CN107715830B - A kind of preparation method of vernadite and its application in the treatment of waste water - Google Patents

A kind of preparation method of vernadite and its application in the treatment of waste water Download PDF

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CN107715830B
CN107715830B CN201711075962.3A CN201711075962A CN107715830B CN 107715830 B CN107715830 B CN 107715830B CN 201711075962 A CN201711075962 A CN 201711075962A CN 107715830 B CN107715830 B CN 107715830B
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vernadite
solution
solid
concentration
activation modification
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CN107715830A (en
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张嵚
程晓迪
姜冠杰
严格
欧阳南琪
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Zhongke ecological restoration (Jiangxi) Innovation Research Institute Co.,Ltd.
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Jiangxi Agricultural 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
    • 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
    • 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
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The invention discloses a kind of preparation methods of vernadite, comprising the following steps: (1) by KMnO4With dense H2SO4It is added to the water and is configured to solution A, and prepares H2O2Solution is as B solution；(2) B solution is added drop-wise in solution A under agitation；(3) stirred 2 hours or more after being added dropwise to complete, solid be collected by filtration, solid is washed with deionized until after washing the conductivity of liquid less than 20 μ s/cm, then solid is dry, be ground up, sieved, both vernadite.Vernadite preparation method used in the present invention belongs to new preparation method, and method is easy to operate, and synthetic material is easy to get, easy to operate, convenient for promoting；Material environmental protection, will not introduce new pollutant, without secondary pollution.

Description

A kind of preparation method of vernadite and its application in the treatment of waste water
Technical field
The invention belongs to the preparation method of technical field of environmental science more particularly to a kind of vernadite and its at waste water Application in reason.
Background technique
With industrial boom, problem of environmental pollution is on the rise, and the direct indirect discharge of a large amount of industrial wastewaters aggravates Water pollution situation accelerates water quality deterioration；Development and industrial exploitation, processing, smelting to heavy metal of the people in mining industry in recent years Refining, manufacture, so that heavy metal also enters water environment, such as Pb, Cu, Cd.Pb is the toxic heavy metal element of a kind of pair of human body, can For biological concentration, and human body is entered by food chain, had to systems such as the nerve of human body, blood, immune, digestion, endocrines Toxic action.Conventional process heavy metal generally uses bioanalysis, physico-chemical process, including precipitating filtering, ion exchange, reverse osmosis Thoroughly, redox, electrolysis and UF membrane etc..It is that typical water pollution repairs skill with adsorbent Adsorption heavy metal contaminants Art.
Vernadite is as a kind of efficient absorption material, with removal efficiency is high, adsorption rate is fast, adsorption capacity is big, behaviour Make simple advantage, is with a wide range of applications in terms of sewage treatment.The chemical formula of vernadite is MnO2·nH2O belongs to In hexagonal crystal system, construct with [MnO6] octahedra for basic framework, it is a kind of layered manganese oxide of weak crystalloid.Manganese ion occupies Less than half of octahedral voids, although its specific structure cell and layer structure feature also not it is clear that it has become clear that The mineral are the variant of birnessite, and structure is very chaotic, upper unordered in crystal layer accumulation.At present to vernadite preparation method Research it is less, mainly react to obtain using MnO4, highly basic and divalent manganesetion, such as " the synthesis of Chinese Academy of Sciences's Master's thesis Manganese mineral and its suction-operated of rare earth element is studied " (Meng Yan, 2006), " vernadite removes in underground water academic paper The influence factor and mechanism of phenol " (environmental project journal, in August, 2017 the 8th phase of volume 11) etc. be in this way.Shen Ask someone to produce vernadite using above-mentioned conventional method for removing the Pb in solution2+Shi Faxian, art methods synthesis Vernadite is to Pb2+The adsorption capacity of ion is very weak, Pb2+Ion is difficult to enter in vernadite hole, Pb2+The absorption of ion Rate is less than 60%, a large amount of Pb2+It stays and exists in the form of free ion in the solution, therefore the vernadite of existing method preparation is difficult To be used in high Pb concentration2+In the technical field of sewage of ion, vernadite efficient absorption is not in full use.
