CN104445565A - Method for removing micro or trace bromate from water by using loaded nanometer iron taking high-molecular fiber as carrier - Google Patents
Method for removing micro or trace bromate from water by using loaded nanometer iron taking high-molecular fiber as carrier Download PDFInfo
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- CN104445565A CN104445565A CN201410576889.8A CN201410576889A CN104445565A CN 104445565 A CN104445565 A CN 104445565A CN 201410576889 A CN201410576889 A CN 201410576889A CN 104445565 A CN104445565 A CN 104445565A
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- bromate
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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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
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses method for removing micro or trace bromate from water by using loaded nanometer iron taking high-molecular fiber as a carrier. The method comprises the following steps: adding a polypropylene fiber loaded nanometer zero-valent iron material into a reaction bottle which contains a bromate solution subjected to nitrogen deoxidization treatment, wherein the amount of the loaded zero-valent iron is 6.5mg/g to 33.3mg/g, and the initial concentration of the bromate is 0.5mg/L to 1.5mg/L; sealing the reaction bottle and oscillating the reaction bottle in a constant-temperature water-bath oscillator at a rotating speed of 170rpm at the temperature of 25 DEG C within a pH range of 2.8 to 12.0 for 1-2 hours. The nanometer zero-valent iron loaded on the surfaces of the fibers is high in reducibility and capable of rapidly reducing trace bromate in the water into bromide ions so as to fulfill the aim of removing the bromate from the water. The method has the advantages of low material usage, high removal rate and the like.
Description
Technical field
The present invention relates to a kind of method removing trace or trace amounts of bromine hydrochlorate in water, belong to purifying water process technique.
Background technology
This disinfection byproduct (DBP) of bromate can be produced after ozonization process.Bromate is considered to have genotoxic potential carcinogen matter; existing " drinking water sanitary standard " (GB5749-2006) of the World Health Organization (WHO), USEPA (USEPA) and China all specifies that the content of bromate in drinking water should lower than 10 μ g/L; and existing water technology can not meet the national standard of bromate, the bromate therefore in processing drinking water is extremely urgent.
The method of current minimizing bromate in drinking water is mainly divided into two classes, and first method is the forming process controlling bromate: reduce the measures such as pH value, ammonification, interpolation hydrogen peroxide and control or reduce the generation of bromate.Second method uses physico-chemical process to remove bromate mainly to comprise: the bromate in active carbon adsorption, nanocrystal iron ore load quartz sand, use ion exchange membrane bioreactor planar water, gac are combined with electrode and bromate can be converted into nontoxic bromide anion, layered double-hydroxide absorbing and reducing method, Pd/Al
2o
3the methods such as catalytic reduction method, ultraviolet irradiation, biological degradation method, Zero-valent Iron reduction method remove bromate.And these remove the equal Shortcomings part of method of bromate, after gac uses for some time, microbial film can be formed on surface, reduce treatment effect; Ion exchange membrane bioreactor processing cost is high and can produce high density bromate waste water, causes pollutent to there occurs transfer, can not reach the object of removal; The long reaction time of biological degradation method, and need very strong aftertreatment technology, to remove biology in water and excessive ethanol; The weak point of layered double-hydroxide is be converted into a-FeOOH and amorphous aluminum hydroxide, cannot realize regeneration; Pd/Al
2o
3the deficiency of catalytic reduction method is that catalyzer not easily reclaims the secondary pollution likely caused in water.Ultraviolet irradiation weak point is that the ultraviolet lamp needing higher-energy carries out irradiation, adds processing cost.
In the method for the above several removal bromate of contrast Zero-valent Iron reduction remove that bromate has efficiently, less energy-consumption, the advantage such as easy to control, be tool drinking water purification process technology with broad prospects for development.
Zero-valent Iron is divided into this three class of Zero-valent Iron of zeroth order iron powder and nano zero valence iron particle and loading type, and wherein use (1) zeroth order iron powder reducing to remove bromate, the dissolved oxygen existed in water and iron react and generates passive film and reduce reduction reaction rate.(2) structure of nano zero valence iron particle has higher specific surface area and surface reaction; favourable condition is provided for improving reduction effect; but to occur owing to lacking surface protection to reunite or oxidized to cause degradation efficiency to reduce due to nanoparticle, and nano particle is difficult to recovery from water and causes secondary pollution.Therefore nano zero-valence iron reducer is fixed on carrier and becomes inevitable trend.Macromolecular fibre is the bromate that the loaded with nano-iron of carrier is used for removing the total trace of water and trace by the present invention, provides a kind of new method.
