CN109133315A - The nanometer iron-copper bi-metal composite material and preparation method of bromate in a kind of removal water body - Google Patents
The nanometer iron-copper bi-metal composite material and preparation method of bromate in a kind of removal water body Download PDFInfo
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- CN109133315A CN109133315A CN201811081319.6A CN201811081319A CN109133315A CN 109133315 A CN109133315 A CN 109133315A CN 201811081319 A CN201811081319 A CN 201811081319A CN 109133315 A CN109133315 A CN 109133315A
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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
- 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
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
Abstract
The present invention relates to a kind of nanometer iron-copper bi-metal composite material and preparation method of bromate in removal water body, the material preparation steps are as follows: the chelating resin investment of nitrogenous pyridyl group functional group is contained Fe3+And/or Fe2+Solution, be added dispersing agent after vibrated；Sodium borohydride is added, is placed in constant temperature oscillation case and vibrates after sealing, cleans chelating resin with deoxidation ultrapure water after oscillation, investment is to containing Cu later2+Solution in, after the reaction was completed with cleaning, dry, obtain the nanometer iron-copper bi-metal composite material of bromate in removal water body.Nanometer iron-copper bi-metal composite material of the present invention is simple and easy to get, it is easy to operate, low in cost, can produce in batches, can be recycled after simple process, material is not reunited, metal ion good fixing effect in material, 98% is more than or equal to bromate removal rate in water body, is expected to become a kind of environmentally friendly, efficient, widely used material.
Description
Technical field
The present invention relates to functional composite material field, the nanometer iron-copper bi-metal of bromate in especially a kind of removal water body
Composite material and preparation method.
Background technique
Currently, domestic many Large Water Works carry out disinfection to drinking water using ozonation technology, and when in tap water
When bromide ion concentration is more than 20 μ g/L, water body is easy to generate bromate after the disinfection of ozone depth.International cancer research institution is
Bromate is set to 2B grades of (higher carcinogenic possibility) potential carcinogens, the existing standard in China " standards for drinking water quality "
(GB5749-2006) BrO is provided3-Concentration is no more than 10 μ g/L in water.Once document points out 12 bottles in supermarket's stochastic buying
Dress mineral water is detected, and having two bottles of mineral waters is more than national water standard；2011, State General Administration for Quality Supervision drank the whole nation
Bottle (bucket) the dress drinking water of waters corporation's production carries out spot check of quality, and having 6, to drink waters corporation's bromate concentration obviously exceeded.Water body
The removal scheme of middle bromate is extremely urgent.
Since the existence form of bromate in water body is stablized, it is difficult to be removed by conventional physical filtering method, existing skill
There is scholar to have studied performance (WANG Xiaohong, the ordered mesopore carbon load nanometer zero of bromate in nano zero valence iron removal water body in art
The performance study of bromate in the preparation of valence iron and its removal water body: [Shandong University's master thesis] Shandong: Shandong University
Environmental project, 2014,16-17.), both there is the bromate in water in the ordered mesoporous carbon material of discovery load nano zero valence iron
Reduction process is also accompanied by adsorption process, and wherein reduction accounts for leading.Nano zero valence iron (nZVI) is 1~100nm of partial size
Zero-valent iron particle has the characteristics that large specific surface area, surface can height and good adsorption effects, reactivity.Simultaneously as
The aggregation for reuniting and being formed chain or bigger (micron order) easily occurs when nZVI is used alone, reduces removal effect, therefore need
It is dispersed by mesoporous carbon, however the synthesis technology of mesoporous carbon is complicated, price is high, and program high production cost is wanted
It is big to be generalized to difficulty in universal tap water purifying.
On the other hand, mesoporous carbon is limited to the fixed function of nano zero valence iron, and digestion of metallic ion is easy to appear in use,
It causes metal ion content in water body exceeded, is not only difficult to ensure water body purification effect, also add new " pollutant ".
Summary of the invention
The purpose of the invention is to overcome bromate removal material in existing water body easy to reunite, metal ion in material
The problem of dissolution, provides a kind of nanometer iron-copper bi-metal composite material and preparation method for removing bromate in water body.
Concrete scheme is as follows:
The preparation method of the nanometer iron-copper bi-metal composite material of bromate in a kind of removal water body, comprising the following steps:
Step 1: the chelating resin investment of nitrogenous pyridyl group functional group is contained into Fe3+And/or Fe2+Solution, be added dispersing agent
After vibrated；
Step 2: sodium borohydride solution is added in the solution finished to the oscillation in step 1, constant temperature vibration is placed on after sealing
It swings in case and vibrates, clean chelating resin with deoxidation ultrapure water after oscillation；
Step 3: the chelating resin after cleaning in step 2 is put into containing Cu2+Solution in, use mechanical stirring, reaction
Chelating resin is cleaned with deoxidation ultrapure water after the completion, placement is dried in a vacuum drying oven, obtains bromate in removal water body
Nanometer iron-copper bi-metal composite material.
