CN109265613A - A kind of functional polystyrene microballoon and its preparation method and application - Google Patents
A kind of functional polystyrene microballoon and its preparation method and application Download PDFInfo
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- CN109265613A CN109265613A CN201810946457.XA CN201810946457A CN109265613A CN 109265613 A CN109265613 A CN 109265613A CN 201810946457 A CN201810946457 A CN 201810946457A CN 109265613 A CN109265613 A CN 109265613A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/54—Polymerisation initiated by wave energy or particle radiation by X-rays or electrons
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Abstract
The invention belongs to water treatment field, the processing method of a kind of functional polystyrene microballoon and its preparation method and application and the body containing aluminum water is specifically disclosed.The functional polystyrene microballoon is radiated by gamma-radiation and/or electron beam irradiation is prepared, and the functional polystyrene microballoon includes polystyrene microsphere and the polymeric layer obtained by functionalization monomer polymerization for being bonded to the Surfaces of Polystyrene Microparticles, the functionalization monomer is unsaturated acids.When by functional polystyrene microballoon provided by the invention be used for body containing aluminum water be especially the acidic aqueous solution containing aluminium handle when, the functional polystyrene microballoon can not only keep enough stability and improve aluminum ions removal efficiency, but also the recycling of water body may be implemented, such as, when the body containing aluminum water is the nitric acid solution containing aluminium, the recycling of nitric acid may be implemented, reduce total nitrogen discharged, great prospects for commercial application.
Description
Technical field
The invention belongs to water treatment fields, and in particular to a kind of functional polystyrene microballoon and its preparation method and application
And the processing method of the body containing aluminum water.
Background technique
It can be generated in aluminum products process at present and many contain aluminum ions acidic aqueous solution.Research confirms, drinks
It is excessively high with aluminum content in water, it will lead to the early stage aging of people, or even show senile dementia.The research table of the World Health Organization
Bright, for the aluminium that human body per kilogram of body weight allows to take in no more than 1 milligram, China provides that aluminum content must not be higher than 0.2 in drinking water
Mg/litre.Environment water eutrophication caused by the discharge of nitrate anion in aqueous solution simultaneously, has caused the height weight of environmental protection administration
Depending on.Therefore, aluminum ions processing has great importance in acidic aqueous solution.
Aluminum ions method for removing in water body mainly includes enhanced coagulation, activated carbon adsorption, film process etc..Its
In, enhanced coagulation is react with aluminium ion to generate by adding coagulant into water to precipitate, this to achieve the purpose that removal
Although method removal efficiency is preferable, operating process is complicated, is easy to produce secondary pollution.Activated carbon adsorption is to utilize active carbon
Absorption is carried out to reach the aluminum ions purpose of removal to aluminium ion, the process is complicated, and it is costly, and adsorbent material is not easy again
It makes profits use；And the method for film process also has disadvantages mentioned above.In short, being gone using existing method to the aluminium ion in water body
It removes, there are problems that process is complicated, costly and adsorbent material is not easy regeneration, especially adsorbed in highly acid water body
It is a up to problem to be solved that the stability of material is not enough and the removal efficiency of metal ion is not high.In addition, so far, nitre
Aluminum ions reasonable processing has not yet to see relevant report in acid solution.
Summary of the invention
It is bad for resin stability in current strongly acidic solution treatment process and metal ion removal efficiency is not high
Problem, present invention design have synthesized crosslinking with radiation functional resin for aluminum ions in the especially aqueous solution of nitric acid of body containing aluminum water
Efficiently removal.Wherein, the present inventor after further investigation by having found, by crosslinking with radiation technology by unsaturated acids key
Being connected to Surfaces of Polystyrene Microparticles functional polystyrene microballoon obtained has unique microstructure, can be significant
Increase the stability of resin, while improving aluminum ions removal efficiency, so as to complete the present invention.
