CN110170311A - Adsorbent material based on modified sodium alginate microballoon and preparation method thereof and its application - Google Patents
Adsorbent material based on modified sodium alginate microballoon and preparation method thereof and its application Download PDFInfo
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- CN110170311A CN110170311A CN201910393311.1A CN201910393311A CN110170311A CN 110170311 A CN110170311 A CN 110170311A CN 201910393311 A CN201910393311 A CN 201910393311A CN 110170311 A CN110170311 A CN 110170311A
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- sodium alginate
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- adsorbent material
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- toluene
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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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of adsorbent material based on modified sodium alginate microballoon and preparation method thereof and its applications, and sodium alginate and polyvinyl alcohol are dissolved in deionized water, is then added dropwise in the boric acid solution of calcium chloride and forms gelled pill；Gel ball is cleaned, is added in the aqueous solution of silane coupling agent and reacts；It disperses the product after reaction in toluene, the reaction of 1,3- propane sultone is added；After reaction, the adsorbent material of modified sodium alginate microballoon successively is obtained with toluene, ethyl alcohol, deionized water elution, drying.Not only preparation process is simple, at low cost for the adsorbent material of modified sodium alginate microballoon provided by the invention, but also stable structure, has good absorption property to caesium and performance is recycled, can be widely applied to salt lake bittern and terrestrial heat resources comprehensive development and utilization.
Description
Technical field
The invention belongs to field of new materials, and in particular to a kind of adsorbent material based on sulfonic group modified sodium alginate micro ball
And preparation method thereof and its application.
Background technique
Caesium is a kind of important rare alkaline metal, and caesium and its compound are widely used in aerospace, electronic device, life
The modern technologies fields such as object medicine.The main source of caesium has two classes, first is that the Solid Mineral based on lepidolite, pollucite etc.,
Second is that the liquid caesium resource based on salt lake bittern, GEOTHERMAL WATER, subsurface brine.Due to the complexity and money of Solid Mineral exploitation
Sight has gradually been turned to the liquid mineral products that rich reserves, extraction process are simple, at low cost by the finiteness in source, people.From salt lake
Separation and Extraction caesium resource in brine, can not only promote the comprehensive development and utilization of salt lake bittern, but also be advantageously implemented economic society
The sustainable development of meeting.
Currently, the method for extracting caesium from aqueous solution mainly has the precipitation method, solvent extraction and absorption method etc..The precipitation method are more
In separation and earlier industry production for radioactive element in fission product, and this method is utilized to divide directly from salt lake bittern
Seldom from the research for extracting caesium, caesium content is lower in mainly salt lake bittern of tracing it to its cause and the serious interference of coexisting ion.
The extractant of solvent extraction mainly has phenol alcohol reagent, crown ether, dipicrylamine and its derivative etc., but due to organic reagent
Using for the seriously polluted of environment, rarely has industrial application report in recent years.In contrast, absorption method is at low cost with its, operates
Simply, the advantages that processing speed is fast, high-efficient, without secondary pollution and by extensive concern, it has also become mention caesium from brine and relatively answer
With one of the method for prospect.
Currently, being directed to the absorption of caesium, studying more adsorbent mainly has ammonium phosphomolybdate, ferrocyanide etc..Organic suction
Attached dose of report is less.Since ammonium phosphomolybdate and ferrocyanide have microstructure, causes to be granulated difficulty, bad mechanical strength, follow
Ring service performance is poor, it is difficult to realize extensive pillar operation.Therefore, Chinese patent CN101518727A discloses one kind and has
Machine-inorganic composite materials, i.e., calcium alginate embedded ammonium phosphomolybdate compound adsorbent, the compound adsorbent change to a certain extent
The mechanical strength of ammonium phosphomolybdate adsorbent has been apt to it, and there is preferable absorption property to caesium, has can be applied to various solution systems
Middle adsorbing separation cesium ion.Nevertheless, still the pore-size of calcium alginate microsphere network is larger, so as to cause ammonium phosphomolybdate
Leakage, influences adsorption effect and reuse rate is not high, without fundamentally solving the problems, such as the granulation of ammonium phosphomolybdate, so that its work
Industry application prospect is undesirable.Therefore, the cesium ion absorption that adsorption efficiency is high, can be recycled, operates suitable for pillar is prepared
Agent is still a urgent problem to be solved.