Summary of the invention
The present invention be directed to the drawback of above-mentioned various method, provide a kind of macromolecular fibre to be the method that the Supported Nano Zero-valent Iron of carrier effectively removes underwater trace bromate.The method has that material usage is low, material can be recycled, remove the advantages such as speed is fast.With coordination reaction, Fe ion is introduced the surface of the polypropylene fibre after grafting, by controlling the pH etc. of the concentration of Fe ion in the percentage of grafting of fiber, coordination reaction, valence state, solution, can be evenly distributed, particle diameter is at the Zero-valent Iron material of nanoscale.In aqueous, the zero-valent iron material reductibility being carried on fiber surface is strong, fast redox reaction can occur, thus bromate is reduced to bromide anion, reach the object removing bromate from water with negatively charged ion bromate.
Summary of the invention
The zero-valent iron material being carried on polypropylene fibre surface to be positioned over containing a certain amount of perbromate ion and in the aqueous solution after nitrogen deoxidation treatment, the zeroth order Nanoscale Iron that fiber surface is fixing and bromate redox reaction fast occur, by BrO
3 -be reduced to Br
-, thus the bromate in tap water is removed.
In the reaction flask of the bromate solution through nitrogen deoxidation treatment, be incorporated in polypropylene fibre loaded with nano Zero-valent Iron material, the zeroth order iron of wherein load is 6.5mg/g-33.3mg/g, and the starting point concentration of bromate is 0.5mg/L-1.5mg/L.Be positioned in water-bath constant temperature oscillator after reaction flask sealing, reaction medium speed is 170rpm, and temperature is 25 DEG C, and pH is 2.8 ~ 12.0 scopes, concussion 1 ~ 2h.
Beneficial effect of the present invention shows the following aspects:
1. the ligand complex effect that have employed macromolecule polypropylene fiber and inorganic iron ion obtains load zeroth order Nanoscale Iron, and this effect not only can be utilized to generate Fe
0precursor (Fe
3+) be fixed on carrier surface, prepare the reductive agent Fe0 particle of loading type.And can also by Fe in reduction bromate
0the Fe ion generated after release electronics retightens and is adsorbed in fiber surface, slows down or prevent the generation of ferriferous oxide, thus is beneficial to maintenance Fe
0reactive behavior, improve Fe
0the efficiency utilized.
2. bromate and Zero-valent Iron react on the surface of fibrous carrier, Nanoscale Iron is removed in bromate process, reaction kinetics excellent property, the penetrating quality that fiber is good, avoids the impact that the internal diffusion that reacts when adopting the porous mass such as gac and zeolite to be carrier causes.
3. fiber-loaded zeroth order Nanoscale Iron is in the process of reduction bromate, Fe ionic weight residual in water is extremely low, most Fe ion is adsorbed by the carboxyl relocation bit of fiber surface, the content < 0.3mg/L of iron ion, reaches " drinking water sanitary standard (GB5749-2006).
4. there is natural organic matter humic acid NOM and several frequently seen inorganic anion in reaction soln, as NO
3 -, HCO
3 -, Cl
-, PO
4 3-, SO
4 2in-time, the removal of bromate is not affected substantially, and this material can be effective to the removal of bromate in impure water body.
5. fiber surface load Zero-valent Iron is remarkable to the removal effect of bromate, and clearance is high, and speed is fast, and possess skills feasibility, easy and simple to handle, and material is easy to get, and has good economy and environment benefit, so it can be made to be applied in actual water treatment.
Accompanying drawing explanation
The corresponding relation of the fiber-loaded iron of Fig. 1 and bromate concentration
The corresponding relation of the different bromate starting point concentration of Fig. 2 and bromate concentration
The corresponding relation of the different pH value of Fig. 3 and bromate
Embodiment
Embodiment 1
The present embodiment is the fiber-loaded Fe of checking
0the impact of amount on bromate reduction reaction.
Use to be configured with in the Erlenmeyer flask of the 50ml of rubber plug and add the BrO that the concentration that configured is 0.5mg/L
3 -reaction solution, vibrates in water bath with thermostatic control vibrator, and temperature of reaction is 25 DEG C, rotating speed is 170r/min, and reaction soln is through logical N
2deoxidation treatment.
The initial pH value regulating reaction solution is 6.72, and add the fiber 0.5g of different nano zero valence iron charge capacity respectively, iron is respectively 6.5mg/g, 8.4mg/g, 16.4mg/g, 33.3mg/g in the charge capacity of fiber surface, reaction times 1h.Dionex-1100 type chromatography of ions is used to detect BrO
3 -ultimate density be respectively 1.15 μ g/L, 1.30 μ g/L, 0.62 μ g/L, 1.5 μ g/L < 10 μ g/L.Using twin-beam ultraviolet spectrophotometer to measure solvability total iron content in end reaction liquid is 0.2mg/L, 0.25mg/L, 0.12mg/L, 0.29mg/L < 0.3mg/L.The BrO detected in final reaction solution
3 -" drinking water sanitary standard " (GB5749-2006) all can be reached with the content of the total iron of solvability.Therefore the present invention effectively can remove bromate.