Specifically, the present invention provides a kind of functional polystyrene microballoons, wherein the functional polystyrene microballoon
It is prepared by gamma-radiation radiation and/or electron beam irradiation, and the functional polystyrene microballoon includes that polystyrene is micro-
Ball and the polymeric layer obtained by functionalization monomer polymerization for being bonded to Surfaces of Polystyrene Microparticles, the functionalization monomer are
Unsaturated acids.
The present invention also provides the preparation methods of the functional polystyrene microballoon, wherein this method includes will be described
Polystyrene microsphere and functionalization monomer carry out gamma-radiation radiation and/or electron beam irradiation in a dispersion medium, so that described
Functionalization monomer polymerization is simultaneously bonded to the Surfaces of Polystyrene Microparticles formation polymeric layer.
The present invention also provides application of the functional polystyrene microballoon in removal body containing aluminum water in aluminium ion.
In addition, this method includes leading to the body containing aluminum water the present invention also provides a kind of processing method of body containing aluminum water
Enter and be filled in the pillar of the functional polystyrene microballoon, aluminium ion therein is removed in a manner of through absorption.
It is water-soluble when being used for functional polystyrene microballoon provided by the invention to be especially body containing aluminum water the acidity containing aluminium
When liquid is handled, which can not only keep enough stability and improve aluminum ions removal effect
Rate, but also the recycling of water body may be implemented can be with for example, when the body containing aluminum water is the aqueous solution of nitric acid containing aluminium
It realizes the recycling of nitric acid, reduces total nitrogen discharged, great prospects for commercial application.
Detailed description of the invention
Exemplary embodiment of the invention is described in more detail in conjunction with the accompanying drawings, it is of the invention above-mentioned and its
Its purpose, feature and advantage will be apparent.
Fig. 1 shows the aluminium ion concentration situation of change in sample after processing of the aqueous solution of nitric acid containing aluminium；
Fig. 2 shows aluminium ion concentration situations of change in eluent in regenerative process；
Fig. 3 absorbs aluminium ion concentration situation of change in water after showing reuse five times；
Aluminium ion concentration situation of change in eluent in regenerative process after Fig. 4 shows reuse five times.
Fig. 5 is infrared (FT-IR) spectrogram of Fourier, wherein the FT-IR spectrogram of resin, b are before a is first time use
The FT-IR spectrogram of resin after last time is reused.
Specific embodiment
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.
Functional polystyrene microballoon provided by the invention is radiated by gamma-radiation and/or electron beam irradiation is prepared,
And the functional polystyrene microballoon include polystyrene microsphere and be bonded to the Surfaces of Polystyrene Microparticles by function
The polymeric layer that monomer polymerization obtains can be changed, the functionalization monomer is unsaturated acids.
According to the present invention, relative to the polystyrene microsphere of 100 parts by weight, the content of the polymeric layer is preferably
1-50 parts by weight, more preferably 5-30 parts by weight enable to the functional polystyrene microballoon to have higher go in this way
Except aluminum ions efficiency.
There is no particular limitation for partial size of the present invention to the polystyrene microsphere, for example, can be 0.2-5 μm, it is more excellent
It is selected as 1-2 μm.
The unsaturated acids is preferably selected from least one of unsaturated phosphoric acid, unsaturated sulfonic acid and unsaturated carboxylic acid.Its
In, the specific example of the unsaturation phosphoric acid includes but is not limited to: vinyl phosphoric acid, acrylic phosphoric acid, vinyl phosphoric acid diformazan
At least one of ester, vinyl phosphoric acid diethylester and acrylic diethyl phosphate.The specific example packet of the unsaturated sulfonic acid
It includes but is not limited to: at least one of vinyl sulfonic acid, methacrylic sulfonic acid and methylpropene sodium sulfonate.The unsaturated carboxylic acid
Preferably acrylic acid and/or methacrylic acid.
