CN107213866A - A kind of preparation method and application for being used to go the zinc oxide modified zeolite adsorbing material of anionic pollutant in water removal - Google Patents
A kind of preparation method and application for being used to go the zinc oxide modified zeolite adsorbing material of anionic pollutant in water removal Download PDFInfo
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- CN107213866A CN107213866A CN201710491756.4A CN201710491756A CN107213866A CN 107213866 A CN107213866 A CN 107213866A CN 201710491756 A CN201710491756 A CN 201710491756A CN 107213866 A CN107213866 A CN 107213866A
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- zinc oxide
- oxide modified
- modified zeolite
- adsorbing material
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
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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
-
- 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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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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- Inorganic Chemistry (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)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Zinc oxide is supported on the preparation method that artificial and natural zeolite surface forms zinc oxide modified zeolite adsorbing material of the zinc oxide content no more than 30% the invention discloses a kind of use salt fusion method, and zinc oxide modified zeolite adsorbing material goes the application of anionic pollutant in water removal, the raw material sources of zinc oxide modified zeolite adsorbing material are extensive, preparation technology is simple, it is with low cost, it is easy to use, heat endurance is good, chemically stable is good, it is to anionic dye, the adsorption capacity of humus and pathogenic microorganism etc. is big, clearance is high, with boundless application prospect.
Description
Technical field
The invention belongs to the water-treatment technology field in water prevention and cure of pollution, it is related to a kind of zinc oxide modified zeolite adsorption material
The preparation method of material, further relates to the application of anionic pollutant in zinc oxide modified zeolite adsorbing material Adsorption water.
Background technology
For a long time, many research works have been carried out in the removal of anion micropollutants of the scholars in recycled water
Make.The anion gone using liquid chlorine disinfection method, ozone disinfection, ultraviolet sterilization and absorption method etc. in water removal is proposed respectively
Pollutant.Because absorption method has the advantages that simple to operate compared with other method and does not cause secondary pollution to environment, obtain
The favor of numerous scholars, is considered as often anionic pollutant removal technology in promising water.Due to the handling of absorption method
Sorbing material is heavily dependent on with removal effect, therefore domestic and international researchers are all strongly finding or developed new
Type, low cost, can effectively remove the sorbing material of anionic pollutant in water body.Activated carbon, which is that one kind is common, to be applied to drink
The sorbing material of water depth handling process, activated carbon is nonpolar in drinking water is removed or hydrophobicity organic matter effect is notable, and
It is not satisfactory to the adsorption effect of the pollutant with negative electrical charge in the range of natural water pH.
The content of the invention
For prior art, the present invention provides a kind of zinc oxide modified zeolite for being used to remove anionic pollutant in water removal
Its preparation method of sorbing material and application, solve activated carbon to the dyestuff with negative electrical charge in the range of natural water pH, corruption is planted
The not satisfactory technical problem of the adsorption effect of matter and pathogenic microorganism.
A kind of preparation method for being used to go the zinc oxide modified zeolite adsorbing material of anionic pollutant in water removal, is used
Zinc oxide is supported on zeolite surface formation zinc oxide modified zeolite adsorbing material by salt fusion method, including following prepare walks
Suddenly：
(1) using Zn (NO3)2·6H2O mixed with deionized water be made into zinc ion concentration be 3 mol/L zinc ion salt it is molten
Liquid, and compound concentration is 1 mol/L salpeter solution；
(2) the zinc ion salting liquid and salpeter solution of various dose are added in the evaporating dish equipped with zeolite, continuous
It is evaporated under stirring in heating on resistance furnace, is subsequently placed in Muffle furnace, 2h is calcined at 300 DEG C, you can Different Zinc oxidation is made
The zinc oxide modified zeolite adsorbing material of thing load capacity.
Further, natural zeolite or artificial zeolite of the zeolite for 50um-200um particle diameters.
Further, the zinc oxide of the zinc oxide modified zeolite adsorbing material load includes ZnO, Zn (OH)2,
Zn(OH)+And Zn2+。
Further, the load capacity of the zinc oxide of the zinc oxide modified zeolite adsorbing material is no more than 30%.
Application for going the zinc oxide modified zeolite adsorbing material of anionic pollutant in water removal, is by zinc oxide
Modified zeolite adsorbing material is placed in the water containing anionic pollutant and adsorbed.
Further, the anionic pollutant includes methyl orange, humic acid and Escherichia coli.
Beneficial effects of the present invention：
The raw material sources of zinc oxide modified zeolite adsorbing material are extensive, preparation technology is simple, with low cost, user
Just, heat endurance is good, chemically stable is good, and its clearance to anionic dye, humus and pathogenic microorganism etc. is high, absorption is held
Amount is big, with boundless application prospect.
Brief description of the drawings
Fig. 1 is Zeta potential figure of the zinc oxide modified zeolite adsorbing material under different solutions pH value.
