CN107694612A - It is a kind of to remove material of bromate and its precursor and its preparation method and application in water removal - Google Patents
It is a kind of to remove material of bromate and its precursor and its preparation method and application in water removal Download PDFInfo
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- CN107694612A CN107694612A CN201710792868.3A CN201710792868A CN107694612A CN 107694612 A CN107694612 A CN 107694612A CN 201710792868 A CN201710792868 A CN 201710792868A CN 107694612 A CN107694612 A CN 107694612A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
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Abstract
Material of bromate and its precursor and its preparation method and application in water removal is removed the invention discloses a kind of.This method comprises the following steps：（1）Under nitrogen protection, by resin swelling in FeCl3·6H2In O ethanol water mixed solution, FeCl is added2·4H2O ethanol water mixed solution, lower mixing is stirred, it is then ultrasonic so that Fe3+And Fe2+It is evenly distributed in the macropore of resin；（2）Under nitrogen protection, to step（1）Sodium hydroxide solution is added dropwise in gained mixed liquor after ultrasound, 60 DEG C -65 DEG C reactions are warming up to after stirring reaction；（3）Reaction is cooled to room temperature after terminating, and refilters, and washs, and dries, obtains magnetization resin, i.e., a kind of to remove the material of bromate and its precursor in water removal.Resin after magnetization is applied to go in water removal in bromate and its precursor by the present invention, have the advantages that material can be recycled for a long time, removal efficiency height, separating rate it is fast.
Description
Technical field
The invention belongs to water-treatment technology field, and in particular to it is a kind of go in water removal the material of bromate and its precursor and
Its preparation method and application.
Background technology
With the propulsion of industrialization and urbanization, the discharge of various industrial wastewaters and sanitary sewage, surface pond is caused
Great harm, makes drinking water source water quality deterioration, causes generally existing drinking water source pollution problem in world wide.Water
Drinking water safety problem serious threat the health of people caused by pollution.With the use of ozonization technique, its is right
Drinking water safety also result in negative effect.Drinking water bromate caused by because of ozone advanced treating is studied by international cancer
Mechanism is set to 2B level potential carcinogens, China《Standards for drinking water quality》(GB5749-2006) bromate limit value is defined
For 10 μ g/L.
Control bromate in drinking water content mainly has two kinds of approach at present.The first is bromic acid in control ozonation
The generation of salt.Mainly by reducing pH value, ammonification plus H2O2Etc. reducing the generation of bromate.But these methods need to draw
Enter other materials, cost should be increased, it is also possible to cause secondary pollution or reduce ozonisation effect.Second is to remove water
The bromate of middle generation.The active charcoal Adsorption method of technology of removal bromate, membrane processing method, ferrous ion reduction remove
Method, Zero-valent Iron reduction removal method, bioanalysis, ultraviolet degradation, Pd/Al203Catalytic reduction method, layered double-hydroxide absorption are also
Former method, activated carbon are combined with electrode is reduced into bromate nontoxic bromide ion etc..And the equal Shortcomings of these methods it
Place, such as active carbon adsorption, when natural organic matter and the other ions of high concentration in water be present can reduce activated carbon removes bromic acid
The ability of salt, and fresh activity charcoal to biological activated carbon (BAC) convert when, the clearance to bromate is in reduction trend, to bromine
The removal effect of hydrochlorate is poor etc.；Membrane processing method cost is too high；Fe2+, the removal of zeroth order iron-deoxidize and bioanalysis to bromate
Although efficiency is very high, Fe is all inevitably produced3+、Fe2+And microbial metabolic products, introduce secondary pollution, and nanometer
Zero-valent Iron is easily oxidized in atmosphere, and stability is poor；The power consumption of ultraviolet degradation method is too big；Layered double-hydroxide absorbing and reducing
Method, which is disadvantageous in that, is being converted into alpha-feooh and amorphous aluminum hydroxide, can not realize regeneration；Pd/Al203Catalysis reduction
The deficiency of method is that catalyst is not easily recycled the secondary pollution being likely to cause in water.
More than contrast several methods for removing bromate, novel magnetic anion exchange resin, which removes bromate, has height
Effect, low energy consumption, materials are few, the advantage such as renewable, are tool drinking water advanced treatment technologies with broad prospects for development.