A preferred embodiment of the invention, the unsaturated acids be unsaturated phosphoric acid and unsaturated sulfonic acid and/
Or the mixture of unsaturated carboxylic acid, that is, the unsaturated acids is the mixture of unsaturated phosphoric acid and unsaturated sulfonic acid, or for not
It is saturated the mixture of phosphoric acid and unsaturated carboxylic acid, or the mixing for unsaturated phosphoric acid, unsaturated sulfonic acid and unsaturated carboxylic acid
Object, at this point, corresponding functional polystyrene microballoon has higher stability and the aluminum ions efficiency of removal.Further
The weight ratio on ground, total dosage of the dosage and unsaturated sulfonic acid and unsaturated carboxylic acid of the unsaturation phosphoric acid is preferably 1:
(1-6), more preferably 1:(2-4).It should be noted that when the unsaturated acids only contains unsaturated sulfonic acid and unsaturated carboxylic acid
One of when, total dosage of the unsaturated sulfonic acid and unsaturated carboxylic acid refers to the dosage of this contained one；When it is described not
When saturated acid contains unsaturated sulfonic acid and unsaturated carboxylic acid simultaneously, total dosage of the unsaturated sulfonic acid and unsaturated carboxylic acid is not
It is saturated the sum of dosage and the dosage of unsaturated carboxylic acid of sulfonic acid.
The preparation method of above-mentioned functional polystyrene microballoon provided by the invention include by the polystyrene microsphere with
Functionalization monomer carries out gamma-radiation radiation and/or electron beam irradiation in a dispersion medium, so that the functionalization monomer polymerization
And it is bonded to the Surfaces of Polystyrene Microparticles and forms polymeric layer.
The present invention radiates the gamma-radiation and the condition of electron beam irradiation and the type of radiation source do not limit particularly
It is fixed, as long as enabling to the functionalization monomer polymerization and being bonded to the Surfaces of Polystyrene Microparticles formation polymeric layer i.e.
Can, for example, the irradiation dose of gamma-radiation radiation and electron beam irradiation can be each independently 10-200kGy；Irradiation source
Can be60Co and/or electron accelerator.
There is no particular limitation for type of the present invention to the decentralized medium, particularly preferably water.In addition, in order to keep away as far as possible
Exempt from the generation of oxygen inhibition, it is also preferable to include reaction system is led to nitrogen to carry out for the preparation method of the functional polystyrene microballoon
Deoxygenation is sealed later.
The present invention also provides the functional polystyrene microballoon aluminum ions applications in removal body containing aluminum water.
In addition, this method includes leading to the body containing aluminum water the present invention also provides a kind of processing method of body containing aluminum water
Enter and be filled in the pillar of above-mentioned functional polystyrene microballoon, aluminium ion therein is removed in a manner of through absorption.
Method provided by the invention is suitable for handling existing various bodies containing aluminum water, molten including the neutrality containing aluminium
Liquid, acid solution containing aluminium etc., to the acidic aqueous solution (such as aqueous solution of nitric acid containing aluminium) containing aluminium
Reason.When the body containing aluminum water is the aqueous solution of nitric acid containing aluminium, [H therein+] it is preferably 0.1-4mol/L, [Al3+] preferably
0.2-2mol/L。
There is no particular limitation for condition of the present invention to the absorption, as long as can remove the aluminium ion in body containing aluminum water
To desired value is lower than, for example, being directed to [H+] it is 0.1-4mol/L and [Al3+] be 0.1-2mol/L nitric acid solution, stream
Speed can be 40-80mL/min, and the residence time can be 5-30min.In addition, in adsorption process, in order to obtain better effect
The body containing aluminum water is preferably passed through adsorption column from top to down by fruit.
A kind of specific embodiment according to the present invention, the processing method of the body containing aluminum water further include when the functionalization
When polystyrene microsphere reaches saturation absorption, is used acid solution to carry out zeolite regeneration, enable to functional poly in this way
Phenylethylene micro ball is reused, and cost is reduced.Wherein, the acid solution for example can be sulfuric acid solution, hydrochloric acid, nitric acid
Solution etc..
The present invention will be described in detail by way of examples below.