Further, the chelating resin of nitrogenous pyridyl group functional group described in step 1 is DOWEXTMM4195 or DOWEXTM
At least one of XFS43084 model chelating resin；
Optional, Fe is contained described in step 13+And/or Fe2+Solution configured using deoxidation ultrapure water, ferro element in solution
Concentration be 2~5g/L, acid, which is added, makes the pH value 2~4 of solution；
Optional, the quality of the chelating resin of nitrogenous pyridyl group functional group described in step 1: the quality of the dispersing agent:
It is described to contain Fe3+Solution quality be 1:8~12:400~450；
It is optional, be added after the dispersing agent vibrate 12 at normal temperature~for 24 hours；
Optional, dispersing agent described in step 1 is polyvinylpyrrolidone, preferably polyvinylpyrrolidone PVP-K30.
Further, sodium borohydride solution using the ethanol water of 20~40 weight % is configured to hydroboration in step 2
Sodium solution, the concentration of sodium borohydride is 0.4~0.7mol/L in the sodium borohydride solution, and alkali, which is added, makes pH=14, the boron
The dosage of sodium hydride solution: the quality of the chelating resin of nitrogenous pyridyl group functional group described in step 1 is 300~400:1；
It is optional, it is placed under anaerobic after being sealed in step 2, temperature is 25~35 DEG C, hunting speed is 100~
1.5~2.5h is vibrated in the constant temperature oscillation case of 200rad/min.
Further, Cu is contained described in step 32+Solution in Cu2+Concentration is 0.08~0.15g/L, described to contain Cu2+'s
The quality of solution: the quality of the chelating resin of nitrogenous pyridyl group functional group described in step 1 is 50~150:1, in oxygen free condition
After 0.25~0.75h of lower reaction, chelating resin is cleaned with deoxidation ultrapure water, places drying in 40~60 DEG C of vacuum oven,
Obtain the nanometer iron-copper bi-metal composite material of bromate in removal water body.
The present invention also protects the preparation method of the nanometer iron-copper bi-metal composite material of bromate in the removal water body
The nanometer iron-copper bi-metal composite material being prepared.
The present invention also protects the purposes of the nanometer iron-copper bi-metal composite material, for removing bromate in water body.
Further, the nanometer iron-copper bi-metal composite material is put into tap water, it is 25~35 DEG C that temperature is put into after sealing, vibration
It swings in the constant temperature oscillation case that speed is 100~200rad/min and reacts 3~5h, filter out a nanometer iron-copper bi-metal composite wood later
Material obtains the tap water of removal bromate.
Further, the tap water is passed through nitrogen 5-15 minutes in advance.
Further, the nanometer iron-copper bi-metal composite material is put into tap water, it is 25 that temperature is put into after sealing
~35 DEG C, hunting speed is that it is water-soluble to take out addition hydrochloric acid after reacting 0.5~1h in the constant temperature oscillation case of 100~200rad/min
Liquid adjusts pH to pH=3~8；It puts into constant temperature oscillation case again later, at 25~35 DEG C, hunting speed is 100~
The reaction was continued under the conditions of 200rad/min 2~4.5h uses filtering with microporous membrane later, obtains the tap water of removal bromate.
Further, the nanometer iron-copper bi-metal composite material to fail after using uses acid solution to clean, the H of the acid solution+Concentration is 10~100mmol/L, and once purged nanometer iron-copper bi-metal composite material is big to the removal rate of bromate in water body
In equal to 98%.
The utility model has the advantages that
In the present invention, using the chelating resin of nitrogenous pyridyl group functional group as carrier, have to metal ion very strong
Chelation not only has higher content of metal, and chelation can also be used to the metal ion that may be dissolved out after reaction will
It is fixed, and avoids the problem that metal ion is exceeded, while the chelating resin of nitrogenous pyridyl group functional group is to the bromic acid in water body
Salt also has absorption enrichment, improves the removal effect of bromate.
Moreover in the present invention, the agglomeration traits of Zero-valent Iron are solved using dispersing agent, further, in the second of sodium borohydride
Under the reduction of alcoholic solution, dispersing agent is matched with ethyl alcohol, not only can content of metal be increased, but also is dispersed equal
It is even, partial size is small, composite property stablize.
Finally, the present invention combines Nanoscale Iron and Nanometer Copper, carried nanometer bi-metal can be in original load nanometer zero
In valence iron base, the removal efficiency of bromate is further increased, reactivity and reaction efficiency are substantially increased.Also, water body
After chelating resin base nanometer iron-copper bi-metal composite material prepared by the present invention processing, the part microorganism in water body is lost
Living, ion is changed into stable lower valency from high-valence state, to improve the quality guarantee period of water body.