Summary of the invention
Based on above-mentioned technical problem, the present invention provides a kind of preparation methods of vernadite, comprising the following steps:
(1) by KMnO4With dense H2SO4It is added to the water and is configured to solution A, and prepares H2O2Solution is as B solution；
(2) B solution is added drop-wise in solution A under agitation；
(3) it is stirred 2 hours or more after being added dropwise to complete, solid is collected by filtration, solid is washed with deionized until after washing The conductivity of liquid less than 20 μ s/cm, then solid is dry, be ground up, sieved, both vernadite.
Further, the step specifically:
(1) KMnO is prepared4Concentration is 100~150mmol/L, H2SO4Concentration is the solution A of 50~80mmol/L, is prepared H2O2Concentration is the B solution of 150~250mmol/L；
(2) according to reaction molar ratio KMnO4: H2O2The ratio of=1:1.25~1.75, by B under conditions of being vigorously stirred Solution is added drop-wise in solution A, occurs a large amount of dark brown solids during being added dropwise, while with O2Release；
(3) it is stirred 2 hours or more after being added dropwise to complete, solid is collected by filtration, solid is washed with deionized until after washing The conductivity of liquid less than 20 μ s/cm, then solid is dry, be ground up, sieved, both vernadite.
Further, KMnO in the solution A4Concentration is 127mmol/L, H2SO4Concentration is 63.2mmol/L, in B solution H2O2Concentration is 190mmol/L, reacts molar ratio KMnO in step (2)4: H2O2=1:1.5, being added dropwise to complete rear mixing time is 3h。
The invention also discloses the application of the above method in the treatment of waste water, and the vernadite is directly launched in waste water In, or filter cake filtered wastewater is made, for the Pb in Adsorption waste water2+Ion.
Further, the vernadite is used further to wastewater treatment, activation modification step after activation modification are as follows:
1) EDTA, sodium carbonate and ethylenediamine tetra-acetic acid tripotassium are dissolved in water and are configured to activation modification liquid, wherein EDTA Concentration is 0.5~1mol/L, and the concentration of sodium carbonate is 1~3mol/L, the concentration of ethylenediamine tetra-acetic acid tripotassium is 0.1~ 0.35mol/L；
2) activation modification liquid pours into reaction vessel, and vernadite obtained is immersed in activation modification liquid, then will be anti- Container is answered to seal, to container vacuum-pumping, so that pressure is between 1000~2000Pa in container；
3) ebuillition of heated, boiling time >=1h are carried out to activation modification liquid；
4) solid is but collected by filtration afterwards, uses deionized water for equalizing reservoir inside and outside differential pressure after the completion of boiling, activation modification liquid cooling It is dry less than 20 μ s/cm, then by solid to wash the conductivity of solid liquid after washing, the vernadite after being activated.
Further, the vernadite is directly launched when being adsorbed in waste water, and adsorption time is no less than 0.5h, water Pb in the input amount and waste water of pyrochroite2+Ion concentration are as follows:
Input amount >=0.5g/L:Pb of vernadite2+Mole number of ions are 1mmol/L.
As can be seen from the above technical solutions, the invention has the advantages that
(1) the vernadite preparation method used in the present invention belongs to new preparation method, and method is easy to operate, synthetic material It is easy to get, it is easy to operate, convenient for promoting；Material environmental protection, will not introduce new pollutant, without secondary pollution.
(2) vernadite of the method for the invention preparation is to Pb2+The adsorption capacity of ion is strong, and repairing effect is obvious, water Pyrochroite is put into waste water, Pb in 1 hour2+Ion remaval rate reaches 95% or more, after activation modification is handled, Pb2+Ion Removal rate even can achieve 98% or more.
(3) present invention is best to the repairing effect of Pb, and adsorbance is maximum, at the same to other heavy metal Cus, Zn, Cd etc. and Organic matter has certain absorption property, also can remove other heavy metal pollutions while repairing Pb pollution and organic matter is dirty Dye.