Ion exchange resin is that one kind carries active function group, can pass through the exchangeable ion and medium of institute's band（It is water, organic
Solvent, gas）In the particulate matter that swaps of other ions.The structure of ion exchange resin is made up of three parts：It is insoluble
The three dimensions mesh skeleton of property；Functional group on skeleton in succession；The opposite charges of functional group institute band it is commutative from
Son.In the aqueous solution, it is connected to the function base that anion exchange resin immobilizes on skeleton and dissociates exchangeable anions（Such as
Cl-、OH-）, the latter can move freely and can be diffused into solution interior in a big way.Meanwhile the same charge ion in solution
（Such as Br-、BrO3 -）Also can be diffused into inside whole resin loose structure, the concentration difference between both ions promotes them mutual
It is exchanged, its concentration difference is bigger, and exchange velocity is faster；Again by certain function base of institute's band on ion exchange resin and respectively
The affinity size of kind ion is different, so under conditions of manual control, function base dissociates the exchangeable ion come
Can exchanges with the same charge ion in solution.
Because the skeleton structure of ion exchange resin immobilizes, ion exchange process is a reversible reaction, it by from
The influence of sub- concentration is very big, and resin can be regenerated using this feature, so can be repeatedly used for a long in theory.
However, traditional anion exchange resin is not easy to keep suspending when reacting with raw water under stirring, and settle
Speed is too slow, therefore, conventional resins carried magnetic ferriferous oxide is made it have into magnetic, keeps suspended state during use, due to
Magnetic has aggtegation, resin can be accelerated to settle, and realizes the quick separating of resin and water.The present invention is by resin-carried magnetic ferrite
Compound is used to remove micro bromate and its precursor in water removal, there is provided a kind of new method.
The content of the invention
The present invention be directed to the drawbacks of prior art, there is provided it is a kind of go in water removal the material of bromate and its precursor and its
Preparation method and application.This method has the advantages that material can be recycled for a long time, removal efficiency is high, separating rate is fast.
The present invention is achieved through the following technical solutions.
A kind of preparation method for removing the material of bromate and its precursor in water removal, comprises the following steps：
（1）Under nitrogen protection, by resin swelling in FeCl3· 6H2In O alcohol-water mixed solution, FeCl is added2·
4H2O alcohol-water mixed solution, lower mixing is stirred, it is then ultrasonic so that Fe3+ And Fe2+It is distributed in the macropore of resin equal
It is even；
（2）Under nitrogen protection, to step（1）Sodium hydroxide solution, the h of stirring reaction 1 ~ 2 is added dropwise in gained mixed liquor after ultrasound
After be warming up to 60 ~ 65 DEG C of 2 ~ 3 h of reaction, reaction equation is：2Fe3+ + Fe2+ + 8OH— → Fe3O4 + 4H2O；It is anti-to ensure
Should be abundant, sodium hydroxide solution volume is approximately more than theoretical value.
（3）Reaction is cooled to room temperature after terminating, and refilters, and washs, and dries, and obtains magnetization resin, i.e. one kind removes bromine in water removal
The material of hydrochlorate and its precursor.
Preferably, step（1）The resin is macropore magnetic anion resin, such as Amberlite FPA90Cl resins,
D730 resins, Amberlite IRA958Cl etc., more preferably Amberlite FPA90Cl resins.
Preferably, step（1）The swelling is 4 ~ 5 h of swelling under 30 ~ 40 DEG C of constant temperature water baths.
Preferably, step（1）The FeCl3·6H2The concentration of O alcohol-water mixed solution is 2 ~ 3 mol/L, described
FeCl2·4H2The concentration of O alcohol-water mixed solution is 1 ~ 1.5 mol/L, and wherein the volume ratio of ethanol and water is 1:1~2.
Preferably, step（1）The FeCl3· 6H2O alcohol-water mixed solution and FeCl2·4H2O alcohol-water
The cumulative volume of mixed solution is 8 ~ 10 times of resin volume.
Preferably, step（1）The FeCl2·4H2The volume of O alcohol-water mixed solution is more than FeCl3·6H2O's
The volume of alcohol-water mixed solution is to prevent Fe2+It is oxidized.