In short, nanometer iron-copper bi-metal composite material of the present invention it is simple and easy to get, it is easy to operate, low in cost, can be with
Batch production can be recycled after simple process, and material is not reunited, metal ion good fixing effect in material, to water body
Middle bromate removal rate is more than or equal to 98%, is expected to become a kind of environmentally friendly, efficient, widely used material.
Specific embodiment
The definition of part term used in the present invention is given below, other terms that do not address have well known in the art
Definition and meaning:
A variety of open water supplies such as bromate in water body, mineral water and mountain spring water are in pair generated after ozonization
Product mainly exists in the form of an ion, such as BrO3-、BrO-、Br-Deng.
It is nitrogenous in removal water body provided by the invention in the preparation method of the nanometer iron-copper bi-metal composite material of bromate
The chelating resin of pyridyl group functional group is preferably DOWEXTMM4195 or DOWEXTMIn XFS43084 model chelating resin extremely
Few one kind, the resin material of above-mentioned model, which has iron and copper, preferably combines effect.
In the present invention, contain Fe3+And/or Fe2+Solution be containing Fe3+And/or Fe2+Aqueous solution, it is preferable to use deoxidation it is ultrapure
Water configures, and the concentration of ferro element is 2~5g/L, preferably 3~4.5g/L, more preferably 3.5~4g/L, pH value 2 in solution
~4, preferably 2.5~3.It should be noted that in solution ferro element concentration, refer to Fe3+And Fe2+Total amount, calculate when
It is calculated with the relative atomic mass of iron.In the present invention, contain Fe3+And/or Fe2+Solution can be sub- using seven hydrated sulfuric acids
The aqueous solution of the soluble ferric iron salt of the routine such as ferrous solution (positive divalent) or ferric chloride hexahydrate solution (positive trivalent), ferrous salt.
In order to make solution ph 2~4, hydrochloric acid can be added and be adjusted.
In the present invention, the effect of dispersing agent is to reduce the reunion of particle, the especially group in zeroth order particle generating process
Poly- phenomenon, the reagent that can play dispersion zeroth order particle in the prior art can use, preferably polyvinylpyrrolidone, especially
It is polyvinylpyrrolidone PVP-K30, plays good improvement result to the dispersion of particle, mechanism mainly passes through
Dispersant adsorption changes the surface charge distribution of particle, generates electrostatic stabilization effect, steric hindrance effect and electrostatic steric hindrance
Stabilizing effect reaches peptizaiton.
Cooperated in the present invention using polyethylene of dispersing agent pyrrolidones and ethyl alcohol, due to including a large amount of free in ethyl alcohol
Highly polar hydroxyl group, under solution state, these groups are easy to form chelate bonds between metal ion, in addition dispersing agent changes
The distribution of charges of group ion is become, so that highly polar hydroxyl group is closely coated on around metal ion, formation one is limited
The finite structure of shape processed limits the nanoparticle size of synthesis, to achieve the purpose that modified.Therefore polyvinyl pyrrole
The reunion that can both reduce Nanoscale Iron is used in combination with ethyl alcohol for alkanone, can also reduce the particle size of Nanoscale Iron.
In the present invention, the quality of the chelating resin of nitrogenous pyridyl group functional group described in the step 1: the dispersing agent
Quality: described to contain Fe3+And/or Fe2+Solution quality be 1:8~12:400~450；Preferably 1:10:400~430, example
Such as 1:10:430.
In the present invention, the step 2 is using sodium borohydride to the Fe of aqueous solution3+And/or Fe2+It is restored, it is preferred to use
The ethanol water of 20~40 weight % is configured to sodium borohydride solution；Meanwhile ethyl alcohol can be in the preparation process of Nanoscale Iron
Play the role of reducing the partial size of Nanoscale Iron.In the case where not adjusting pH, sodium borohydride needs are ready-to-use, because it can divide
Solution, having macroscopic has hydrogen generation.Boron hydrogen can be made if pH value of solution to be adjusted to 14 (being adjusted using sodium hydroxide solution)
Change sodium solution to stablize, does not adjust pH compared to direct preparation, advantage is disposably to prepare spare, easy to operate, saving program
And it is quantitative more acurrate.Above-mentioned reduction process preferably carries out under oxygen-free environment, and carrying out sealing treatment is to avoid one kind of oxidation
Mode can also protect lower carry out with oxygen-free atmosphere.
In the present invention, contain Cu2+Solution be containing Cu2+Aqueous solution, it is preferable to use deoxidation ultrapure water configuration, in solution
Cu2+Concentration is 0.08~0.15g/L, it should be noted that Cu in solution2+Concentration, calculate when with the relative atom matter of copper
Amount is calculated.For example, Cu can be configured to using copper sulphate2+Concentration is the aqueous solution of 0.1g/L, or using two hydration chlorine
Change copper, is configured to Cu2+Concentration is the aqueous solution of 0.15g/L.
