CN105148885B - For removing BrO3‑And ClO4‑Nanometer ferrimanganic modified zeolite and its preparation and application - Google Patents
For removing BrO3‑And ClO4‑Nanometer ferrimanganic modified zeolite and its preparation and application Download PDFInfo
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- CN105148885B CN105148885B CN201510520084.6A CN201510520084A CN105148885B CN 105148885 B CN105148885 B CN 105148885B CN 201510520084 A CN201510520084 A CN 201510520084A CN 105148885 B CN105148885 B CN 105148885B
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Abstract
It is used to remove BrO the invention discloses one kind3 ‑And ClO4 ‑Nanometer ferrimanganic modified zeolite and its preparation and application.The preparation method is specially：First natural clinoptilolite is crushed and screened, acid-base pretreatment, then in the polyglycol solution at 120~140 DEG C, by zeolite and FeCl3、MnSO4Add and stir by weight mixing, NaOH solution to black suspension thing is added not to be further added by into mixed liquor after 10~20min of reaction, continue to filter mixture after reacting 20~30min, elute, solid, which is dried to constant weight, can be prepared by described being used to remove BrO3 ‑And ClO4 ‑Nanometer ferrimanganic modified zeolite.The inventive method raw material is easy to get, producing process is simple, produces that cost is relatively low, and the use of nonhazardous raw and auxiliary material is particularly suitable for use in causing BrO of concern in recent years3 ‑、ClO4 ‑Micro-polluted raw processing, has a extensive future.
Description
Technical field
The invention belongs to environmental protection and chemical separating field, and in particular to one kind is used to remove BrO3 -And ClO4 -Receive
Rice ferrimanganic modified zeolite and its preparation and application.
Background technology
Bromate (BrO3 -) and perchlorate (ClO4 -) it is two kinds of oxygen-containing acid groups of halogen.Bromate in drinking water is main
The accessory substance produced from brominated surface water or underground water during ozonization, perchlorate in addition to being enriched with naturally, people
Mainly there are oxidant-ammonium perchlorate, the part potassium nitrate agricultural chemicals in the solid propellant of rocket, fireworks etc., and portion for source
Divide the discharge of gunpowder and fireworks manufacturing enterprise.Bromate has strong carcinogenicity, and long-term quote can trigger the organs such as liver, thyroid gland
Canceration, perchlorate then can severe jamming human thyroglobulin function, influence human normal metabolic function.Therefore to its
The research of presence, source and secure threshold in drinking water causes the attention of Environmental Studies person.《Sanitary standard for drinking water
(GB5749-2006)》Middle regulation bromate limit value is 0.01mgL-1, and high chlorine in Environmental Protection in America portion (EPA) regulation drinking water
Hydrochlorate limit value is 24.5 μ gL-1.Because two kinds of pollutants exist with dissolubility ionic state, the routine generally used at present is " mixed
Retrogradation shallow lake-filtering-sterilization " handling technology of water supply can not be removed effectively.It is conceived to the removal of bromate in Raw Drinking Water, at present
There is part Patents report (a kind of efficient absorption pillars detected for bromate in drinking water of CN203247158U), and it is high
Use complex membrane separating method more the removal of chlorate, also there is the research using new organic adsorption material
(device of the selective film technology of CN101439889 synchronous adsorption-desorptions, method and its application；CN102502911A one kind is inhaled
The method of perchlorate in attached degradation water).But these methods are with high costs, or easily produce secondary pollution.
Zeolite is as the natural minerals that distribution is wide, reserves are big, with larger specific surface area and charging performance, modified
After processing can have it is a variety of catalysis and absorption property (CN102671623A fly ash base Zeolite/alumina composite adsorbing materials
Preparation method；The method of dyestuff in the species zeolitic imidazolate framework material decolorization adsorption water of CN102267736A mono-).Study
It is a kind of safely and effectively reducing agent that person, which notices that fe is made, and uses finished product Nanoscale Iron, is acted on by physical adhesion, with reference to
In zeolite granular surface (a kind of preparation methods of Nanoscale Iron modified zeolite of CN103464094A), but the patent application is to use into
Product Nanoscale Iron is acted on by physical adhesion, with reference on zeolite granular surface；The poor dispersion of Nanoscale Iron, short grained table
Face is combined can more big easier conglomeration, it is impossible to be more evenly distributed in zeolite surface, and internal layer Nanoscale Iron can not be played effectively also
Former efficiency；Additionally, due to being to be combined together by adhesive effect with zeolite, if being immersed in water and having stirring shear action
Under, Nanoscale Iron is easier to separate with zeolite granular.