Summary of the invention
The present invention provides a kind of adsorbent material and preparation method thereof based on modified sodium alginate microballoon, and the adsorbent material is steady
It is qualitative good, to rare and scatter element caesium in salt lake bittern have good adsorption capacity, and preparation process it is simple, it is at low cost, can follow
Ring regeneration uses.
The purpose of the present invention is to provide a kind of adsorbent material based on modified sodium alginate microballoon, the adsorbent material is preferable
Ground solves the problems, such as traditional cesium ion adsorbent bad mechanical strength, is granulated difficult and is difficult to recycle and/or defect, has
Good higher value application prospect.
The object of the invention is also to provide a kind of preparation methods of the adsorbent material of novel cesium ion adsorbent.
A kind of adsorbent material and preparation method thereof based on modified sodium alginate microballoon of the invention, comprising the following steps:
(1) sodium alginate and polyvinyl alcohol are dissolved in deionized water, are then added dropwise to the boric acid solution of calcium chloride
Middle formation gelled pill；
(2) it is added in the aqueous solution of silane coupling agent after at room temperature cleaning gelled pill, it is stirred to react 12~for 24 hours；
(3) it disperses above-mentioned product in toluene, addition 1,3- propane sultone reaction 12~for 24 hours；
(4) after reaction, modified sodium alginate microballoon successively is obtained with toluene, ethyl alcohol, deionized water elution, drying
Adsorbent material.
Moreover, the weight ratio of sodium alginate and polyvinyl alcohol is 1:10~1:1.
Moreover, the silane coupling agent is KH-550, KH-560, A151, one or more of A171's is mixed
Close object.
Moreover, the mass concentration of calcium chloride is 1~10% in the boric acid solution of the calcium chloride, the mass concentration of boric acid
It is 1~5%.
Moreover, the mass concentration of the aqueous solution of silane coupling agent is 0.5%~10%, silane coupling agent and ammonium alginate
Mass ratio is 2:1~5:1.
Moreover, mass concentration of 1, the 3- propane sultone in toluene be 5%~20%, 1,3- propane sultone with
The mass ratio of sodium alginate is 2:1~5:1.
A kind of selection of the adsorbent material based on modified sodium alginate microballoon for rare and scatter element caesium in salt lake bittern
Property absorption.
In view of the deficiencies of the prior art, the present invention is directly with Material synthesis nontoxic, stable, cheap and easy to get sodium alginate
Microballoon increases the stability of microballoon, and introduce function by base material of this microballoon by introducing polyvinyl alcohol in microballoon
Change sulfonic acid group, is prepared for a kind of adsorbent material based on modified sodium alginate microballoon.This composite material manufacturing process is simpler
It is single, it is of less demanding to experiment condition.This is stable rich in sulfonic adsorbent material and has good absorption property to caesium, has
Biggish use value and wide application prospect.
The advantages of the present invention:
(1) not only preparation process is simple, at low cost for a kind of adsorbent material based on modified sodium alginate microballoon of the invention
It is honest and clean, effectively absorption caesium, and with good stability and recycling.
(2) a kind of adsorbent material based on modified sodium alginate microballoon of the invention can effectively solve traditional cesium ion absorption
Agent bad mechanical strength is granulated difficulty and is difficult to the problem of recycling or defect.
Detailed description of the invention
Fig. 1 is that the present invention introduces sulfonic synthetic route chart into sodium alginate micro ball；
Fig. 2 be the present invention be not introduced into sulfonic sodium alginate micro ball (Fig. 2 a) and introducing sulfonic group after sodium alginate it is micro-
The infrared comparison spectrogram of ball (Fig. 2 b)；
Fig. 3 is the recycling performance of modified sodium alginate microballoon in Application Example 1 of the present invention.
Specific embodiment
The present invention will be further described in the following with reference to the drawings and specific embodiments.
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent, such as without special
Illustrate, commercially obtains.
Embodiment 1:
A kind of adsorbent material and preparation method thereof based on modified sodium alginate microballoon, comprising the following steps:
Step 1: 1g sodium alginate and 1g polyvinyl alcohol are dissolved in 25mL deionized water, are heated at 80 DEG C, are sufficiently stirred
It mixes uniformly, boric acid solution (mass concentration 5% of boric acid solution, the mass concentration of calcium chloride of calcium chloride is then added dropwise
10%) gelled pill is formed in；
Gel ball: being washed with deionized water by step 2 at room temperature, is added in the aqueous solution of 25mL 1%KH550, stirring
React 12h；
Step 3: dispersing above-mentioned product in 25mL toluene, and 1g 1 is added, and 3- propane sultone reacts 12h；
Step 4: after reaction, successively with toluene, ethyl alcohol, deionized water elution, drying, modified sodium alginate is obtained
Micro-sphere absorption material.