Therefore the removal effect of difference on bromate of fiber-loaded nano zero-valence iron does not affect substantially, and clearance can reach more than 99%, illustrates and uses fiber-loaded nano zero valence iron to remove bromate rapidly and efficiently, as shown in Figure 1.
Embodiment 2
The present embodiment is checking different B rO
3 -starting point concentration is on the impact of bromate reduction reaction.
The concentration configured is the BrO of 0.524mg/L, 0.722mg/L, 1.476mg/L 3 kinds of concentration
3 -reaction solution.Use 3 respectively and be configured with in the Erlenmeyer flask of the 50ml of rubber plug the three kinds of concentration BrO adding and configured
3 -reaction solution, reaction soln is through logical N
2deoxidation treatment.In water bath with thermostatic control vibrator, carry out continuous oscillation, temperature of reaction is 25 DEG C, rotating speed is 170r/min.
The initial pH value regulating reaction solution is 6.7, and in reaction flask, loaded with nano Zero-valent Iron fiber adds 0.5g, and Nanoscale Iron is 8.4mg/g at fiber surface content, reaction times 1.5h.Dionex-1100 type chromatography of ions is used to detect BrO
3 -concentration be respectively 3.84 μ g/L, 9.57 μ g/L, 10.2 μ g/L≤10 μ g/L.Using twin-beam ultraviolet spectrophotometer to measure solvability total iron content in end reaction liquid is 0.08mg/L, 0.27mg/L, 0.11mg/L < 0.3mg/L.The BrO detected in final reaction solution
3 -the requirement of " drinking water sanitary standard " (GB5749-2006) all can be reached with the content of the total iron of solvability.Therefore the present invention effectively can remove bromate.
Therefore the removal effect of different starting point concentration bromate on fiber-loaded Zero-valent Iron reduction bromate has impact, and illustrate under certain starting point concentration, the experimental technique that fiber-loaded Zero-valent Iron removes bromate is feasible, as shown in Figure 2.
Embodiment 3
The present embodiment is that the different initial pH value of checking is on the impact of bromate reduction reaction.
Use to be configured with in the Erlenmeyer flask of the 50ml of rubber plug and add the BrO that the concentration that configured is 0.5mg/L
3 -reaction solution, carries out continuous oscillation in water bath with thermostatic control vibrator, and temperature of reaction is 25 DEG C, rotating speed is 170r/min, and reaction soln is through logical N
2deoxidation treatment.
The initial pH value regulating reaction solution is respectively 2.8,6.7,12.0, and in reaction flask, loaded with nano Zero-valent Iron fiber adds 0.5g, and Nanoscale Iron is 8.4mg/g at fiber surface content, reaction times 1.5h.Dionex-1100 type chromatography of ions is used to detect BrO
3 -concentration be respectively 102 μ g/L, 0.56 μ g/L < 10 μ g/L, 91.4 μ g/L.Using twin-beam ultraviolet spectrophotometer to measure solvability total iron content in end reaction liquid is 0.5mg/L, 0.08mg/L < 0.3mg/L, 0.3mg/L.The BrO detected in final reaction solution
3 -the requirement of " drinking water sanitary standard " (GB5749-2006) to be reached at neutral range with the content of the total iron of solvability.Therefore investigate different pH value to show bromate removal response situation, the clearance reacted under neutrallty condition is apparently higher than under acidity and alkaline condition.Illustrate that pH value removes bromate impact very greatly to fiber-loaded nano zero valence iron, as shown in Figure 3.
Embodiment 4
The present embodiment is the inorganic NO contained in checking solution
3 -, HCO
3 -, Cl
-, PO
4 3-, SO
4 2-ion and organic substance humic acid NOM, on the impact of fiber-loaded nano zero-valence Fe3+ reduction bromate reaction.
Use to be configured with in the Erlenmeyer flask of the 50ml of rubber plug and add the BrO that the concentration that configured is 0.5mg/L
3 -reaction solution, carries out continuous oscillation in water bath with thermostatic control vibrator, and temperature of reaction is 25 DEG C, rotating speed is 170r/min, and reaction soln is through logical N
2deoxidation treatment.