Detailed description of the invention
Fig. 1 is the SEM figure of the vernadite of the embodiment of the present invention 1, embodiment 3 and the preparation of 5 the method for embodiment；
Fig. 2 is the X-ray diffracting spectrum of the vernadite of 1~5 the method for embodiment of the present invention preparation.
Specific embodiment
A kind of preparation method of vernadite, comprising the following steps:
(1) by KMnO4With dense H2SO4It is added to the water and is configured to solution A, and prepares H2O2Solution is as B solution；
(2) B solution is added drop-wise in solution A under agitation；
(3) it is stirred 2 hours or more after being added dropwise to complete, solid is collected by filtration, solid is washed with deionized until after washing The conductivity of liquid less than 20 μ s/cm, then solid is dry, be ground up, sieved, both vernadite.
Using the vernadite of above method preparation to Pb2+The adsorption capacity of ion is strong, and repairing effect is obvious, vernadite It puts into waste water, Pb in 1 hour2+Ion remaval rate reaches 95% or more.
It is described in detail below with reference to embodiment:
Embodiment 1
A kind of preparation method of vernadite, the step are as follows:
(1) KMnO is prepared4Concentration is 100mmol/L, H2SO4Concentration is the solution A of 50mmol/L, prepares H2O2Concentration is The B solution of 150mmol/L；
(2) according to reaction molar ratio KMnO4: H2O2The ratio of=1:1.25, drips B solution under conditions of being vigorously stirred It is added in solution A, occurs a large amount of dark brown solids during being added dropwise, while with O2Release；
(3) it is stirred 2 hours after being added dropwise to complete, solid is collected by filtration, solid liquid after washing is washed with deionized Conductivity less than 20 μ s/cm, then solid is dry, be ground up, sieved, both vernadite.
The micromorphology of gained vernadite powder is observed using scanning electron microscope (SEM).Take appropriate vernadite Ultrasonic disperse 10min in ethanol solution is placed in then suspension is brushed on copper fine-structure mesh and dried with hairbrush, so at suspension Vacuum metal spraying afterwards observes vernadite microscopic appearance.Amplification 104SEM figure again is as shown in Figure 1.
It takes 0.2g or so powder tabletted by powder pressing method, then carries out X-ray diffraction (XRD) analysis, gained knot Fruit such as Fig. 2.
Using the manganese oxidizability (Kijima et al.2001) in Oxalic Acid Method measurement vernadite.Its measuring method such as China Middle agriculture university's Master's thesis " δ-MnO2Substructure conversion and todorokite chemical forming feature " it is described.Described in the present embodiment Manganese oxidizability in vernadite is as shown in table 1.
Prepare Pb2+Ion concentration is the lead nitrate solution 1L of 3mmol/L, and vernadite obtained by the present embodiment is directly launched It is adsorbed into above-mentioned lead nitrate solution, adsorption time 0.5h, the input amount of vernadite is 1.67g.After the completion of absorption, Using Pb in solution after the measurement absorption of chelate extraction method described in standard GB/T/T7475-19872+Ion concentration, Pb2+From Sub- removal rate=(Pb in original solution2+Pb in solution after ion concentration-absorption2+Ion concentration) Pb in ÷ original solution2+Ion concentration × 100%, the results are shown in Table 1.
Embodiment 2
A kind of preparation method of vernadite, the step specifically:
(1) KMnO is prepared4Concentration is 118mmol/L, H2SO4Concentration is the solution A of 60mmol/L, prepares H2O2Concentration is The B solution of 170mmol/L；
(2) according to reaction molar ratio KMnO4: H2O2The ratio of=1:1.35, drips B solution under conditions of being vigorously stirred It is added in solution A, occurs a large amount of dark brown solids during being added dropwise, while with O2Release；
(3) it is stirred 3 hours after being added dropwise to complete, solid is collected by filtration, solid liquid after washing is washed with deionized Conductivity less than 20 μ s/cm, then solid is dry, be ground up, sieved, both vernadite.