Embodiment 1
(1) preparation of functional polystyrene microballoon:
In 1L round-bottomed flask be added vinyl phosphoric acid (30g), vinyl sulfonic acid (30g), polystyrene microsphere (280g,
Partial size is 0.5-3 μm) and deionized water (500mL), magnetic agitation, lead to nitrogen 20 minutes to remove the oxygen in solution, seals.
Then above-mentioned round-bottomed flask is placed in60100kGy is irradiated under Co irradiation source.Flask is opened after irradiation, mixture fills in bottle
Column is washed with deionized water, spare to remove unreacted monomer and homopolymer.It should prevent from depositing in packing layer when filling column
Stay bubble.
(2) aluminum ions Adsorption in aqueous solution of nitric acid:
Aluminum ions nitric acid waste water ([H will be contained+]=0.1-2mol/L, [Al3+]=0.2-1.0mol/L) from capital with
The flow velocity of 60mL/min, which is passed through in filled column, carries out absorption exchange, residence time 10min.By the water outlet after exchange adsorption according to
It is secondary that be placed in 300 volumes be that (number 1-300, each sample take 3 to be added dropwise to 3mLNaOH solution in the sample cell of 10mL
In (0.2mol/L), discovery, which begins with obvious sediment from No. 82 sample, to be occurred, and is illustrated since No. 82 samples, Al3+Concentration compared with
Greatly, Al (OH) is produced3Precipitating.
For each sample concentration after accurate measurement processing, ICP-AES (inductive coupling is used after samples with water is diluted 500 times
Atomic Emission Spectrometer AES) measure wherein aluminium ion concentration.As a result as shown in Figure 1, it will be seen from figure 1 that No. 50 sample with
It is preceding all to keep lower aluminium ion concentration (lower than 900ppm).
(3) zeolite regeneration of resin is adsorbed:
Use aqueous sulfuric acid ([H+]=5mol/L) resin in filled column is regenerated, specifically, using 500mL
Aqueous sulfuric acid (2-3 times of resin volume), which is passed through in filled column from capital with the flow velocity of 60mL/min, is rinsed resin, punching
Washing out water and being sequentially placed into 300 volumes is to rinse water outlet aluminium ion concentration situation of change such as Fig. 2 institute in the sample cell of 10mL
Show, figure it is seen that aluminium ion concentration variation remains unchanged substantially in the 50th sample in actified solution, shows to elute
Terminate.Then the resin after rinsing through aqueous sulfuric acid is rinsed with deionized water to pH value 5.36, save it in from
It is spare in sub- water.
(4) resin reuses:
Step (2) and step (3) five times are repeated, the variation of aluminium ion concentration in gained absorption water outlet and actified solution water outlet
It is as shown in Figure 3 and Figure 4 respectively.From the result of Fig. 3 and Fig. 4 can be seen that acquired results substantially with first time using the resin into
The result of row processing is consistent, it can be seen that, which has ability of the stable processing containing aluminum ions aqueous solution of nitric acid.This
Outside, the resin before first time use and after last time reuse is made into Fourier's infrared test respectively, it is resulting
FT-IR spectrogram still keeps stable by its structure after being used for multiple times as shown in figure 5, can be seen that resin from the result of Fig. 5,
Substantially there is no variations.
Embodiment 2
(1) preparation of functional polystyrene microballoon:
Vinyl phosphoric acid (10g), vinyl sulfonic acid (30g), acrylic acid (30g), polyphenyl second are added in 1L round-bottomed flask
Alkene microballoon (280g, partial size are 0.5-3 μm) and deionized water (500mL), magnetic agitation, lead to nitrogen 20 minutes to remove in solution
Oxygen, sealing.Then above-mentioned round-bottomed flask is placed in60100kGy is irradiated under Co irradiation source.Flask is opened after irradiation,
Mixture fills column in bottle, is washed with deionized water, spare to remove unreacted monomer and homopolymer.It should prevent when filling column
Only bubble is retained in packing layer.