Step 3 reaction of the present invention carries out under anaerobic, and metal is avoided to be oxidized.The present invention first prepares Nanoscale Iron and makes again
Standby Nanometer Copper, utilizes Fe0With Cu2+Reaction obtains Cu0, a small amount of Fe0Become Fe after reaction2+, most of Fe0With Cu0It constitutes and receives together
Rice iron-copper bi-metal composite material.The material can be such that Escherichia coli inactivate, multiple by nanometer iron-copper bi-metal of the present invention
Microorganism is reduced in condensation material treated water body, and ion is reduced into the relatively stabilizing ion of lower valency, to extend water body
Shelf-life.
Nanometer iron-copper bi-metal composite material prepared by the present invention is for removing bromate in water body, using simple vibration
Bromate can significantly be removed by swinging operation, specifically, the nanometer iron-copper bi-metal composite material is put into tap water, sealing
After to be put into temperature be 25~35 DEG C, hunting speed is that 3~5h, later mistake are reacted in the constant temperature oscillation case of 100~200rad/min
Filter a nanometer iron-copper bi-metal composite material, it is preferred to use filtering with microporous membrane filters bromate concentration in gained water sample and meets
Drinking water quality requires " standards for drinking water quality " (GB5749-2006).It is taken out when reacting 0.5~1h and 3~6 drops is added dropwise
Hydrochloric acid solution, adjust pH is reduced the reason is that solution ph can be risen in reaction process using hydrochloric acid solution to pH=3~8
The pH value of solution.Facilitate that the ironing surface oxide layer of nanometer is prevented to be formed in acid condition, while a part of hydrogen ion quilt
The hydrogen that nZVI reduction generates can maintain to react required anaerobic environment and promote reduction.
Before to water treatment, nitrogen is passed through 5~15 minutes to tap water in advance, removes the dissolved oxygen in water removal, it can be with
The removal effect to bromate is further promoted, the reason is that the dissolved oxygen in water can consume the nanometer iron-copper bi-metal composite wood
Material, makes latter portion be oxidized and fail.
Nanometer iron-copper bi-metal composite material prepared by the present invention may be reused, the nanometer gone out by simple filtration
It can be used repeatedly for iron-copper bi-metal composite material, and when material inactive, regeneration method is cleaned using acid solution
Restore reactivity, once purged nanometer iron-copper bi-metal composite material is more than or equal to the removal rate of bromate in water body
98%.
Keep the mode of reaction system anaerobic can be to pass through inert gas into reaction system, for example, nitrogen in the present invention
At least one of gas and periodic table of elements group 0 element gas can know this those skilled in the art, not make herein
It repeats.
Oscillation, constant temperature, cleaning, filtering involved in nanometer iron-copper bi-metal composite material and preparation method thereof provided by the invention
And other implementations can be same as the prior art, this those skilled in the art can be known, therefore not to repeat here.
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.It is real
It applies and particular technique or condition person is not specified in example, according to the literature in the art described technology or conditions or according to product
Specification carries out.Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.Under
In the embodiment in face, such as it is not known and illustrates, " % " refers both to weight percent.
Test method used below includes:
Bromate content detection in water body: the chromatography of ions selects Switzerland ten thousand to lead to 883 type chromatographs, chromatographic column
5150 anion chromatographic column of Metrosep ASUPP, eluent 3.2mmol/L Na2CO3: 1mmol/L NaHCO3,0.7mL/
Min flow velocity, 27 degree of column temperatures, 20uL sampling volume.
Embodiment 1
The nanometer iron-copper bi-metal composite material of bromate in preparation removal water body, steps are as follows:
Step 1: by the chelating resin DOWEX of nitrogenous pyridyl group functional groupTMM4195 investment contains Fe3+Solution, Fe3+It is dense
Degree be 3g/L, pH value 3, be added PVP-K30, at normal temperature vibrate 12~for 24 hours, the chelating resin of nitrogenous pyridyl group functional group,
PVP-K30 with contain Fe3+Solution mass ratio be 1:10:425；
Step 2: sodium borohydride is added in the solution finished to the oscillation in step 1, constant temperature oscillation case is placed on after sealing
Middle oscillation, sodium borohydride by 20~40 weight % ethanol water (ethyl alcohol account for ethanol water gross weight 20~40%) configuration, it is dense
Degree is 0.5mol/L, and the ethanol water pH=14 that sodium hydroxide adjusts sodium borohydride is added, and the reaction time is 1.5~2.5h,
Whole process need to carry out under anaerobic.The chelating resin of nitrogenous pyridyl group functional group and the mass ratio of sodium borohydride solution are
1:350 cleans chelating resin with deoxidation ultrapure water after oscillation；
Step 3: the chelating resin after cleaning in step 2 is put into containing Cu2+Solution in, contain Cu2+Solution matter
Amount: the quality of the chelating resin of nitrogenous pyridyl group functional group described in step 1 is 80:1, contains Cu2+The concentration of solution is 0.15g/
L, reaction time are 0.25~0.75h, and using mechanical stirring, whole process need to carry out under anaerobic, use after the reaction was completed
It deoxygenates ultrapure water and cleans chelating resin, place dry in 40-60 DEG C of vacuum oven, obtain receiving for bromate in removal water body
Rice iron-copper bi-metal composite material.