Preferably, step（2）The concentration of the sodium hydroxide solution is 10 ~ 12 mol/L；The sodium hydroxide solution exists
Dripped within 30 ~ 50 min.
Preferably, step（2）The dosage of the sodium hydroxide solution is FeCl3· 6H2O alcohol-water mixed solution body
Long-pending 0.8 ~ 1 times.
Preferably, step（3）The washing is that filtrate is washed with distilled water to after product is filtered as neutrality, then with anhydrous
Ethanol washs 2 ~ 3 times.
Preferably, step（3）The drying is that 48 h are dried in 60 DEG C of vacuum drying chambers.
Magnetize resin as made from above-described preparation method, the magnetization resin be applied to go water removal in bromate and its
Precursor.
Compared with prior art, the invention has the advantages that：
1st, the resin after present invention magnetization is applied to go in water removal in bromate and its precursor, and there is material, which can circulate for a long time, makes
It is high with, removal efficiency（>90%）, the advantages that separating rate is fast.
2nd, the resin after present invention magnetization within a short period of time may be used for the bromate of higher concentration under relatively low dosage
To be drawn off to below 10 μ g, meet《Water hygiene standard is applied in life》Requirement.
3rd, the raw material that the present invention needs, cheap and easy to get such as iron chloride, frerrous chloride and sodium hydroxide wide material sources, industry
Upper operating cost is low, can extensive use.
4th, application of the present invention is wider, can effectively be carried out under 15 ~ 55 DEG C of temperature conditionss, and in wider pH value model
Enclose（4~9）Interior reaction can be smoothed out.
5th, it is renewable in salting liquid such as sodium chloride solution after the resin adsorption saturation after present invention magnetization, and regenerate
Resin adsorption efficiency is very high, i.e., power of regeneration is strong, regeneration technology is simple.
6th, the present invention has the advantages of technique is simple, low to operational management requirement.
Brief description of the drawings
Fig. 1 a, Fig. 1 b are the scanning electron microscope (SEM) photograph before the magnetization of FPA90Cl resins in embodiment 1；
Fig. 1 c, Fig. 1 d are the scanning electron microscope (SEM) photograph after the magnetization of FPA90Cl resins in embodiment 1；
In Fig. 2 A, B be respectively in embodiment 1 FPA90Cl resins magnetization before and after FTIR spectrum figure；
Fig. 3 is the effect curve figure of the FPA90Cl resins removal bromate and bromide after magnetizing in embodiment 1；
Fig. 4 is the effect curve figure of the FPA90Cl resins removal bromate and bromide after magnetizing in embodiment 2；
Fig. 5 is the effect curve figure of the FPA90Cl resins removal bromate and bromide after magnetizing in embodiment 3；
Fig. 6 is that the dynamics of the FPA90Cl resins removal bromate after magnetizing in embodiment 1,2,3 is fitted schematic diagram；
Fig. 7 removes the effect curve figure of bromate for the resin after magnetization in embodiment 6 under different initial soln pH.
Embodiment
It is further described below in conjunction with accompanying drawing and specific implementation of the example to the present invention, but embodiments of the present invention
Not limited to this.
Embodiment 1
（1）In N2Under protection, by 20 ml FPA90Cl resin anion (R.A.)s and the mol/L of 100 ml 2 FeCl3· 6H2O second
Alcohol-water mixed solution（The volume ratio of ethanol and water is 1:1）Add in 500 ml three-necked flasks, in 30 DEG C of constant temperature water baths, continue
4 h of the lower swelling of stirring；Then the mol/L of 100 ml 1 FeCl is added2·4H2O alcohol-water mixed solution（Ethanol and water
Volume ratio is 1:1）, 1 h is mixed under continuous stirring；Again by 2 h of gained mixed solution ultrasound so that Fe3+ And Fe2+Setting
It is evenly distributed in the macropore of fat.