The content of the invention
In place of shortcoming and defect to solve prior art, primary and foremost purpose of the invention is to provide a kind of for removing
BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite preparation method.
BrO is removed another object of the present invention is to being used for of providing that above-mentioned preparation method obtains3 -And ClO4 -Nanoscale Iron
Manganese modified zeolite.The modified zeolite material is by the natural zeolite with high adsorption activity, the mixture of load Nanoscale Iron nanostructured manganese
Composition, specific surface area is big, and active site position is more, can be with ClO4 -、BrO3 -Produce stronger Electrostatic Absorption and reduction effect, adaptability
By force, the rate of adsorption is fast, and removal efficiency is high.
It is used to remove BrO it is yet a further object of the present invention to provide above-mentioned3 -And ClO4 -Nanometer ferrimanganic modified zeolite
Using.
For achieving the above object, the present invention is adopted the following technical scheme that：
One kind is used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite preparation method, comprise the following steps：
(1) after crushing natural zeolite, sieve, cleaning, under normal temperature condition, soaked with HCl solution and NaOH solution, so
Filter, wash afterwards, drying obtains Wessalith CS；
(2) Wessalith CS and FeCl for obtaining step (1)3、MnSO4Added after mixing in polyglycol solution, and stir equal
Even, 120~140 DEG C of constant temperature fully react 10~20min, obtain zeolite suspension；Wherein Wessalith CS and FeCl3Weight ratio is (5
~10):1, Wessalith CS and MnSO4Weight ratio is (15~20):1；
(3) add NaOH solution to black suspension thing not to be further added by the zeolite suspension obtained to step (2), then proceed to
React 20~30min；Eluted after mixed liquor is filtered, elution no longer changes to pH, drying to constant weight can be prepared by described be used for
Remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite.
The nanometer ferrimanganic modified zeolite produced is preferably closed to be placed in shady and cool dry place's preservation.
Step (1) described soak time is 5~10min；The washing refers to clean 3~5min with deionized water, described
Drying temperature is 100~105 DEG C.
Natural zeolite described in step (1) is clinoptilolite or modenite, and the sieving refers to 100~150 mesh sieves
Point.
Step (1) the HCl solution concentration is 0.1~0.2molL-1, NaOH solution concentration is 0.1~0.2molL-1, HCl solution and NaOH solution soak time are 5~10min.Can also may be used first with being soaked after HCl solution with NaOH solution
With first with being soaked after NaOH solution with HCl solution.The weight ratio of step (2) polyglycol solution and Wessalith CS be 50~
100：1；The molecular weight polyethylene glycol is 2000~3000.
The polyglycol solution refers to that polyethylene glycol is heated to 120~140 DEG C of lysigenous homogeneous phase solutions.The present invention
By the reproducibility of polyethylene glycol under high temperature, molysite and manganese salt are reduced into zero-valent metal simultaneously, mixed in zeolite surface generation
Nanoscale Iron and nanostructured manganese particle.
Step (3) the NaOH solution concentration is 1molL-1。
Step (3) elution no longer changes to pH to be referred to 0.1~0.2molL-1NaOH solution rinse 3~
5min, is then eluted to leacheate pH with deionized water and no longer changed；The drying temperature is 50~60 DEG C.
What above-mentioned preparation method was obtained is used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite, this nanometer of ferrimanganic change
Property zeolite in Nanoscale Iron and nanostructured manganese weight ratio be 1:3~1:5, Nanoscale Iron and nanostructured manganese account for this nanometer of ferrimanganic modified zeolite gross weight
The 5~10% of amount.
It is above-mentioned to be used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite remove raw water of micropolluted water in BrO3 -
Or ClO4 -In application.
Above-mentioned application is concretely comprised the following steps：It is in the SS (suspension in water quality) of pending raw water of micropolluted water
10mg·L-1Below, pH be 6~9 under conditions of, will be used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite press 1.0
~.5gL-1Throwing amount add into pending raw water of micropolluted water adsorption reaction and stirred, after the completion of reaction lead to
Enter sedimentation basin, add 0.5~5mgL-1PFS coagulant (i.e. bodied ferric sulfate) or PAC coagulant (i.e. aluminium polychloride),
Precipitate 0.3~0.5h, completion processing.