Embodiment 2:
A kind of adsorbent material and preparation method thereof based on modified sodium alginate microballoon, comprising the following steps:
Step 1: 1g sodium alginate and 1.5g polyvinyl alcohol are heated at 80 DEG C and are dissolved in 30mL deionized water, sufficiently
It stirs evenly, boric acid solution (mass concentration 2% of boric acid solution, the mass concentration of calcium chloride of calcium chloride is then added dropwise
5%) gelled pill is formed in；
Gel ball: being washed with deionized water by step 2 at room temperature, is added in the aqueous solution of 30mL4%KH550, and stirring is anti-
Answer 12h；
Step 3: dispersing above-mentioned product in 25mL toluene, and 1g 1 is added, and 3- propane sultone reacts 12h；
Step 4: after reaction, successively with toluene, ethyl alcohol, deionized water elution, drying, modified sodium alginate is obtained
Micro-sphere absorption material.
Embodiment 3:
A kind of adsorbent material and preparation method thereof based on modified sodium alginate microballoon, comprising the following steps:
Step 1: 1g sodium alginate and 8g polyvinyl alcohol are heated at 80 DEG C and are dissolved in 30mL deionized water, is sufficiently stirred
It mixes uniformly, boric acid solution (mass concentration 1% of boric acid solution, the mass concentration of calcium chloride of calcium chloride is then added dropwise
1%) gelled pill is formed in；
Gel ball: being washed with deionized water by step 2 at room temperature, is added in the aqueous solution of 30mL4%A171, and stirring is anti-
Answer 20h；
Step 3: dispersing above-mentioned product in 25mL toluene, and 5g 1 is added, and 3- propane sultone reacts 20h；
Step 4: after reaction, successively with toluene, ethyl alcohol, deionized water elution, drying, modified sodium alginate is obtained
Micro-sphere absorption material.
Embodiment 4:
A kind of adsorbent material and preparation method thereof based on modified sodium alginate microballoon, comprising the following steps:
Step 1: 1g sodium alginate and 8g polyvinyl alcohol are heated at 80 DEG C and are dissolved in 30mL deionized water, is sufficiently stirred
It mixes uniformly, boric acid solution (mass concentration 1% of boric acid solution, the mass concentration of calcium chloride of calcium chloride is then added dropwise
1%) gelled pill is formed in；
Gel ball: being washed with deionized water by step 2 at room temperature, is added in the aqueous solution of 30mL 4%KH-560, stirring
Reaction is for 24 hours；
Step 3: dispersing above-mentioned product in 25mL toluene, and 3g 1 is added, and 3- propane sultone reacts for 24 hours；
Step 4: after reaction, successively with toluene, ethyl alcohol, deionized water elution, drying, modified sodium alginate is obtained
Micro-sphere absorption material.
The function of sodium alginate micro ball after sulfonic group is not introduced into and introduced by FTIR spectrum (Tensor 27) characterization
Unity structure, as shown in Figure 2, wherein being not introduced into sulfonic sodium alginate micro ball infrared spectrum is Fig. 2 a, introduces sulfonic sea
Mosanom microballoon infrared spectrum is 2b.As can be seen that wavelength is in 3410cm from Fig. 2 a-1Absorption peak be not introduced into it is sulfonic
The stretching vibration of-OH in sodium alginate micro ball.It can be seen that, wavelength is in 1098cm from Fig. 2 b-1, 598cm-1And 530cm-1's
Absorption peak, which corresponds to, is introduced into-SO in sulfonic sodium alginate micro ball3The eigen vibration peak of H.Infrared comparison spectrogram demonstrates sulphur
Acidic group has successfully been introduced into sodium alginate micro ball neutrality.