（2）In N2To step under protection, lasting stirring and ultrasonic wave added（1）80 ml 10 are added dropwise in gained mixed liquor
Mol/L sodium hydroxide solution, dripped within 30 min, being warming up to 65 DEG C after continuation stirring reaction 1 h continues reaction 2
h。
（3）Reaction is cooled to room temperature after terminating, and filtrate is washed with distilled water to after product is filtered as neutrality, then with anhydrous
Ethanol is washed 3 times, and 48 h, the FPA90Cl resin anion (R.A.)s after must magnetizing are dried in 60 DEG C of vacuum drying chambers.The present embodiment
Scanning electron microscope (SEM) photograph before the magnetization of FPA90Cl resins is as shown in Figure 1 a, 1 b, it can be seen that resin surface is smooth before magnetization, without attached
Thing, duct is clear, cavity；The scanning electron microscope (SEM) photograph of FPA90Cl resins after magnetization is as shown in Fig. 1 c, Fig. 1 d, it can be seen that magnetic
Resin surface rough after change, there is ferriferous oxide attachment, clearly duct loses, and is full of by ferriferous oxide.Magnetize forward and backward resin
Infared spectrum respectively as shown in A, B in Fig. 2, it can be seen that be the absworption peak of Fe-O keys at 465 and 627.
（4）Under normal temperature, 500 ml BrO are added in 1000 ml beakers3 -And Br-Mixed solution, wherein BrO3 -Concentration is
50 μ g/L, Br-Concentration is 200 μ g/L.The FPA90Cl resin anion (R.A.)s added thereto after 0.5000 g magnetization, use magnetic force
Agitator continuously stirs 60 min under 300 rpm, is sampled at different time interval, with chromatography of ions (ICS -900；
Dionex BrO in solution) is determined3 -And Br-Concentration.
In the present embodiment, the pH for testing initial soln is not made adjustments as 6.19；As shown in figure 3, after 30 min of reaction, bromine
Phosphate content is dropped to below 10 μ g/L, reaches GB5749-2006 requirements.Reaction is measured in reaction solution after carrying out 60min
BrO3 -Concentration is 3.40 μ g/L, Br-Concentration is 5.69 μ g/L, and resin is to its clearance close to 95%.
Embodiment 2
（1）In N2Under protection, by 25ml FPA90Cl resin anion (R.A.)s and 3 mol/L FeCl3· 6H2O alcohol-water mixes
Close solution（The volume ratio of ethanol and water is 1:1）Add in 500 ml three-necked flasks, it is molten under 30 DEG C of constant temperature water baths, lasting stirring
Swollen 5 h；Then the mol/L of 100 ml 1.5 FeCl is added2·4H2O alcohol-water mixed solution（The volume ratio of ethanol and water
For 1:1）, 2 h are mixed under continuous stirring；Again by 2 h of gained mixed solution ultrasound so that Fe3+ And Fe2+In the big of resin
It is evenly distributed in hole.
（2）In N2To step under protection, lasting stirring and ultrasonic wave added（1）90 ml 10 are added dropwise in gained mixed liquor
Mol/L sodium hydroxide solution, dripped within 40 min, being warming up to 65 DEG C after continuation stirring reaction 1 h continues reaction 3
h。
（3）Reaction is cooled to room temperature after terminating, and filtrate is washed with distilled water to after product is filtered as neutrality, then with anhydrous
Ethanol is washed 3 times, and 48 h, the FPA90Cl resin anion (R.A.)s after must magnetizing are dried in 60 DEG C of vacuum drying chambers.
（4）Under normal temperature, 500 ml BrO are added in 1000 ml beakers3 -And Br-Mixed solution, wherein BrO3 -Concentration is
100 μ g/L, Br-Concentration is 300 μ g/L.The FPA90Cl resin anion (R.A.)s added thereto after 0.5000 g magnetization, use magnetic
Power agitator continuously stirs 120 min under 300 rpm, is sampled at different time interval, with chromatography of ions (ICS -900；
Dionex BrO in solution) is determined3 -And Br-Concentration.
In the present embodiment, the pH for testing initial soln is not made adjustments as 6.19；As shown in figure 4, after 60 min of reaction, bromine
Phosphate content is dropped to below 10 μ g/L, reaches GB5749-2006 requirements.Reaction is measured in reaction solution after carrying out 120 min
BrO3 -Concentration is 2.47 μ g/L, Br-Concentration is 3.41 μ g/L, and resin is to its clearance close to 95%.