If containing BrO3 -Or ClO4 -Pending raw water of micropolluted water in ss suspended solid >=100mgL-1, need to first pass through
Better simply Pre-coagulation precipitates (2~5mgL-1High-molecular coagulant adopting, the 10~20min of sedimentation time such as PFS/PAM) by water
SS is reduced to 10mgL-1Below；If raw water pH is more than 9 or less than 6, in the range of regulation to 6~9, then by the Nanoscale Iron of preparation
Manganese modified zeolite presses 1.0~.5gL-1Throwing amount, added with dry type dosing method into pending raw water of micropolluted water,
BrO in accessing pending water3 -Concentration is not higher than 0.1mgL-1Or ClO4 -Concentration is not higher than 0.245mgL-1；Adsorption reaction can be used
Batch (-type) (SBR) or plug flow reactor (PFR), preferably using mechanical agitation, stirring intensity is not produced with keeping adsorbent to suspend
Precipitation is advisable；Adsorb 0.5~1h (BrO3 -) or 2~2.5h (ClO4 -) enter sedimentation basin afterwards, while adding 0.5~5mgL-1's
PFS or PAC coagulant, the sedimentation time is 0.3~0.5h, supernatant overflow discharge, BrO in water outlet3 -Concentration is not higher than
0.01mg·L-1Or ClO4 -Concentration is not higher than 0.0245mgL-1.Sedimentation basin body refuse should be determined as danger by leaching test
Dangerous waste or household waste are acted upon.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) nanometer ferrimanganic modified zeolite surface of the invention is constituted by arranging close nanometer ferrimanganic confusion, compares table
Area is big, the active site position rich in fe and simple substance manganese, and ferrimanganic particle surface is in electropositive, can be with electronegative BrO3 -Or
ClO4 -Stronger Electrostatic Absorption effect is produced, while BrO of the partial adsorbates in ferrimanganic particle surface3 -Or ClO4 -Can be with nanometer ferrimanganic
The reaction of generation redox chemistry is as follows：
nBrO3 -+3Fe0→3FeOn+nBr- (1)
nBrO3 -+3Mn0→3MnOn+nBr- (2)
nClO4 -+4Fe0→4FeOn+nCl- (3)
nClO4 -+4Mn0→4MnOn+nCl- (4)
Further, since ferrimanganic particulate is combined together, micro cell effect can be produced, by reacting (5) by electronics to receiving
The extra-granular transfer of rice ferrimanganic：
Mn0+FeOn→MnOn+Fe0 (5)
So that internal granular layer Zero-valent Iron, zeroth order manganese not with BrO3 -Or ClO4 -In the case of directly contacting, also can
Give full play to reduction.Therefore, simple Nanoscale Iron is compared to, the obtained nanometer ferrimanganic modified zeolite of the present invention adapts to energy
Power is strong, and the rate of adsorption is fast, and adsorption capacity is high, and removal efficiency is high.
(2) natural zeolite that uses of the present invention and the iron of load, manganese Metal are composition present in nature and people
The necessary element of body, without any bio-toxicity, uses safety non-pollution.
(3) the nanometer ferrimanganic modified zeolite in the present invention, ferrimanganic is carried on zeolite surface with nanoscale thin layer, can be abundant
With BrO3 -Or ClO4 -React without causing Nanoscale Iron manganese material costly to waste.
(4) the nanometer ferrimanganic modified zeolite preparation method in the present invention is relatively simple, and PEG repeated multiple times can be used, cost
It is cheap；It is easy to use, it can be applied without existing Water purification structures are carried out with large-scale redevelopment or large scale equipment is added；Receive
Rice ferrimanganic modified zeolite material preservation is convenient, and effect is lasting.