Embodiment 2
The nanometer iron-copper bi-metal composite material of bromate in preparation removal water body, steps are as follows:
Step 1: by the chelating resin DOWEX of nitrogenous pyridyl group functional groupTMM4195 investment contains Fe2+Solution, Fe2+It is dense
Degree be 2.5g/L, pH value 2, be added PVP-K30, at normal temperature vibrate 12~for 24 hours, the chelating tree of nitrogenous pyridyl group functional group
Rouge, PVP-K30 with contain Fe3+Solution mass ratio be 1:10:415；
Step 2: sodium borohydride is added in the solution finished to the oscillation in step 1, constant temperature oscillation case is placed on after sealing
Middle oscillation, sodium borohydride are configured by the ethanol water of 20~40 weight %, and concentration 0.6mol/L is added sodium hydroxide and adjusts boron hydrogen
Change the ethanol water pH=14 of sodium, the reaction time is 1.5~2.5h, and whole process need to carry out under anaerobic.Nitrogenous pyrrole
The chelating resin of piperidinyl functional group and the mass ratio of sodium borohydride solution are 1:325, are cleaned after oscillation with deoxidation ultrapure water
Chelating resin；
Step 3: the chelating resin after cleaning in step 2 is put into containing Cu2+Solution in, contain Cu2+Solution matter
Amount: the quality of the chelating resin of nitrogenous pyridyl group functional group described in step 1 is 110:1, contains Cu2+The concentration of solution is 0.1g/
L, reaction time are 0.25~0.75h, and using mechanical stirring, whole process need to carry out under anaerobic, use after the reaction was completed
It deoxygenates ultrapure water and cleans chelating resin, place dry in 40-60 DEG C of vacuum oven, obtain receiving for bromate in removal water body
Rice iron-copper bi-metal composite material.
Embodiment 3
The nanometer iron-copper bi-metal composite material of bromate in preparation removal water body, steps are as follows:
Step 1: by the chelating resin DOWEX of nitrogenous pyridyl group functional groupTMXFS43084 investment contains Fe3+And Fe2+It is molten
Liquid, ferro element concentration be 5g/L, pH value 4, be added PVP-K30, at normal temperature vibrate 12~for 24 hours, nitrogenous pyridyl group functional group
Chelating resin, PVP-K30 with contain Fe3+Solution mass ratio be 1:10:440；
Step 2: sodium borohydride is added in the solution finished to the oscillation in step 1, constant temperature oscillation case is placed on after sealing
Middle oscillation, sodium borohydride are configured by the ethanol water of 20~40 weight %, and concentration 0.7mol/L is added sodium hydroxide and adjusts boron hydrogen
Change the ethanol water pH=14 of sodium, the reaction time is 1.5~2.5h, and whole process need to carry out under anaerobic.Nitrogenous pyrrole
The chelating resin of piperidinyl functional group and the mass ratio of sodium borohydride solution are 1:400, are cleaned after oscillation with deoxidation ultrapure water
Chelating resin；
Step 3: the chelating resin after cleaning in step 2 is put into containing Cu2+Solution in, contain Cu2+Solution matter
Amount: the quality of the chelating resin of nitrogenous pyridyl group functional group described in step 1 is 50:1, contains Cu2+The concentration of solution is 0.15g/
L, reaction time are 0.25~0.75h, and using mechanical stirring, whole process need to carry out under anaerobic, use after the reaction was completed
It deoxygenates ultrapure water and cleans chelating resin, place dry in 40-60 DEG C of vacuum oven, obtain receiving for bromate in removal water body
Rice iron-copper bi-metal composite material.