It takes 0.2g or so powder tabletted by powder pressing method, then carries out X-ray diffraction (XRD) analysis, gained knot Fruit such as Fig. 2.
Using the manganese oxidizability (Kijima et al.2001) in Oxalic Acid Method measurement vernadite.Its measuring method such as China Middle agriculture university's Master's thesis " δ-MnO2Substructure conversion and todorokite chemical forming feature " it is described.Described in the present embodiment Manganese oxidizability in vernadite is as shown in table 1.
Prepare Pb2+Ion concentration is the lead nitrate solution 1L of 3mmol/L, and vernadite obtained by the present embodiment is directly launched It is adsorbed into above-mentioned lead nitrate solution, adsorption time 0.5h, the input amount of vernadite is 1.67g.After the completion of absorption, Using Pb in solution after the measurement absorption of chelate extraction method described in standard GB/T/T7475-19872+Ion concentration, Pb2+From Sub- removal rate=(Pb in original solution2+Pb in solution after ion concentration-absorption2+Ion concentration) Pb in ÷ original solution2+Ion concentration × 100%, the results are shown in Table 1.
Embodiment 3
A kind of preparation method of vernadite, the step specifically:
(1) KMnO is prepared4Concentration is 127mmol/L, H2SO4Concentration is the solution A of 63.2mmol/L, prepares H2O2Concentration is The B solution of 190mmol/L；
(2) according to reaction molar ratio KMnO4: H2O2The ratio of=1:1.5, B solution is added dropwise under conditions of being vigorously stirred Into solution A, occur a large amount of dark brown solids during being added dropwise, while with O2Release；
(3) it is stirred 3 hours after being added dropwise to complete, solid is collected by filtration, solid liquid after washing is washed with deionized Conductivity less than 20 μ s/cm, then solid is dry, be ground up, sieved, both vernadite.
The micromorphology of gained vernadite powder is observed using scanning electron microscope (SEM).Take appropriate vernadite Ultrasonic disperse 10min in ethanol solution is placed in then suspension is brushed on copper fine-structure mesh and dried with hairbrush, so at suspension Vacuum metal spraying afterwards observes vernadite microscopic appearance.Amplification 6 × 104SEM figure again is as shown in Figure 1.
It takes 0.2g or so powder tabletted by powder pressing method, then carries out X-ray diffraction (XRD) analysis, gained knot Fruit such as Fig. 2.
The manganese oxidizability in vernadite described in the present embodiment, result such as 1 institute of table are measured according to 2 the method for embodiment Show.
Prepare Pb2+Ion concentration is the lead nitrate solution 1L of 3mmol/L, and vernadite obtained by the present embodiment is directly launched It is adsorbed into above-mentioned lead nitrate solution, adsorption time 0.5h, the input amount of vernadite is 1.67g.After the completion of absorption, Using Pb in solution after the measurement absorption of chelate extraction method described in standard GB/T/T7475-19872+Ion concentration, Pb2+From Sub- removal rate=(Pb in original solution2+Pb in solution after ion concentration-absorption2+Ion concentration) Pb in ÷ original solution2+Ion concentration × 100%, the results are shown in Table 1.
Embodiment 4
A kind of preparation method of vernadite, the step specifically:
(1) KMnO is prepared4Concentration is 143mmol/L, H2SO4Concentration is the solution A of 71mmol/L, prepares H2O2Concentration is The B solution of 220mmol/L；
(2) according to reaction molar ratio KMnO4: H2O2The ratio of=1:1.65, drips B solution under conditions of being vigorously stirred It is added in solution A, occurs a large amount of dark brown solids during being added dropwise, while with O2Release；
(3) it is stirred 3 hours after being added dropwise to complete, solid is collected by filtration, solid liquid after washing is washed with deionized Conductivity less than 20 μ s/cm, then solid is dry, be ground up, sieved, both vernadite.