Brief description of the drawings
Fig. 1 is for removing BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite preparation technology flow chart；
Fig. 2 is for removing BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite processing it is micro- pollution contain BrO3 -Or ClO4 -Water
Process chart；
Fig. 3 is that natural zeolite removes BrO with being used for3 -And ClO4 -Nanometer ferrimanganic modified zeolite adsorbing material surface scan
Electron microscope；
Fig. 4 is the reaction time to BrO3 -And ClO4 -The influence of clearance；
Fig. 5 is BrO3 -And ClO4 -Initial concentration to BrO3 -And ClO4 -The influence of clearance；
Fig. 6 is for removing BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite processing simulation polluted water breakthrough curve.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
(1) it is used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite material preparation, concrete technology flow process such as Fig. 1
It is shown：
(1) natural zeolite is chosen, mechanical crushing, 100~150 mesh sieves are cleaned after dividing with distilled water, under normal temperature condition, first
Use 0.1molL-1NaOH solution immersion 10min, then with terylene or polyvinyl filter-cloth filtering；0.1molL is used again-1HCl is molten
Immersion steeps 10min, and 3~5min is cleaned with deionized water after filtering again, and drying obtains Wessalith CS at 100~105 DEG C；
(2) low molecular poly (PEG 2000) of 100 times of Wessalith CS consumption (weight ratio) is taken, with cooling back
Being heated to 120~140 DEG C in stream device and magnetic stirring apparatus flask makes its dissolving form homogeneous phase solution；Step (1) is made
Wessalith CS and FeCl3、MnSO4Add into polyglycol solution, and stir after mixing, 120~140 DEG C of constant temperature are fully anti-
10~20min is answered, zeolite suspension is obtained；Wherein Wessalith CS and FeCl3Weight compares 10:1, Wessalith CS and MnSO4Weight compares 20:1；
(3) 1molL is added dropwise into zeolite suspension-110~20mL of NaOH solution be not further added by black suspension thing,
Continue to react 20~30min；It will be eluted after mixed liquor glass fiber filter, with 0.1~0.2molL-1NaOH solution punching
3~5min is washed, is then eluted to leacheate pH and no longer changed with deionized water, low temperature drying to constant weight can be made at 50~60 DEG C
It must be used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite.
(2) using step (1) preparation for removing BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite material process drink
With water raw water ClO4 -Contamination accident, technological process is as shown in Figure 2：
Certain river is due to being contaminated, ClO4 -Concentration is 0.23mgL-1, more than 9 times of EPA recommended values, raw water pH 7~
7.5, TOC 3~10mgL-1.Now using conventional coagulation-settlement process to ClO4 -Clearance is only 15%.Therefore, using
Set up pre-reaction pond before coagulant dosage, bottom sets agitating device, design hydraulic detention time is 2.5h, and with the dry type side of adding
Formula add step (1) preparation be used for remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite, dosage is 2.0gL-1；Or
Directly use existing long distance water transfer canal for plug flow reactor, mechanical stirring device is suitably set up in bottom, not produce alluvial
It is limited, hydraulic detention time is 2~2.5h.After absorbing and reducing, into follow-up coagulating sedimentation, 2.0mgL is added-1Precipitated after PFS
0.5h, has adsorbed ClO4 -Modified zeolite particle separated by precipitation, water outlet can meet ClO after processing4 -≤
0.0245mg·L-1Water quality standard for drinking water.
Fig. 3 is that natural zeolite removes BrO with being used for3 -And ClO4 -Nanometer ferrimanganic modified zeolite surface scan electron microscope (a
It is natural zeolite, b is to be used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite).Surface scan Electronic Speculum result shows, passes through
The loose granule foreign of zeolite surface after modification greatly reduces.The increase of specific surface area is conducive to adsorbate on surface
Absorption and duct transmission, are also beneficial to combining closely for zeolite granular and iron and manganese oxides.Surface Creation arrangement simultaneously is fine and close,
The Nanoscale Iron and nanostructured manganese granulate mixture of crystal structure, good interface environment is provided for the progress of redox reaction.My god
Pore structure parameter before and after right Zeolite modifying is as shown in table 1.
The natural zeolite of table 1 before modified after pore structure parameter
Note：Modified zeolite in table, which refers to that the present embodiment is obtained, to be used to remove BrO3 -And ClO4 -Nanometer ferrimanganic be modified
Zeolite.
Pore structure parameter analysis shows, compared with natural zeolite, for removing BrO3 -And ClO4 -Nanometer ferrimanganic be modified boiling
Stone specific surface area is not dramatically increased, but significant change occurs for pore structure, and the specific surface area and volume of micropore have certain increase.