Embodiment 4
The nanometer iron-copper bi-metal composite material of bromate in preparation removal water body, steps are as follows:
Step 1: by the chelating resin DOWEX of nitrogenous pyridyl group functional groupTMXFS43084 investment contains Fe2+Solution, Fe2+
Concentration is 2g/L, pH value 2, and PVP-K30 is added, vibrate 12 at normal temperature~for 24 hours, the chelating tree of nitrogenous pyridyl group functional group
Rouge, PVP-K30 with contain Fe3+Solution mass ratio be 1:10:400；
Step 2: sodium borohydride is added in the solution finished to the oscillation in step 1, constant temperature oscillation case is placed on after sealing
Middle oscillation, sodium borohydride are configured by the ethanol water of 20~40 weight %, and concentration 0.4mol/L is added sodium hydroxide and adjusts boron hydrogen
Change the ethanol water pH=14 of sodium, the reaction time is 1.5~2.5h, and whole process need to carry out under anaerobic.Nitrogenous pyrrole
The chelating resin of piperidinyl functional group and the mass ratio of sodium borohydride solution are 1:300, are cleaned after oscillation with deoxidation ultrapure water
Chelating resin；
Step 3: the chelating resin after cleaning in step 2 is put into containing Cu2+Solution in, contain Cu2+Solution matter
Amount: the quality of the chelating resin of nitrogenous pyridyl group functional group described in step 1 is 150:1, contains Cu2+The concentration of solution is 0.08g/
L, reaction time are 0.25~0.75h, and using mechanical stirring, whole process need to carry out under anaerobic, use after the reaction was completed
It deoxygenates ultrapure water and cleans chelating resin, place dry in 40-60 DEG C of vacuum oven, obtain receiving for bromate in removal water body
Rice iron-copper bi-metal composite material.
Embodiment 5
The nanometer iron-copper bi-metal composite material of bromate in preparation removal water body, steps are as follows:
Step 1: by the chelating resin DOWEX of nitrogenous pyridyl group functional groupTMM4195 investment contains Fe3+Solution, Fe3+It is dense
Degree be 5g/L, pH value 4, be added PVP-K30, at normal temperature vibrate 12~for 24 hours, the chelating resin of nitrogenous pyridyl group functional group,
PVP-K30 with contain Fe3+Solution mass ratio be 1:10:450；
Step 2: sodium borohydride is added in the solution finished to the oscillation in step 1, constant temperature oscillation case is placed on after sealing
Middle oscillation, sodium borohydride are configured by the ethanol water of 20~40 weight %, and concentration 0.7mol/L is added sodium hydroxide and adjusts boron hydrogen
Change the ethanol water pH=14 of sodium, the reaction time is 1.5~2.5h, and whole process need to carry out under anaerobic.Nitrogenous pyrrole
The chelating resin of piperidinyl functional group and the mass ratio of sodium borohydride solution are 1:400, are cleaned after oscillation with deoxidation ultrapure water
Chelating resin；
Step 3: the chelating resin after cleaning in step 2 is put into containing Cu2+Solution in, contain Cu2+Solution matter
Amount: the quality of the chelating resin of nitrogenous pyridyl group functional group described in step 1 is 110:1, contains Cu2+The concentration of solution is 0.15g/
L, reaction time are 0.25~0.75h, and using mechanical stirring, whole process need to carry out under anaerobic, use after the reaction was completed
It deoxygenates ultrapure water and cleans chelating resin, place dry in 40-60 DEG C of vacuum oven, obtain receiving for bromate in removal water body
Rice iron-copper bi-metal composite material.
Embodiment 6
Nanometer iron-copper bi-metal composite material prepared by embodiment 1 is used to handle Xiamen City, Fujian Province Jimei District tap water
Sample, through detecting, bromate ion is 0.77mg/L in untreated water sample, and " standards for drinking water quality " that China is existing
(GB5749-2006) BrO is provided3-Concentration is no more than 10 μ g/L in water, it is seen that BrO in untreated water sample3-Content is above standard
77 times, bromate in tap water is removed very necessary.
Processing method is as follows: taking the above-mentioned water sample of 250mL to 250mL conical flask, is passed through 10 minutes nitrogen, throws into reactor
The nanometer iron-copper bi-metal composite material for adding 1.1g embodiment 1 to prepare, and seal, it is put into shaking table and is vibrated with 150r/min, it will be warm
Degree is set as 30 DEG C, samples after reacting 4h, takes out in reaction process in 0.5~1h, and aqueous hydrochloric acid solution is added and adjusts pH value of solution
It is 4.It is stored in ion chromatography pipe after sampling by 0.22 μm of filtering with microporous membrane, by ion chromatograph test sample
The content of anion to be measured.The result shows that after processing, BrO in water sample3-Concentration is 0.001mg/L, bromate ion removal rate
It can reach 99.87%.
Acid solution is used to clean in the nanometer iron-copper bi-metal composite material to fail after using, the H of acid solution+Concentration be 10~
100mmol/L, once purged nanometer iron-copper bi-metal composite material are more than or equal to 98% to the removal rate of bromate in water body.
Embodiment 7
Nanometer iron-copper bi-metal composite material prepared by embodiment 2 is used to handle Xiamen City, Fujian Province Jimei District tap water
Sample, through detecting, bromate ion is 0.77mg/L in untreated water sample, and " standards for drinking water quality " that China is existing
(GB5749-2006) BrO is provided3-Concentration is no more than 10 μ g/L in water, it is seen that BrO in untreated water sample3-Content is above standard
77 times, bromate in tap water is removed very necessary.
