ 、Cd 2+ 、Cu 2+ ) Is a mixed solution of (a) and (b). 25mL of a Tl (I) -containing mixed solution was measured and introduced for 5min N 2 Dissolved oxygen was removed, 0.005g PB@nZVI was added and the reactor was placed on a constant temperature shaking table at 25.+ -. 0.2 ℃ at a speed of 250r/min for a reaction time of 4h. The concentration of Tl (I) in the solution was determined by ICP-OES.
The specific results are shown in FIG. 6. K (K) + 、Ni 2+ 、Pb 2+ 、Zn 2+ 、Ca 2+ 、Mg 2+ 、Cd 2+ The influence on the removal of Tl (I) by PB@nZVI is small (the removal rate is more than 95 percent), cu 2+ The influence on the removal of Tl (I) by PB@nZVI is obvious, but the removal rate still reaches 80%, and excellent selectivity is shown.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the Prussian blue-nano zero-valent iron composite material is characterized by comprising the following steps of:
NaBH is carried out 4 Added to K 4 [Fe(CN) 6 ]·3H 2 Forming a mixed solution in the O solution, and then adding the mixed solution into FeCl dropwise 3 And (3) uniformly stirring in the solution to fully react, centrifuging and collecting the precipitate, and washing to obtain the Prussian blue-nanometer zero-valent iron composite material, wherein the PB@nZVI is marked.
2. The method for preparing Prussian blue-nano zero-valent iron composite according to claim 1, wherein the NaBH 4 With FeCl 3 The molar ratio of (3) to (1) to (3.5) to (1).
3. The method for preparing Prussian blue-nano zero-valent iron composite according to claim 1, wherein the FeCl is 3 And K is equal to 4 [Fe(CN) 6 ]·3H 2 The molar ratio of O is 4:3-8:3.
4. A Prussian blue-nano zero valent iron composite produced by the method of any one of claims 1-3.
5. The use of the Prussian blue-nano zero-valent iron composite according to claim 4 for removing Tl (I) from wastewater, comprising the steps of:
adding Prussian blue-nano zero-valent iron composite material into wastewater containing Tl (I), carrying out constant-temperature oscillation, and detecting the concentration of the solution Tl (I) after the reaction.
6. The use of a Prussian blue-nano zero-valent iron composite according to claim 5, to remove Tl (I) from wastewater, wherein the pH of the wastewater containing Tl (I) is 3-11.
7. The use of a Prussian blue-nano zero valent iron composite according to claim 5, for removing Tl (I) from wastewater, wherein the initial concentration of Tl (I) in wastewater is in the range of 1-100mg/L.
8. The application of the Prussian blue-nano zero-valent iron composite material in removing Tl (I) in wastewater, according to claim 5, wherein the adding amount of the Prussian blue-nano zero-valent iron composite material in the wastewater containing Tl (I) is 0.1-0.5g/L.
9. The use of a Prussian blue-nano zero valent iron composite according to claim 5, for removing Tl (I) from wastewater, wherein the pH of the Tl (I) -containing wastewater is 3-9; the initial concentration range of Tl (I) in the wastewater is 1-20mg/L; the additive amount of the Prussian blue-nano zero-valent iron composite material in the wastewater containing Tl (I) is 0.2-0.5g/L.
10. The application of the Prussian blue-nano zero-valent iron composite material in removing Tl (I) in wastewater, according to claim 5, wherein the reaction temperature of constant-temperature oscillation is 25+/-0.2 ℃, the reaction time is 4 hours, and the rotating speed is 250r/min.
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