It takes 0.2g or so powder tabletted by powder pressing method, then carries out X-ray diffraction (XRD) analysis, gained knot Fruit such as Fig. 2.
The manganese oxidizability in vernadite described in the present embodiment, result such as 1 institute of table are measured according to 2 the method for embodiment Show.
Prepare Pb2+Ion concentration is the lead nitrate solution 1L of 3mmol/L, and vernadite obtained by the present embodiment is directly launched It is adsorbed into above-mentioned lead nitrate solution, adsorption time 0.5h, the input amount of vernadite is 1.67g.After the completion of absorption, Using Pb in solution after the measurement absorption of chelate extraction method described in standard GB/T/T7475-19872+Ion concentration, Pb2+From Sub- removal rate=(Pb in original solution2+Pb in solution after ion concentration-absorption2+Ion concentration) Pb in ÷ original solution2+Ion concentration × 100%, the results are shown in Table 1.
Embodiment 5
A kind of preparation method of vernadite, the step specifically:
(1) KMnO is prepared4Concentration is 150mmol/L, H2SO4Concentration is the solution A of 80mmol/L, prepares H2O2Concentration is The B solution of 250mmol/L；
(2) according to reaction molar ratio KMnO4: H2O2The ratio of=1:1.75, drips B solution under conditions of being vigorously stirred It is added in solution A, occurs a large amount of dark brown solids during being added dropwise, while with O2Release；
(3) it is stirred 3 hours after being added dropwise to complete, solid is collected by filtration, solid liquid after washing is washed with deionized Conductivity less than 20 μ s/cm, then solid is dry, be ground up, sieved, both vernadite.
The micromorphology of gained vernadite powder is observed using scanning electron microscope (SEM).Take appropriate vernadite Ultrasonic disperse 10min in ethanol solution is placed in then suspension is brushed on copper fine-structure mesh and dried with hairbrush, so at suspension Vacuum metal spraying afterwards observes vernadite microscopic appearance.Amplification 6 × 104SEM figure again is as shown in Figure 1.
It takes 0.2g or so powder tabletted by powder pressing method, then carries out X-ray diffraction (XRD) analysis, gained knot Fruit such as Fig. 2.
The manganese oxidizability in vernadite described in the present embodiment, result such as 1 institute of table are measured according to 2 the method for embodiment Show.
Prepare Pb2+Ion concentration is the lead nitrate solution 1L of 3mmol/L, and vernadite obtained by the present embodiment is directly launched It is adsorbed into above-mentioned lead nitrate solution, adsorption time 0.5h, the input amount of vernadite is 1.67g.After the completion of absorption, Using Pb in solution after the measurement absorption of chelate extraction method described in standard GB/T/T7475-19872+Ion concentration, Pb2+From Sub- removal rate=(Pb in original solution2+Pb in solution after ion concentration-absorption2+Ion concentration) Pb in ÷ original solution2+Ion concentration × 100%, the results are shown in Table 1.
Comparative example 1
A kind of preparation method of vernadite, method and step, technological parameter etc. are identical with embodiment 3, and difference is only It is, the vernadite is used further to wastewater treatment, activation modification step after activation modification are as follows:
1) EDTA, sodium carbonate and ethylenediamine tetra-acetic acid tripotassium are dissolved in water and are configured to activation modification liquid, wherein EDTA Concentration is 0.5mol/L, and the concentration of sodium carbonate is 2mol/L, and the concentration of ethylenediamine tetra-acetic acid tripotassium is 0.25mol/L；
2) activation modification liquid pours into reaction vessel, and vernadite obtained is immersed in activation modification liquid, then will be anti- Container is answered to seal, to container vacuum-pumping, so that pressure is between 1000~2000Pa in container；
3) ebuillition of heated, boiling time 1h are carried out to activation modification liquid；
4) solid is but collected by filtration afterwards, uses deionized water for equalizing reservoir inside and outside differential pressure after the completion of boiling, activation modification liquid cooling It is dry less than 20 μ s/cm, then by solid to wash the conductivity of solid liquid after washing, the vernadite after being activated.