Application Example 1:
It is 100mg/L that modified sodium alginate microballoon after taking the drying prepared in 0.05g embodiment 2, which is added to 50mL concentration,
Caesium solution in, the pH of solution is adjusted to 8；It is placed in shaking table oscillation 12h, is measured and is adsorbed with inductive coupling plasma emission spectrograph
Cesium ion concentration in the solution of front and back；Then the ammonium nitrate solution that 1mol/L is added is desorbed, and the material after regeneration continues
Adsorption experiment calculates separately each circulation experiment resin to the adsorption capacity of caesium.As shown in figure 3, being recycled by 5 times, the present invention
Adsorbent material still there is good recycling performance and stability, the adsorption capacity of cesium ion can reach 50mg/g.
The technical solution that embodiment or attached drawing of the invention has been shown and described above, embodies of the invention
A kind of adsorbent material and preparation method thereof based on modified sodium alginate microballoon.It should be understood that for those skilled in the art
For member, it can be modified or changed according to the above description, and all these modifications and variations all should belong to appended by the present invention
Scope of protection of the claims.
Claims (8)
1. a kind of preparation method of the adsorbent material based on modified sodium alginate microballoon, it is characterised in that: the following steps are included:
(1) sodium alginate and polyvinyl alcohol are dissolved in deionized water, are then added dropwise to shape in the boric acid solution of calcium chloride
At gelled pill；
(2) it is added in the aqueous solution of silane coupling agent after at room temperature cleaning gelled pill, it is stirred to react 12~for 24 hours；
(3) it disperses above-mentioned product in toluene, addition 1,3- propane sultone reaction 12~for 24 hours；
(4) after reaction, the absorption of modified sodium alginate microballoon successively is obtained with toluene, ethyl alcohol, deionized water elution, drying
Material.
2. preparation method according to claim 1, it is characterised in that: the weight ratio of sodium alginate and polyvinyl alcohol is 1:10
~1:1.
3. preparation method according to claim 1, it is characterised in that: the silane coupling agent be KH-550, KH-560,
The mixture of one or more of A151, A171.
4. preparation method according to claim 1, it is characterised in that: calcium chloride in the boric acid solution of the calcium chloride
Mass concentration is 1~10%, and the mass concentration of boric acid is 1~5%.
5. preparation method according to claim 1, it is characterised in that: the mass concentration of the aqueous solution of silane coupling agent is
0.5%~10%, the mass ratio of silane coupling agent and sodium alginate is 2:1~5:1.
6. preparation method according to claim 1, it is characterised in that: quality of 1, the 3- propane sultone in toluene is dense
Degree is 5%~20%, and the mass ratio of 1,3- propane sultone and sodium alginate is 2:1~5:1.
7. preparation method described in a kind of any claim according to claim 1~6 obtains micro- based on modified sodium alginate
The adsorbent material of ball.
8. a kind of application of adsorbent material described in claim 1 in salt lake bittern in separation and Extraction caesium.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112755979A (en) * | 2021-01-12 | 2021-05-07 | 陕西科技大学 | Magnetic gel ball adsorption material and preparation method thereof |
| CN115608330A (en) * | 2022-09-29 | 2023-01-17 | 一重集团大连工程技术有限公司 | Composite microsphere adsorbent for removing radioactive cesium and preparation method thereof |
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| CN103769062B (en) * | 2014-02-27 | 2017-02-01 | 江南大学 | Functionalized polyvinyl alcohol hydrogel and preparation method thereof |
| CN107055810A (en) * | 2017-01-17 | 2017-08-18 | 湖南大学 | A kind of preparation method and applications for having magnetic Bio-Nano-Materials |
| CN107973559A (en) * | 2017-11-22 | 2018-05-01 | 广西大学 | The preparation method and applications of porous geological polymer microballoon |
-
2019
- 2019-05-13 CN CN201910393311.1A patent/CN110170311B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769062B (en) * | 2014-02-27 | 2017-02-01 | 江南大学 | Functionalized polyvinyl alcohol hydrogel and preparation method thereof |
| CN107055810A (en) * | 2017-01-17 | 2017-08-18 | 湖南大学 | A kind of preparation method and applications for having magnetic Bio-Nano-Materials |
| CN107973559A (en) * | 2017-11-22 | 2018-05-01 | 广西大学 | The preparation method and applications of porous geological polymer microballoon |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112755979A (en) * | 2021-01-12 | 2021-05-07 | 陕西科技大学 | Magnetic gel ball adsorption material and preparation method thereof |
| CN115608330A (en) * | 2022-09-29 | 2023-01-17 | 一重集团大连工程技术有限公司 | Composite microsphere adsorbent for removing radioactive cesium and preparation method thereof |
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