In reaction flask, the fiber of loaded with nano Zero-valent Iron adds 0.5g, and Nanoscale Iron is 8.4mg/g at fiber surface content, reaction times 1.5h.。Dionex-1100 type chromatography of ions is used to detect BrO
3 -concentration, contrast do not add mineral ion and organic reaction system, BrO
3 -the final all < 10 μ g/L of concentration.Several mineral ion HCO existed in solution
3 -, Cl
-, PO
4 3-, SO
4 2-and organic substance humic acid NOM the clearance that bromate is final is not affected substantially, NO
3 -slightly reduce BrO
3 -removal speed, but do not affect final clearance.
The interpretation of result of accompanying drawing
1, accompanying drawing 1 interpretation of result
In fig. 1, when fiber adds 0.5g, when fiber-loaded nano zero-valence iron is respectively 6.5mg/g, 8.4mg/g, 16.4mg/g, 33.3mg/g, when iron is 16mg/g and the speed of response of bromate the fastest, 6.5mg/g, 8.4mg/g speed of response is taken second place, when iron is 32mg/g and the reaction of bromate the slowest.Result shows that the increase of iron can strengthen bromate removal effect, but removal effect can decline on the contrary to some extent when iron exceedes certain limit.
2, accompanying drawing 2 interpretation of result
In fig 2, when the starting point concentration of bromate is 0.524mg/L, 0.722mg/L, 1.476mg/L, bromate starting point concentration is 0.524mg/L and Fe
0speed of response the fastest, the clearance of reaction is the highest.The final content of bromate is 10 μ g/L of 3.8 μ g/L < national Specifications.When the starting point concentration of bromate is 1.476mg/L, with Fe
0reaction effect the poorest, clearance only has about 50%, and the increase that result shows when bromate starting point concentration inhibits the removal effect of bromate.Therefore the bromate of low concentration should be selected in actual use to process.
3, accompanying drawing 3 interpretation of result
In fig. 3,3 kinds of selected pH value are respectively: 2.8,6.7,12.0.Fe when pH is 6.7
0the fastest with the speed of response of bromate, clearance is maximum.And speed of response is more or less the same when acid (2.8) and alkalescence (12.0), being all less than pH is under 6.7 conditions.Illustrating that the redox reaction of this Zero-valent Iron and bromate is subject to the impact of pH comparatively greatly, all there is certain restraining effect to reaction in acid and alkalescence.The reduction reaction of further proof bromate carries out effect better in neutral conditions, and reaction conditions is gentle.Therefore apply in the water treatment of reality the method remove bromic acid time pH value of solution be in neutrality, good removal effect can be reached.
Claims (4)
1. macromolecular fibre is the method for bromate in the Supported Nano Zero-valent Iron removal water of carrier, it is characterized in that: described macromolecular fibre is the loaded nano-iron material PP-g-AA-Fe of carrier
0be added to the water and react with bromate, this material is by BrO
3-be reduced to Br-thus realize BrO
3-removal.
2. macromolecular fibre is the Supported Nano Zero-valent Iron PP-g-AA-Fe of carrier according to claim 1
0remove the method for bromate in water, it is characterized in that in this material, load iron is 6.5mg/g-33.3mg/g.
3. macromolecular fibre is the Supported Nano Zero-valent Iron PP-g-AA-Fe of carrier according to claim 1
0remove the method for bromate in water, it is characterized in that the pH value of water solution regulating bromate is 2.8 ~ 12.0 scopes.
4. macromolecular fibre is the Supported Nano Zero-valent Iron PP-g-AA-Fe of carrier according to claim 1
0remove the method for bromate in water, it is characterized in that the starting point concentration of bromate is 0.5mg/L-1.5mg/L.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113664214A (en) * | 2021-08-06 | 2021-11-19 | 浙江双良商达环保有限公司 | Nano zero-valent iron filler, preparation method thereof and application thereof in denitrification |
CN115155525A (en) * | 2022-07-28 | 2022-10-11 | 安徽农业大学 | Iron ion-loaded aminated polypropylene fiber and preparation method and application thereof |
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-
2014
- 2014-10-22 CN CN201410576889.8A patent/CN104445565B/en not_active Expired - Fee Related
Patent Citations (4)
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CN102277742A (en) * | 2011-05-13 | 2011-12-14 | 天津工业大学 | Preparation method of cleaning material of heavy metal ions in reusable water |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113664214A (en) * | 2021-08-06 | 2021-11-19 | 浙江双良商达环保有限公司 | Nano zero-valent iron filler, preparation method thereof and application thereof in denitrification |
CN113664214B (en) * | 2021-08-06 | 2023-09-29 | 浙江双良商达环保有限公司 | Nanometer zero-valent iron filler, preparation method thereof and application thereof in denitrification |
CN115155525A (en) * | 2022-07-28 | 2022-10-11 | 安徽农业大学 | Iron ion-loaded aminated polypropylene fiber and preparation method and application thereof |
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