Embodiment 3
（1）In N2Under protection, by 25 ml FPA90Cl resin anion (R.A.)s and the mol/L of 100ml 2 FeCl3· 6H2O second
Alcohol-water mixed solution（The volume ratio of ethanol and water is 1:2）Add in 500 ml three-necked flasks, in 35 DEG C of constant temperature water baths, continue
4 h of the lower swelling of stirring；Then the mol/L of 100 ml 1 FeCl is added2·4H2O alcohol-water mixed solution（Ethanol and water
Volume ratio is 1:2）, 2 h are mixed under continuous stirring；Again by 2 h of gained mixed solution ultrasound so that Fe3+ And Fe2+Setting
It is evenly distributed in the macropore of fat.
（2）In N2To step under protection, lasting stirring and ultrasonic wave added（1）100ml 11 is added dropwise in gained mixed liquor
Mol/L sodium hydroxide solution, dripped within 50 min, being warming up to 60 DEG C after continuation stirring reaction 2 h continues reaction 2
h。
（3）Reaction is cooled to room temperature after terminating, and filtrate is washed with distilled water to after product is filtered as neutrality, then with anhydrous
Ethanol is washed 3 times, and 48 h, the FPA90Cl resin anion (R.A.)s after must magnetizing are dried in 60 DEG C of vacuum drying chambers.
（4）Under normal temperature, 500 ml BrO are added in 1000 ml beakers3 -And Br-Mixed solution, wherein BrO3 -Concentration is
200 μ g/L, Br-Concentration is 400 μ g/L.The FPA90Cl resin anion (R.A.)s added thereto after 0.5000 g magnetization, 300
180 min are continuously stirred under rpm, are sampled at different time interval, with chromatography of ions (ICS -900；Dionex) determine in solution
BrO3 -And Br-Concentration.
In the present embodiment, the pH for testing initial soln is not made adjustments as 6.19；As shown in figure 5, after 80 min of reaction, bromine
Phosphate content is dropped to below 10 μ g/L, reaches GB5749-2006 requirements.Reaction is measured in reaction solution after carrying out 180 min
BrO3 -Concentration is 2.28 μ g/L, Br-Concentration is 3.41 μ g/L, and resin is to its clearance close to 95%.
As shown in fig. 6, under conditions of embodiment 1,2 and 3, the adsorption process of bromate meets plan first _ order kinetics equation.
Embodiment 4
（1）In N2Under protection, by 25 ml FPA90Cl resin anion (R.A.)s and 100 ml3 mol/L FeCl3· 6H2O second
Alcohol-water mixed solution（The volume ratio of ethanol and water is 1:1）Add in 500 ml three-necked flasks, in 40 DEG C of constant temperature water baths, continue
4 h of the lower swelling of stirring；Then the mol/L of 100ml 1.5 FeCl is added2·4H2O alcohol-water mixed solution（Ethanol and water
Volume ratio be 1:1）, 1 h is mixed under continuous stirring；Again by 2 h of gained mixed solution ultrasound so that Fe3+ And Fe2+
It is evenly distributed in the macropore of resin.
（2）In N2To step under protection, lasting stirring and ultrasonic wave added（1）90 ml 12 are added dropwise in gained mixed liquor
Mol/L sodium hydroxide solution, dripped within 40 min, being warming up to 60 DEG C after continuation stirring reaction 2 h continues reaction 3
h。
（3）Reaction is cooled to room temperature after terminating, and filtrate is washed with distilled water to after product is filtered as neutrality, then with anhydrous
Ethanol is washed 3 times, and 48 h, the FPA90Cl resin anion (R.A.)s after must magnetizing are dried in 60 DEG C of vacuum drying chambers.
（4）Respectively at a temperature of 288K, 298K, 308K, 318K and 328K, 500 ml are added in 1000 ml beakers
BrO3 -And Br-Mixed solution, wherein BrO3 -Concentration is 50 μ g/L, Br-Concentration is 100 μ g/L.0.5000 g is added thereto
FPA90Cl resin anion (R.A.)s after magnetization, 60 min are continuously stirred under 300 rpm with magnetic stirring apparatus, between different time
Every sampling, with chromatography of ions (ICS -900；Dionex BrO in solution) is determined3 -And Br-Concentration.