This has dissolved the non-skeleton constituent impurity of part surface attachment mainly due to alkali process, has dredged the pore passage structure of zeolite, this
Outer modified nanometer ferrimanganic particle is attached to surface, also can produce influence to the measure of pore size distribution and pore structure.
Embodiment 2
(1) it is used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite material preparation：The present embodiment and embodiment 1
The difference is that Wessalith CS and FeCl3Weight ratio be 5:1 and MnSO4Weight ratio be 15:1；Other steps and parameter and embodiment
1 is identical.
(2) using step (1) preparation for removing BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite material administer
BrO in micro-polluted raw3 -Excessive problem：Drinking water BrO3 -Up to 0.08mgL-1, pH is 7~8.5, using stream as shown in Figure 4
Journey, i.e., first add 2.0gL-1Prepared by step (1) is used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite, during absorption
Between be 30min, then add 1.5mgL-1PFS coagulations after precipitate water outlet after 30min, quartz sand filtration and can be reduced to
0.008mg·L-1Hereinafter, drinking water standard is met.
Fig. 4 is to be used to remove BrO with embodiment 1 is obtained3 -And ClO4 -The nanometer ferrimanganic modified zeolite test reaction time
To BrO3 -And ClO4 -The influence of clearance, Fig. 5 is to be used to remove BrO with embodiment 1 is obtained3 -And ClO4 -Nanometer ferrimanganic change
Property zeolite test b rO3 -And ClO4 -Initial concentration to BrO3 -And ClO4 -The influence of clearance is (in Fig. 4 and Fig. 5：PH=7.0 ±
0.2, C (BrO3 -) 0=0.1mgL-1, C (ClO4 -) 0=0.245mgL-1, m=1.0gL-1, dosage m=1.2gL-1), the reaction time t=120min in Fig. 5.
As shown in figure 4, nanometer ferrimanganic modified zeolite is to BrO3 -And ClO4 -Absorption be all in 10~20min of beginning
The rate of adsorption is most fast, then gradually reduces, and reaches 90%, remaining BrO in 30min and 120min clearances respectively3 -And ClO4 -
Reach processing standard.Because there is nanometer ferrimanganic modified zeolite larger specific surface area and absorption duct to be inhaled there is provided substantial amounts of
Dot position, therefore in the initial reaction stage, the rate of adsorption is higher；After adsorption point position is occupied, inhaled under diffusion
Attached matter continues to spread into duct, and the rate of adsorption is also decreased.ClO4 -For positive tetrahedron structure, molecular configuration stabilization can be also
Originality is significantly worse than the BrO of four sides taper3 -。
As shown in figure 5, nanometer ferrimanganic modified zeolite is to BrO3 -And ClO4 -Clearance with BrO3 -And ClO4 -Initial concentration
Increase and reduce.The two initial concentration is from 0.1mgL-1Increase to 0.8mgL-1, clearance also respectively from 93.4%,
98.1% drops to 63.6% and 74.1%.The increase of initial concentration mean solution and adsorbent surface liquid film concentration difference and
The increasing of concentration gradient, is conducive to absorption to carry out, but because the value added of concentration exceedes the value added of adsorbance, therefore show as
The decline of clearance.
Embodiment 1 is obtained for removing BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite material dress post, lucite
Column internal diameter 8cm, packed height 165cm, filling apparent density are 2.6 × 103kg·m-3.Experiment is using simulation BrO3 -/ClO4 -It is dirty
Contaminate surface water and carry out dynamic filtration experiment, as a result as shown in Figure 6.As a result show, for removing BrO3 -And ClO4 -Nanometer ferrimanganic
Modified zeolite is to the two effective clearance 93~96%, but difference occur larger for the two time of break-through, and bromate is in absorption
Start to occur substantially leakage during 150~155min, and perchlorate is under then the clearance in 100~110min has started to significantly
Drop.Using clearance less than 10% as breakthrough point, the two reaches failure in 200min and 165min respectively.By adsorption time with
100min, 150min are counted, for removing BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite the two dynamic adsorption capacity is distinguished
For 20.8mgg-1、15.5mg·g-1。
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. one kind is used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite preparation method, it is characterised in that including following
Step：
(1) after crushing natural zeolite, sieve, cleaning, soaked with HCl solution and NaOH solution, then filter, wash, drying
Obtain Wessalith CS；
(2) Wessalith CS and FeCl for obtaining step (1)3、MnSO4Add in polyglycol solution, and stir after mixing,
120~140 DEG C of 10~20min of isothermal reaction, obtain zeolite suspension；Wherein Wessalith CS and FeCl3Weight ratio is (5~10):1,
Wessalith CS and MnSO4Weight ratio is (15~20):1；
(3) add NaOH solution to black suspension thing not to be further added by the zeolite suspension obtained to step (2), then proceed to reaction
20~30min；Eluted after mixed liquor is filtered, elution no longer changes to pH, drying to constant weight is to be made described to be used to remove
BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite.