(2) aluminum ions Adsorption in aqueous solution of nitric acid:
Aluminum ions nitric acid waste water ([H will be contained+]=0.1-2mol/L, [Al3+]=0.2-1.0mol/L) from capital with
The flow velocity of 60mL/min, which is passed through in filled column, carries out absorption exchange, residence time 10min.By the water outlet after exchange adsorption according to
Secondary to be placed in 100 volumes be (number 1-100) in the sample cell of 10mL, and each sample takes 3 to be added dropwise to 3mLNaOH solution
In (0.2mol/L), discovery, which begins with obvious sediment from No. 85 sample, to be occurred, and is illustrated since No. 85 samples, Al3+Concentration compared with
Greatly, Al (OH) is produced3Precipitating.
For each sample concentration after accurate measurement processing, wherein aluminium is measured with ICP-AES after samples with water is diluted 500 times
Ion concentration.The result shows that all keeping lower aluminium ion concentration before No. 55 sample (lower than 900ppm).
(3) zeolite regeneration of resin is adsorbed:
Use aqueous sulfuric acid ([H+]=5mol/L) resin in filled column is regenerated, specifically, using 500mL
Aqueous sulfuric acid (2-3 times of resin volume), which is passed through in filled column from capital with the flow velocity of 60mL/min, is rinsed resin, punching
Washing out water and being sequentially placed into 300 volumes is in the sample cell of 10mL, the results showed that, aluminium ion concentration variation exists in actified solution
It remains unchanged substantially when the 52nd sample, shows that elution terminates.Then by the resin after being rinsed through aqueous sulfuric acid spend from
Sub- water is rinsed to pH value 5.36, is saved it in spare in deionized water.
(4) resin reuses:
Step (2) and step (3) five times are repeated, the variation of aluminium ion concentration in gained absorption water outlet and actified solution water outlet
It is as a result substantially consistent with the result that first time is handled using the resin, it can be seen that, which there is stable processing to contain
The ability of aluminium ion aqueous solution of nitric acid.In addition, by the resin point before first time use and after last time reuse
Do not make Fourier's infrared test, the results showed that, resin still keeps stable by its structure after being used for multiple times, substantially there is no
Variation.
Embodiment 3
(1) preparation of functional polystyrene microballoon:
Vinyl phosphoric acid (20g), vinyl sulfonic acid (20g), acrylic acid (20g), polyphenyl second are added in 1L round-bottomed flask
Alkene microballoon (280g, partial size are 0.5-3 μm) and deionized water (500mL), magnetic agitation, lead to nitrogen 20 minutes to remove in solution
Oxygen, sealing.Then above-mentioned round-bottomed flask is placed in60100kGy is irradiated under Co irradiation source.Flask is opened after irradiation,
Mixture fills column in bottle, is washed with deionized water, spare to remove unreacted monomer and homopolymer.It should prevent when filling column
Only bubble is retained in packing layer.
(2) aluminum ions Adsorption in aqueous solution of nitric acid:
Aluminum ions nitric acid waste water ([H will be contained+]=0.1-2mol/L, [Al3+]=0.2-1.0mol/L) from capital with
The flow velocity of 60mL/min, which is passed through in filled column, carries out absorption exchange, residence time 10min.By the water outlet after exchange adsorption according to
Secondary to be placed in 100 volumes be (number 1-100) in the sample cell of 10mL, and each sample takes 3 to be added dropwise to 3mLNaOH solution
In (0.2mol/L), discovery, which begins with obvious sediment from No. 78 sample, to be occurred, and is illustrated since No. 78 samples, Al3+Concentration compared with
Greatly, Al (OH) is produced3Precipitating.
For each sample concentration after accurate measurement processing, wherein aluminium is measured with ICP-AES after samples with water is diluted 500 times
Ion concentration.The result shows that all keeping lower aluminium ion concentration before No. 46 sample (lower than 900ppm).