Processing method is as follows: taking the above-mentioned water sample of 250mL to 250mL conical flask, is passed through 5 minutes nitrogen, throws into reactor
The nanometer iron-copper bi-metal composite material for adding 1.1g embodiment 1 to prepare, and seal, it is put into shaking table and is vibrated with 100r/min, it will be warm
Degree is set as 35 DEG C, samples after reacting 3h, takes out in reaction process in 0.5~1h, and aqueous hydrochloric acid solution is added and adjusts pH value of solution
It is 3.It is stored in ion chromatography pipe after sampling by 0.22 μm of filtering with microporous membrane, by ion chromatograph test sample
The content of anion to be measured.The result shows that after processing, BrO in water sample3-Concentration is 0.002mg/L, bromate ion removal rate
It can reach 99.74%.
Embodiment 8
Nanometer iron-copper bi-metal composite material prepared by embodiment 3 is used to handle Xiamen City, Fujian Province Jimei District tap water
Sample, through detecting, bromate ion is 0.77mg/L in untreated water sample, and " standards for drinking water quality " that China is existing
(GB5749-2006) BrO is provided3-Concentration is no more than 10 μ g/L in water, it is seen that BrO in untreated water sample3-Content is above standard
77 times, bromate in tap water is removed very necessary.
Processing method is as follows: taking the above-mentioned water sample of 250mL to 250mL conical flask, is passed through 15 minutes nitrogen, throws into reactor
The nanometer iron-copper bi-metal composite material for adding 1.1g embodiment 1 to prepare, and seal, it is put into shaking table and is vibrated with 200r/min, it will be warm
Degree is set as 25 DEG C, samples after reacting 5h, takes out in reaction process in 0.5~1h, and aqueous hydrochloric acid solution is added and adjusts pH value of solution
It is 8.It is stored in ion chromatography pipe after sampling by 0.22 μm of filtering with microporous membrane, by ion chromatograph test sample
The content of anion to be measured.The result shows that after processing, BrO in water sample3-Concentration is 0.002mg/L, bromate ion removal rate
It can reach 99.74%.
Comparative example 1
Resin-base nano iron material is prepared, steps are as follows:
Step 1: by the chelating resin DOWEX of nitrogenous pyridyl group functional groupTMM4195 investment contains Fe3+Solution, Fe3+It is dense
Degree is 2g/L, and pH value 2 is added PVP-K30, vibrates at normal temperature for 24 hours, chelating resin, the PVP- of nitrogenous pyridyl group functional group
K30 with contain Fe3+Solution mass ratio be 1:10:400；
Step 2: sodium borohydride is added in the solution finished to the oscillation in step 1, constant temperature oscillation case is placed on after sealing
Middle oscillation, sodium borohydride solution are configured by the ethanol water of 20 weight %, and concentration 0.4mol/L is added sodium hydroxide and adjusts boron hydrogen
Change the ethanol water pH=14 of sodium, reaction time 1.5h, whole process need to carry out under anaerobic.Nitrogenous pyridyl group official
The mass ratio of the chelating resin and sodium borohydride solution that can roll into a ball is 1:300, cleans chelating tree with deoxidation ultrapure water after oscillation
Rouge places drying in 40 DEG C of vacuum oven, obtains resin-base nano iron material.
Xiamen City, Fujian Province Jimei District originally water sample is handled with prepared resin-base nano iron material, through detecting, not
Handling bromate ion in water sample is 0.77mg/L, and processing method is as follows: taking the above-mentioned water sample of 250mL to 250mL conical flask, is passed through
10 minutes nitrogen adds the resin-base nano iron material of the preparation of 1.1g comparative example 1 into reactor, and seals, be put into shaking table with
Temperature is set as 35 DEG C, samples after reacting 1h, take out in reaction process in 1h, it is water-soluble that hydrochloric acid is added by 150r/min oscillation
It is 4 that liquid, which adjusts pH value of solution,.It is stored in ion chromatography pipe after sampling by 0.22 μm of filtering with microporous membrane, passes through ion chromatography
The content of anion to be measured in instrument test sample.The result shows that after processing, BrO in water sample3-Concentration is 0.059mg/L, bromic acid
Radical ion removal rate can reach 92.3%.The removal that bromate obtains in water sample after processing, but still it is unsatisfactory for existing " life
Sanitary standard for drinking water " (GB5749-2006) regulation BrO3-Concentration is no more than the requirement of 10 μ g/L in water.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. the preparation method of the nanometer iron-copper bi-metal composite material of bromate in a kind of removal water body, it is characterised in that: including
Following steps:
Step 1: the chelating resin investment of nitrogenous pyridyl group functional group is contained into Fe3+And/or Fe2+Solution, be added dispersing agent it is laggard
Row oscillation；
Step 2: sodium borohydride solution is added in the solution finished to the oscillation in step 1, constant temperature oscillation case is placed on after sealing
Middle oscillation cleans chelating resin with deoxidation ultrapure water after oscillation；
Step 3: the chelating resin after cleaning in step 2 is put into containing Cu2+Solution in, use mechanical stirring, reaction complete
Chelating resin is cleaned with deoxidation ultrapure water afterwards, placement is dried in a vacuum drying oven, obtains the nanometer of bromate in removal water body
Iron-copper bi-metal composite material.