The manganese oxidizability in vernadite described in this comparative example, result such as 1 institute of table are measured according to 3 the method for embodiment Show.
Prepare Pb2+Ion concentration is the lead nitrate solution 1L of 3mmol/L, and vernadite obtained by the present embodiment is directly launched It is adsorbed into above-mentioned lead nitrate solution, adsorption time 0.5h, the input amount of vernadite is 1.67g.After the completion of absorption, Using Pb in solution after the measurement absorption of chelate extraction method described in standard GB/T/T7475-19872+Ion concentration, Pb2+From Sub- removal rate=(Pb in original solution2+Pb in solution after ion concentration-absorption2+Ion concentration) Pb in ÷ original solution2+Ion concentration × 100%, the results are shown in Table 1.
Comparative example 2
A kind of preparation method of vernadite, method and step, technological parameter etc. are identical with embodiment 3, and difference is only It is, the vernadite is used further to wastewater treatment, activation modification step after activation modification are as follows:
1) EDTA, sodium carbonate and ethylenediamine tetra-acetic acid tripotassium are dissolved in water and are configured to activation modification liquid, wherein EDTA Concentration is 0.8mol/L, and the concentration of sodium carbonate is 1mol/L, and the concentration of ethylenediamine tetra-acetic acid tripotassium is 0.35mol/L；
2) activation modification liquid pours into reaction vessel, and vernadite obtained is immersed in activation modification liquid, then will be anti- Container is answered to seal, to container vacuum-pumping, so that pressure is between 1000~2000Pa in container；
3) ebuillition of heated, boiling time 2h are carried out to activation modification liquid；
4) solid is but collected by filtration afterwards, uses deionized water for equalizing reservoir inside and outside differential pressure after the completion of boiling, activation modification liquid cooling It is dry less than 20 μ s/cm, then by solid to wash the conductivity of solid liquid after washing, the vernadite after being activated.
The manganese oxidizability in vernadite described in this comparative example, result such as 1 institute of table are measured according to 3 the method for embodiment Show.
Prepare Pb2+Ion concentration is the lead nitrate solution 1L of 3mmol/L, and vernadite obtained by the present embodiment is directly launched It is adsorbed into above-mentioned lead nitrate solution, adsorption time 0.5h, the input amount of vernadite is 1.67g.After the completion of absorption, Using Pb in solution after the measurement absorption of chelate extraction method described in standard GB/T/T7475-19872+Ion concentration, Pb2+From Sub- removal rate=(Pb in original solution2+Pb in solution after ion concentration-absorption2+Ion concentration) Pb in ÷ original solution2+Ion concentration × 100%, the results are shown in Table 1.
Comparative example 3
A kind of preparation method of vernadite, method and step, technological parameter etc. are identical with embodiment 3, and difference is only It is, the vernadite is used further to wastewater treatment, activation modification step after activation modification are as follows:
1) EDTA, sodium carbonate and ethylenediamine tetra-acetic acid tripotassium are dissolved in water and are configured to activation modification liquid, wherein EDTA Concentration is 1mol/L, and the concentration of sodium carbonate is 3mol/L, and the concentration of ethylenediamine tetra-acetic acid tripotassium is 0.1mol/L；
2) activation modification liquid pours into reaction vessel, and vernadite obtained is immersed in activation modification liquid, then will be anti- Container is answered to seal, to container vacuum-pumping, so that pressure is between 1000~2000Pa in container；
3) ebuillition of heated, boiling time 1h are carried out to activation modification liquid；
4) solid is but collected by filtration afterwards, uses deionized water for equalizing reservoir inside and outside differential pressure after the completion of boiling, activation modification liquid cooling It is dry less than 20 μ s/cm, then by solid to wash the conductivity of solid liquid after washing, the vernadite after being activated.
The manganese oxidizability in vernadite described in this comparative example, result such as 1 institute of table are measured according to 3 the method for embodiment Show.