(3) zeolite regeneration of resin is adsorbed:
Use aqueous sulfuric acid ([H+]=5mol/L) resin in filled column is regenerated, specifically, using 500mL
Aqueous sulfuric acid (2-3 times of resin volume), which is passed through in filled column from capital with the flow velocity of 60mL/min, is rinsed resin, punching
Washing out water and being sequentially placed into 300 volumes is in the sample cell of 10mL, the results showed that, aluminium ion concentration variation exists in actified solution
It remains unchanged substantially when the 48th sample, shows that elution terminates.Then by the resin after being rinsed through aqueous sulfuric acid spend from
Sub- water is rinsed to pH value 5.36, is saved it in spare in deionized water.
(4) resin reuses:
Step (2) and step (3) five times are repeated, the variation of aluminium ion concentration in gained absorption water outlet and actified solution water outlet
It is as a result substantially consistent with the result that first time is handled using the resin, it can be seen that, which there is stable processing to contain
The ability of aluminium ion aqueous solution of nitric acid.In addition, by the resin point before first time use and after last time reuse
Do not make Fourier's infrared test, the results showed that, resin still keeps stable by its structure after being used for multiple times, substantially there is no
Variation.
Embodiment 4
Prepare according to the method for embodiment 1 functional polystyrene microballoon, aluminum ions Adsorption in aqueous solution of nitric acid,
Adsorb resin zeolite regeneration, unlike, in the preparation process of functional polystyrene microballoon, by irradiation source by60Co is replaced
It is changed to electron beam and radiation resistance is 100kGy.The result shows that being taken during aluminum ions Adsorption from No. 78 sample
3 are added dropwise to 3mL NaOH solution (0.2mol/L), begin with obvious sediment appearance, illustrate since No. 78 samples, Al3+Concentration compared with
Greatly, Al (OH) is produced3Precipitating.In addition, through ICP-AES detect it is found that all kept before No. 47 sample lower aluminium from
Sub- concentration (being lower than 900ppm).
Embodiment 5
Prepare according to the method for embodiment 1 functional polystyrene microballoon, aluminum ions Adsorption in aqueous solution of nitric acid,
The zeolite regeneration of resin is adsorbed, unlike, in the preparation process of functional polystyrene microballoon, vinyl sulfonic acid is used
The vinyl phosphoric acid of identical weight substitutes.The result shows that taking 3 drops from No. 50 sample during aluminum ions Adsorption
It is added 3mL NaOH solution (0.2mol/L), begins with obvious sediment appearance, illustrate since No. 50 samples, Al3+Concentration is larger,
Produce Al (OH)3Precipitating.In addition, detecting through ICP-AES it is found that all keeping lower aluminium ion dense before No. 35 sample
Degree (is lower than 900ppm).
Comparative example 1
Adsorption is carried out to the aluminium ion in aqueous solution of nitric acid according to the method for embodiment 4, adsorbs the elution of resin again
It is raw, unlike, functional polystyrene microballoon is substituted using unmodified polystyrene microsphere.The result shows that aluminium from
During the Adsorption of son, takes 3 to be added dropwise to 3mL NaOH solution (0.2mol/L) from No. 5 sample, begin with obvious sediment
Occur, illustrates since No. 5 samples, Al3+Concentration is larger, produces Al (OH)3Precipitating.In addition, through ICP-AES detection it is found that
Lower aluminium ion concentration was all kept before No. 2 sample (lower than 900ppm).