Fig. 2 is the design sketch before and after zinc oxide modified zeolite adsorbing material absorption methyl orange.
Fig. 3 is the design sketch before and after zinc oxide modified zeolite adsorbing material absorption humic acid.
Fig. 4 a are the fluorescence micrograph of zinc oxide modified zeolite adsorbing material；
Fig. 4 b are the fluorescence micrograph of Escherichia coli bacteria liquid；
Fig. 4 c are fluorescence micrograph of the Escherichia coli absorption on zinc oxide modified zeolite surface.
Fig. 5 is the Escherichia coli bacteria liquid flat board culture photo of different adsorption times.
Embodiment
Purpose：Prepare zinc oxide modified zeolite adsorbing material, effective Adsorption dyes, humus and cause of disease
Microorganism.
Technical scheme：Zinc oxide is supported on artificial and natural zeolite surface using salt fusion method and forms zinc oxygen by the present invention
Compound content is no more than 30% zinc oxide modified zeolite adsorbing material, changes the surface charging property of the material, makes its grade electricity
Point about 11.2, and Zeta potential is basically unchanged as shown in figure 1, so as to effectively improve it in wider solution in the range of pH 5-9
To the absorption property of anionic pollutant in pH value range.The raw material sources of zinc oxide modified zeolite adsorbing material are extensive, system
Standby technique is simple, with low cost, and easy to use, heat endurance is good, chemically stable is good, and it is to anionic dye, humus and disease
The clearance of pathogenic microorganism etc. is high, adsorption capacity is big, with boundless application prospect.
Preparation process is as follows：
(1) using Zn (NO3)2·6H2O mixed with deionized water be made into zinc ion concentration be 3mol/L zinc ion salt it is molten
Liquid, and compound concentration is 1mol/L salpeter solution；
(2) a certain amount of zinc ion salting liquid and salpeter solution are added in the evaporating dish equipped with zeolite, constantly stirred
Mix down and be evaporated in heating on resistance furnace, be subsequently placed in Muffle furnace, 2h is calcined at 300 DEG C, you can different zinc oxides are made
The zinc oxide modified zeolite adsorbing material of load capacity.
Zinc oxide modified zeolite adsorbing material goes the application of anionic pollutant in water removal
Methyl orange in embodiment 1- Adsorption water bodys
At 21 ± 1 DEG C, the zinc oxide modified zeolite adsorbing material of 0.5g zinc oxides load capacity 30% is weighed, is placed in
In 250ml 100mg/L methyl orange solution, after magnetic agitation mixing 15min, 1 day is stood, zinc oxide modified zeolite is obtained
Design sketch before and after sorbing material absorption methyl orange, as shown in Figure 2.Zinc oxide modified zeolite adsorbing material is taken to adsorb first respectively
Supernatant liquor before and after base orange, with spectrophotometer at methyl orange maximum absorption wavelength 462nm, carries out colorimetric estimation methyl orange
The concentration of solution, it is 45mg/g to the saturated extent of adsorption of methyl orange to calculate zinc oxide modified zeolite adsorbing material.
Humic acid in embodiment 2- Adsorption water bodys
At 21 ± 1 DEG C, the zinc oxide modified zeolite adsorbing material of 0.05g zinc oxides load capacity 30% is weighed, is put
In the vial of 40 mL with closures, 25mL 140mgCL are filled in bottle respectively-1Humic acid solution, screw small glass
The closure of glass bottle, vial is placed on vertical rotary mixed instrument (50r/min), mixes 15min, after then standing 5 days,
The design sketch before and after zinc oxide modified zeolite adsorbing material absorption humic acid is obtained, as shown in Figure 3.Zinc oxide is taken to change respectively
Property zeolite adsorption material absorption humic acid before and after supernatant liquor, filtered with 0.2um filters (PVDF filtrates, Whatman, USA),
The organic carbon content of solution is finally determined with Shimadzu TOC instrument, zinc oxide modified zeolite adsorbing material is calculated to humic
The saturated extent of adsorption of acid is 140mgC/g.
Escherichia coli in embodiment 3- Adsorption water bodys
(1) adsorption effect of the fluorescence inverted microscope observation zinc oxide modified zeolite adsorbing material to Escherichia coli
3 holes are chosen on 12 orifice plates, 0.5mL sterilized water is added dropwise in one of hole, and two other hole is added dropwise 0.5 respectively
ML concentration is 2 × 109The CFU/mL Escherichia coli bacteria liquid for being transferred to green fluorescence protein gene, toward the hole of dress sterilized water and wherein
The zinc oxide load capacity for adding 0.02g in the hole of one dress bacterium solution respectively is 30% zinc oxide modified zeolite adsorption material
Material, hole of another dress bacterium solution is not loaded as blank control, and after 15min, 12 orifice plates are placed under fluorescence inverted microscope, if
Multiplication factor is put for 200 times, checks zinc oxide modified zeolite adsorbing material to being transferred to by observing the power of fluorescence intensity
The adsorption effect of the Escherichia coli (plasmid containing puc19-EGFP) of green fluorescence protein gene.Comparing result such as Fig. 4 a, Fig. 4 b, figure
Shown in 4c.From fluorescence micrograph it can be seen that zinc oxide modified zeolite adsorbing material is in itself without fluorescence；It is transferred to green glimmering
The green fluorescence of the Escherichia coli bacteria liquid of aequorin is evenly distributed；And add the zinc oxygen that zinc oxide load capacity is 30%
The fluorescence micrograph of the Escherichia coli bacteria liquid for being transferred to green fluorescence protein gene of compound modified zeolite adsorbing material shows to turn
The Escherichia coli for entering green fluorescence protein gene concentrate absorption on the surface of zinc oxide modified zeolite adsorbing material, and bacterium is basic
Exist in the form of blocking envelope, the fluorescence intensity of material surface significantly raises and sends green-yellow light.