In the present embodiment, the pH for testing initial soln is not made adjustments as 6.19；Reaction is measured in 288K after carrying out 60 min,
BrO in reaction solution at a temperature of 298K, 308K, 318K and 328K3 -Concentration is respectively 4.02,3.40,2.00,<2.00,<2.00
μ g/L, Br-Concentration is 6.68,5.70,3.74,3.08,2.00 μ g/L, and resin is to BrO in large temperature range3 -And Br-Go
Except rate is above 90%, and bromate residual reaches GB5749-2006 requirements.
Embodiment 5
（1）In N2Under protection, by 30 ml FPA90Cl resin anion (R.A.)s and the mol/L of 100ml 3 FeCl3· 6H2O second
Alcohol-water mixed solution（The volume ratio of ethanol and water is 1:1.5）Add in 500 ml three-necked flasks, in 40 DEG C of constant temperature water baths, hold
5 h of the lower swelling of continuous stirring；Then the mol/L of 100ml 1.5 FeCl is added2·4H2O alcohol-water mixed solution（Ethanol with
The volume ratio of water is 1:1.5）, 1 h is mixed under continuous stirring；Again by 2 h of gained mixed solution ultrasound so that Fe3+ With
Fe2+It is evenly distributed in the macropore of resin.
（2）In N2To step under protection, lasting stirring and ultrasonic wave added（1）100 ml are dripped in gained mixed liquor and add 12
Mol/L sodium hydroxide solution, dripped within 50 min, being warming up to 65 DEG C after continuation stirring reaction 2 h continues reaction 3
h。
（3）Reaction is cooled to room temperature after terminating, and filtrate is washed with distilled water to after product is filtered as neutrality, then with anhydrous
Ethanol is washed 3 times, and 48 h, the FPA90Cl resin anion (R.A.)s after must magnetizing are dried in 60 DEG C of vacuum drying chambers.
（4）500 ml BrO are added in 1000 ml beakers3 -And Br-Mixed solution, BrO3 -Concentration is 100 μ g/L, Br-
Concentration is 300 μ g/L.The FPA90Cl resin anion (R.A.)s being separately added into thereto after 0.1,0.2,0.3,0.4 and 0.5g magnetization,
180 min are continuously stirred under 300 rpm with magnetic stirring apparatus, are sampled in different time interval, with chromatography of ions (ICS-
900；Dionex BrO in solution) is determined3 -And Br-Concentration.
In the present embodiment, the pH for testing initial soln is not made adjustments as 6.19；When resin usage amount is 0.5 g, reaction
Reach balance in 120 min, now BrO3 -Concentration is 2.47 μ g/L, Br-Concentration is 3.41 μ g/L；When resin usage amount is
During 0.4 g, react and reach balance in 120 min, now BrO3 -Concentration is 2.24 μ g/L, Br-Concentration is 3.74 μ g/L；Work as tree
When fat usage amount is 0.3g, reacts and reach balance in 150 min, now BrO3 -Concentration is 2.47 μ g/L, Br-Concentration is 3.41
μg/L；When resin usage amount is 0.2g, reacts and reach balance in 180min, now BrO3 -Concentration is 3.87 μ g/L, Br-It is dense
Spend for 5.70 μ g/L；When resin usage amount is 0.1g, reacts and still not up to balanced in 180min, now BrO3 -Concentration is
9.91 μ g/L, Br-Concentration is 17.46 μ g/L；Understand, at higher concentrations, resin is to BrO3 -And Br-Still there is higher go
Except rate, and bromate residual reaches GB5749-2006 requirements.
Embodiment 6
（1）In N2Under protection, by 30 ml FPA90Cl resin anion (R.A.)s and the mol/L of 100 ml 3 FeCl3· 6H2O second
Alcohol-water mixed solution（The volume ratio of ethanol and water is 1:2）Add in 500 ml three-necked flasks, in 40 DEG C of constant temperature water baths, magnetic force
4 h of the lower swelling of stirring；Then the mol/L of 100ml 1.5 FeCl is added2·4H2O alcohol-water mixed solution（Ethanol and water
Volume ratio be 1:2）, 1 h is mixed under continuous stirring；Again by 2 h of gained mixed solution ultrasound so that Fe3+ And Fe2+
It is evenly distributed in the macropore of resin.