Comparative example 2
Adsorption is carried out to the aluminium ion in aqueous solution of nitric acid according to the method for embodiment 4, adsorbs the elution of resin again
It is raw, unlike, functional polystyrene microballoon is caused using initiator heat rather than is modified by the way of radiation, specific to walk
It is rapid as follows: vinyl phosphoric acid (60g), polystyrene microsphere (280g, partial size are 0.5-3 μm) being added in 1L round-bottomed flask and goes
Ionized water (500mL) and 50mg azo-bis-isobutyl cyanide, magnetic agitation leads to nitrogen 20 minutes to remove the oxygen in solution, close
Envelope.Above-mentioned round-bottomed flask is then heated to 90 DEG C of reaction 300min.Flask is opened after reaction, mixture fills column in bottle,
It is washed with deionized water, it is spare to remove unreacted monomer and homopolymer, it should prevent from retaining gas in packing layer when filling column
Bubble.The result shows that taking 3 to be added dropwise to 3mL NaOH solution (0.2mol/ from No. 8 sample during aluminum ions Adsorption
L), obvious sediment appearance is begun with, is illustrated since No. 8 samples, Al3+Concentration is larger, produces Al (OH)3Precipitating.In addition, through
ICP-AES detection before No. 3 sample it is found that all kept lower aluminium ion concentration (lower than 900ppm).
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. a kind of functional polystyrene microballoon, which is characterized in that the functional polystyrene microballoon is radiated by gamma-radiation
And/or electron beam irradiation is prepared, and the functional polystyrene microballoon includes polystyrene microsphere and is bonded to institute
The polymeric layer of Surfaces of Polystyrene Microparticles obtained by functionalization monomer polymerization is stated, the functionalization monomer is unsaturated acids.
2. functional polystyrene microballoon according to claim 1, wherein the polyphenyl second relative to 100 parts by weight
Alkene microballoon, the content of the polymeric layer are 1-50 parts by weight.
3. functional polystyrene microballoon according to claim 1, wherein the partial size of the polystyrene microsphere is 0.2-
5μm。
4. functional polystyrene microballoon described in any one of -3 according to claim 1, wherein
The unsaturated acids is selected from least one of unsaturated phosphoric acid, unsaturated sulfonic acid and unsaturated carboxylic acid；
Preferably, the unsaturated acids is the mixture of unsaturated phosphoric acid and unsaturated sulfonic acid and/or unsaturated carboxylic acid；
Preferably, the weight ratio of the dosage and total dosage of the unsaturated sulfonic acid and unsaturated carboxylic acid of the unsaturated phosphoric acid is
1:(1-6)；
Preferably, the unsaturated phosphoric acid is selected from vinyl phosphoric acid, acrylic phosphoric acid, vinyl phosphoric acid dimethyl ester, vinyl phosphorus
At least one of diethyl phthalate and acrylic diethyl phosphate；
Preferably, the unsaturated sulfonic acid in vinyl sulfonic acid, methacrylic sulfonic acid and methylpropene sodium sulfonate at least
It is a kind of；
Preferably, the unsaturated carboxylic acid is acrylic acid and/or methacrylic acid.
5. the preparation method of functional polystyrene microballoon described in any one of claim 1-4, which is characterized in that the party
Method includes that the polystyrene microsphere and functionalization monomer are carried out gamma-radiation radiation and/or electron beam spoke in a dispersion medium
It penetrates, so that the functionalization monomer polymerization and being bonded to the Surfaces of Polystyrene Microparticles and forming polymeric layer.
6. preparation method according to claim 5, wherein the irradiation dose of the gamma-radiation radiation and electron beam irradiation
It is each independently 10-200kGy；Irradiation source is60Co and/or electron accelerator.
7. functional polystyrene microballoon described in any one of claim 1-4 is in removal body containing aluminum water in aluminium ion
Using.
8. a kind of processing method of body containing aluminum water, which is characterized in that this method includes that the body containing aluminum water is passed through filling to have the right
Benefit requires to remove wherein in a manner of through absorption in the pillar of functional polystyrene microballoon described in any one of 1-4
Aluminium ion.
9. processing method according to claim 8, wherein
The body containing aluminum water is the aqueous solution of nitric acid containing aluminium；
Preferably, [H in the aqueous solution of nitric acid containing aluminium+] it is 0.1-4mol/L, [Al3+] it is 0.1-2mol/L.
10. processing method according to claim 8 or claim 9, wherein this method further includes when the functional polystyrene is micro-
When ball reaches saturation absorption, acid solution is used to carry out zeolite regeneration.
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