(2) the method for plate culture count determines adsorbance of the zinc oxide modified zeolite adsorbing material to Escherichia coli.
The accurate Escherichia coli solution for pipetting 1mL concentration knowns, is put into the test tube equipped with 9mL sterile salines, uses
Ventilative silica gel test tube plug clogs test tube mouthful, and this is the bacterium solution of 10 times of dilution.The bacterium solution for diluting 10 times is well mixed, accurately pipetted
1mL is into 9mL sterile salines, and this is 102The bacterium solution diluted again.By that analogy, then respectively 10 are prepared3、104、105It is dilute again
The E. coli suspension released.It is 2 × 10 toward 10mL initial concentrations are equipped with4Add in the test tube of CFU/mL E. coli suspension
Enter 0.02g zinc oxide modified zeolite adsorbing material, under 25 DEG C, the experiment condition that pH value is 7, respectively in the reaction time
During for 0min, 60min, 120min, the uL of upper strata E. coli suspension 100 is taken to be spread evenly across equipped with having sterilized and cooled down solidifying
Solid LB solid mediums in, by culture dish be inverted be placed in 37 DEG C of constant temperature biochemical cultivation case cultivate 20h after, taking-up clapped
According to, the Escherichia coli bacteria liquid flat board culture photo of acquisition differential responses time, as shown in Figure 5.Can also be substantially from Fig. 5
Go out, over time, the quantity of Escherichia coli has the trend being decreased obviously, it is possible thereby to prove, zinc oxide is modified
Zeolite adsorption material has obvious Adsorption effect to Escherichia coli.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that for clarity, those skilled in the art should
Using specification as an entirety, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
It may be appreciated other embodiment.
Claims (6)
1. a kind of preparation method for being used to go the zinc oxide modified zeolite adsorbing material of anionic pollutant in water removal, its feature
Be, using salt fusion method by zinc oxide be supported on zeolite surface formation zinc oxide modified zeolite adsorbing material, including with
Lower preparation process：
(1) using Zn (NO3)2·6H2O mixes the zinc ion salting liquid for being made into that zinc ion concentration is 3mol/L with deionized water, and
Compound concentration is 1mol/L salpeter solution；
(2) the zinc ion salting liquid and salpeter solution of various dose are added in the evaporating dish equipped with zeolite, are being stirred continuously
Under on resistance furnace heating be evaporated, be subsequently placed in Muffle furnace, 2h be calcined at 300 DEG C, you can be made different zinc oxides bear
The zinc oxide modified zeolite adsorbing material of carrying capacity.
2. a kind of zinc oxide modified zeolite adsorption material for being used to remove anionic pollutant in water removal according to claim 1
The preparation method of material, it is characterised in that natural zeolite or artificial zeolite of the zeolite for 50um-200um particle diameters.
3. a kind of zinc oxide modified zeolite adsorption material for being used to remove anionic pollutant in water removal according to claim 1
The preparation method of material, it is characterised in that the zinc oxide of the zinc oxide modified zeolite adsorbing material load includes ZnO, Zn
(OH)2, Zn (OH)+And Zn2+。
4. a kind of zinc oxide modified zeolite adsorption material for being used to remove anionic pollutant in water removal according to claim 3
The preparation method of material, it is characterised in that the load capacity of the zinc oxide of the zinc oxide modified zeolite adsorbing material is no more than
30%.
5. being used for as described in claim 1-4 any one goes the zinc oxide modified zeolite of anionic pollutant in water removal to inhale
The application of enclosure material, is that zinc oxide modified zeolite adsorbing material is placed in the water containing anionic pollutant to be adsorbed.
6. application according to claim 5, it is characterised in that the anionic pollutant includes methyl orange, humic acid and
Escherichia coli.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111362510A (en) * | 2020-03-24 | 2020-07-03 | 浙江省海洋水产养殖研究所 | Water body ecological balance restoration method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111362510A (en) * | 2020-03-24 | 2020-07-03 | 浙江省海洋水产养殖研究所 | Water body ecological balance restoration method |
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