2. according to claim 1 be used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite preparation method, it is special
Levy and be, step (1) described soak time is 5~10min；The washing refers to clean 3~5min with deionized water, the baking
Dry temperature is 100~105 DEG C.
3. according to claim 1 be used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite preparation method, it is special
Levy and be, the natural zeolite described in step (1) is clinoptilolite or modenite, the sieving refers to 100~150 mesh sieves
Point.
4. according to claim 1 be used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite preparation method, it is special
Levy and be, step (1) the HCl solution concentration is 0.1~0.2molL-1, NaOH solution concentration is 0.1~0.2molL-1, HCl solution and NaOH solution soak time are 5~10min.
5. according to claim 1 be used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite preparation method, it is special
Levy and be, step (2) described polyglycol solution refers to that polyethylene glycol is heated to 120~140 DEG C of lysigenous homogeneous phase solutions,
The weight ratio of polyglycol solution and Wessalith CS is 50~100：1；The molecular weight polyethylene glycol is 2000~3000.
6. according to claim 1 be used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite preparation method, it is special
Levy and be, the concentration of step (3) described NaOH solution is 1molL-1。
7. according to claim 1 be used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite preparation method, it is special
Levy and be, step (3) elution no longer changes to pH to be referred to 0.1~0.2molL-1NaOH solution rinse 3~5min,
Then eluted to leacheate pH and no longer changed with deionized water；The drying temperature is 50~60 DEG C.
8. one kind is used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite, it is characterised in that it is by claim 1 to 7 times
Being used for described in one removes BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite preparation method obtain, this is used to remove BrO3 -
And ClO4 -Nanometer ferrimanganic modified zeolite in Nanoscale Iron and nanostructured manganese weight ratio be 1:3~1:5, Nanoscale Iron and nanostructured manganese account for this and received
The 5~10% of rice ferrimanganic modified zeolite gross weight.
9. being used for described in claim 8 removes BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite application, it is characterised in that institute
State to apply and refer to be used to remove BrO by this3 -And ClO4 -Nanometer ferrimanganic modified zeolite be used for remove in raw water of micropolluted water
BrO3 -Or ClO4 -。
10. according to claim 9 be used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite application, its feature exists
In by this for removing BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite be used to remove BrO in raw water of micropolluted water3 -
Or ClO4 -Concretely comprise the following steps：It is 10mgL in the SS of pending raw water of micropolluted water-1Below, pH is 6~9 condition
Under, it will be used to remove BrO3 -And ClO4 -Nanometer ferrimanganic modified zeolite press 1.0~2.5gL-1Throwing amount add to pending micro-
Adsorption reaction and stirred in polluted drinking water raw water, sedimentation basin is passed through after the completion of reaction, 0.5~5mgL is added-1PFS
Coagulant or PAC coagulant precipitate 0.3~0.5h, completion processing.
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| CN107931317A (en) * | 2017-11-08 | 2018-04-20 | 马鞍山菌菌食品科技有限公司 | A kind of modified zeolite ferriferous oxide composite soil in-situ immobilization agent and preparation method thereof |
| CN108993384A (en) * | 2018-07-18 | 2018-12-14 | 中国地质大学（北京） | A kind of load iron lotus charcoal and preparation method thereof removing bromate in water removal |
| CN113998787A (en) * | 2020-07-28 | 2022-02-01 | 松山湖材料实验室 | Microbial composite material and preparation method and application thereof |
| CN112958036A (en) * | 2021-02-02 | 2021-06-15 | 暨南大学 | Zero-valent iron-manganese composite modified carbon nanotube and preparation method and application thereof |
| CN116161756B (en) * | 2022-10-28 | 2023-07-21 | 中南大学 | Preparation method of heavy medium for treating wastewater containing multiple pollutants |
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