（2）In N2To step under protection, lasting stirring and ultrasonic wave added（1）100 ml10 are added dropwise in gained mixed liquor
Mol/L sodium hydroxide solution, dripped within 50 min, being warming up to 65 DEG C after continuation stirring reaction 2 h continues reaction 3
h。
（3）Reaction is cooled to room temperature after terminating, and filtrate is washed with distilled water to after product is filtered as neutrality, then with anhydrous
Ethanol is washed 3 times, and 48 h, the FPA90Cl resin anion (R.A.)s after must magnetizing are dried in 60 DEG C of vacuum drying chambers.
（4）500 ml BrO are added in 1000 ml beakers3 -Solution, BrO3 -Concentration is 200 μ g/L.Using HCl and
NaOH solution, it is 2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0,10.0,11.0 to adjust the initial pH of solution respectively.Thereto
The FPA90Cl resin anion (R.A.)s being separately added into after 0.2 g magnetization, 12 h are continuously stirred extremely with magnetic stirring apparatus under 300 rpm
Adsorption equilibrium, with chromatography of ions (ICS -900；Dionex BrO in solution) is determined3 -Concentration.
As shown in fig. 7, ought (2.0 ~ 11.0) magnetic resin has larger adsorption rate to bromate under pH value in a big way；And
When initial pH value of solution is respectively 4.0,5.0,6.0,7.0,8.0,9.0, BrO when balance3 -Concentration is respectively 7.74 μ g/L,
5.73 μ g/L, 2.78 μ g/L, 5.73 μ g/L, 9.60 μ g/L, 9.91 μ g/L；Reach GB5749-2006 requirements.Especially exist
Close under neutrallty condition, resin is to BrO3 -Clearance highest.
Claims (10)
1. a kind of preparation method for removing the material of bromate and its precursor in water removal, it is characterised in that comprise the following steps：
（1）Under nitrogen protection, by resin swelling in FeCl3· 6H2In O alcohol-water mixed solution, FeCl is added2·
4H2O alcohol-water mixed solution, lower mixing is stirred, it is then ultrasonic so that Fe3+ And Fe2+It is distributed in the macropore of resin equal
It is even；
（2）Under nitrogen protection, to step（1）Sodium hydroxide solution, stirring reaction 1-2 is added dropwise in gained mixed liquor after ultrasound
60-65 DEG C of 2-3 h of reaction are warming up to after h；
（3）Reaction is cooled to room temperature after terminating, and refilters, and washs, and dries, and obtains magnetization resin, i.e. one kind removes bromate in water removal
And its material of precursor.
2. preparation method according to claim 1, it is characterised in that step（1）The resin is Amberlite
One or more in FPA90Cl resins, D730 resins and Amberlite IRA958Cl resins.
3. preparation method according to claim 1, it is characterised in that step（1）The swelling is in 30-40 DEG C of water-baths
4-5 h are swelled under constant temperature.
4. preparation method according to claim 1, it is characterised in that step（1）The FeCl3·6H2O alcohol-water mixes
The concentration for closing solution is 2-3 mol/L, the FeCl2·4H2The concentration of O alcohol-water mixed solution is 1-1.5 mol/L,
Wherein the volume ratio of ethanol and water is 1:1~2.
5. preparation method according to claim 1, it is characterised in that step（1）The FeCl3· 6H2O alcohol-water
Mixed solution and FeCl2·4H2The cumulative volume of O alcohol-water mixed solution is 8-10 times of resin volume.
6. preparation method according to claim 1, it is characterised in that step（1）The FeCl2·4H2O alcohol-water mixes
The volume for closing solution is more than FeCl3·6H2The volume of O alcohol-water mixed solution.
7. preparation method according to claim 1, it is characterised in that step（2）The concentration of the sodium hydroxide solution is 8
~10 mol/L；The sodium hydroxide solution drips within 30 ~ 50 min.
8. preparation method according to claim 1, it is characterised in that step（2）The dosage of the sodium hydroxide solution is
FeCl3· 6H20.8 ~ 1 times of O alcohol-water mixed liquor volume.
9. as a kind of preparation method system for removing the material of bromate and its precursor in water removal described in claim any one of 1-8
The magnetization resin obtained.
10. the magnetization resin described in claim 9 is applied to remove bromate and its precursor in water removal.
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