2. the preparation method of the nanometer iron-copper bi-metal composite material of bromate in removal water body according to claim 1,
It is characterized by: the chelating resin of nitrogenous pyridyl group functional group described in step 1 is DOWEXTMM4195 or
DOWEXTMAt least one of XFS43084 model chelating resin；
Optional, Fe is contained described in step 13+And/or Fe2+Solution configured using deoxidation ultrapure water, ferro element is dense in solution
Degree is 2~5g/L, and acid, which is added, makes the pH value 2~4 of solution；
Optional, the quality of the chelating resin of nitrogenous pyridyl group functional group described in step 1: the quality of the dispersing agent: described
Containing Fe3+Solution quality be 1:8~12:400~450；
It is optional, be added after the dispersing agent vibrate 12 at normal temperature~for 24 hours；
Optional, dispersing agent described in step 1 is polyvinylpyrrolidone, preferably polyvinylpyrrolidone PVP-K30.
3. the preparation method of the nanometer iron-copper bi-metal composite material of bromate in removal water body according to claim 1,
It is characterized by: sodium borohydride solution using the ethanol water of 20~40 weight % is configured to sodium borohydride solution in step 2,
The concentration of sodium borohydride is 0.4~0.7mol/L in the sodium borohydride solution, and alkali, which is added, makes pH=14, and the sodium borohydride is molten
The dosage of liquid: the quality of the chelating resin of nitrogenous pyridyl group functional group described in step 1 is 300~400:1；
It is optional, it is placed under anaerobic after being sealed in step 2, temperature is 25~35 DEG C, hunting speed is 100~
1.5~2.5h is vibrated in the constant temperature oscillation case of 200rad/min.
4. the nanometer iron-copper bi-metal composite material of bromate in removal water body according to any one of claim 1-3
Preparation method, it is characterised in that: contain Cu described in step 32+Solution in Cu2+Concentration is 0.08~0.15g/L, described to contain Cu2+
Solution quality: the quality of the chelating resin of nitrogenous pyridyl group functional group described in step 1 be 50~150:1, in anaerobic item
After reacting 0.25~0.75h under part, chelating resin is cleaned with deoxidation ultrapure water, places in 40~60 DEG C of vacuum oven and does
It is dry, obtain the nanometer iron-copper bi-metal composite material of bromate in removal water body.
5. the preparation of the nanometer iron-copper bi-metal composite material of bromate in removal water body of any of claims 1-4
The nanometer iron-copper bi-metal composite material that method is prepared.
6. the purposes of nanometer iron-copper bi-metal composite material described in claim 5, for removing bromate in water body.
7. the purposes of according to claim 6 nanometer of iron-copper bi-metal composite material, it is characterised in that: by the Nanoscale Iron
Copper bi-metal composite material is put into tap water, and it is 25~35 DEG C that temperature is put into after sealing, and hunting speed is 100~200rad/
3~5h is reacted in the constant temperature oscillation case of min, filters out a nanometer iron-copper bi-metal composite material later, obtains removal bromate
Tap water.
8. the purposes of according to claim 7 nanometer of iron-copper bi-metal composite material, it is characterised in that: the tap water is pre-
First it is passed through nitrogen 5~15 minutes.
9. the purposes of according to claim 7 nanometer of iron-copper bi-metal composite material, it is characterised in that: by the Nanoscale Iron
Copper bi-metal composite material is put into tap water, and it is 25~35 DEG C that temperature is put into after sealing, and hunting speed is 100~200rad/
It after reacting 0.5~1h in the constant temperature oscillation case of min, takes out and aqueous hydrochloric acid solution is added, adjust pH to pH=3~8；It throws again later
Enter in constant temperature oscillation case, at 25~35 DEG C, the reaction was continued under the conditions of hunting speed is 100~200rad/min 2~4.5h, later
With filtering with microporous membrane, the tap water of removal bromate is obtained.
10. the purposes of nanometer iron-copper bi-metal composite material according to any one of claim 6-9, it is characterised in that:
The nanometer iron-copper bi-metal composite material to fail after using uses acid solution to clean, the H of the acid solution+Concentration be 10~
100mmol/L, once purged nanometer iron-copper bi-metal composite material are more than or equal to 98% to the removal rate of bromate in water body.
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