Prepare Pb2+Ion concentration is the lead nitrate solution 1L of 3mmol/L, and vernadite obtained by the present embodiment is directly launched It is adsorbed into above-mentioned lead nitrate solution, adsorption time 0.5h, the input amount of vernadite is 1.67g.After the completion of absorption, Using Pb in solution after the measurement absorption of chelate extraction method described in standard GB/T/T7475-19872+Ion concentration, Pb2+From Sub- removal rate=(Pb in original solution2+Pb in solution after ion concentration-absorption2+Ion concentration) Pb in ÷ original solution2+Ion concentration × 100%, the results are shown in Table 1.
Such as Fig. 2, prepared product is vernadite in processing step of the present invention and parameter area.By table 1 it is found that prepared vernadite removes Pb with very excellent in process parameters range of the present invention2+Ion effect, This may be the adsorptivity for having benefited from vernadite prepared by the present invention itself and its tridimensional network (such as Fig. 1 It is shown), wherein number is best using the vernadite performance prepared under technological parameter described in embodiment 3 again.
Comparative example 3 and comparative example 1~3 are it is found that using the vernadite of the method for the invention preparation through overactivation After modification, Pb2+The removal rate of ion can further increase, it might even be possible to reach 98% or more.
Table 1
Test group Manganese oxidizability Pb2+Ion remaval rate
Embodiment 1 3.81 96.67%
Embodiment 2 3.83 96.82%
Embodiment 3 3.90 97.42%
Embodiment 4 3.96 96.34%
Embodiment 5 3.97 96.79%
Comparative example 1 3.88 99.08%
Comparative example 2 3.93 99.13%
Comparative example 3 3.90 99.11%
Technical solution provided by the present invention is described in detail above, for those of ordinary skill in the art, Thought according to an embodiment of the present invention, there will be changes in the specific implementation manner and application range, in conclusion this theory Bright book content should not be construed as limiting the invention.

Claims (2)

1. a kind of application of vernadite in the treatment of waste water, which is characterized in that launch vernadite in waste water, or system At filter cake filtered wastewater, for the Pb in Adsorption waste water2+, the preparation method of the vernadite the following steps are included:
1) by KMnO4With dense H2SO4It is added to the water and is configured to solution A, and prepares H2O2Solution is as B solution；
2) B solution is added drop-wise in solution A under agitation；
3) it is stirred 2 hours or more after being added dropwise to complete, solid is collected by filtration, solid liquid after washing is washed with deionized Conductivity less than 20 μ s/cm, then solid is dry, be ground up, sieved to get vernadite；
The vernadite is used further to wastewater treatment, activation modification step after activation modification are as follows:
1) EDTA, sodium carbonate and ethylenediamine tetra-acetic acid tripotassium are dissolved in water and are configured to activation modification liquid, wherein EDTA concentration For 0.5~1mol/L, the concentration of sodium carbonate is 1~3mol/L, and the concentration of ethylenediamine tetra-acetic acid tripotassium is 0.1~0.35mol/L；
2) activation modification liquid pours into reaction vessel, and vernadite obtained is immersed in activation modification liquid, then reaction is held Device sealing, to container vacuum-pumping, so that pressure is between 1000~2000Pa in container；
3) ebuillition of heated, boiling time >=1h are carried out to activation modification liquid；
4) solid is but collected by filtration afterwards, is washed with deionized for equalizing reservoir inside and outside differential pressure after the completion of boiling, activation modification liquid cooling The conductivity of solid liquid after washing is dry less than 20 μ s/cm, then by solid, the vernadite after being activated.
2. a kind of application of vernadite according to claim 1 in the treatment of waste water, which is characterized in that the water hydroxyl manganese When mine dispensing is adsorbed in waste water, adsorption time is no less than 0.5h, Pb in the input amount and waste water of vernadite2+Concentration ratio Are as follows:
Input amount >=0.5g/L:Pb of vernadite2+Concentration is 1mmol/L.
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CN101402471A (en) * 2008-10-24 2009-04-08 中国科学院电工研究所 Process for producing layered delta-MnO2 nano-particle
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