CN103170301A - Preparation method of <131>I<-> high-efficiency adsorbent in nuclear wastewater - Google Patents
Preparation method of <131>I<-> high-efficiency adsorbent in nuclear wastewater Download PDFInfo
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- CN103170301A CN103170301A CN201210513045XA CN201210513045A CN103170301A CN 103170301 A CN103170301 A CN 103170301A CN 201210513045X A CN201210513045X A CN 201210513045XA CN 201210513045 A CN201210513045 A CN 201210513045A CN 103170301 A CN103170301 A CN 103170301A
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Abstract
The invention discloses a preparation method of a <131>I<-> high-efficiency adsorbent in nuclear wastewater, which comprises the following steps: synthesizing sodium titanate nanotubes and nano fibers by a hydrothermal process, and doping and curing nano silver oxide particles to obtain the high-efficiency adsorbent. The high-efficiency adsorbent can quickly and efficiently adsorb and filter nuclear pollution wastewater, can be used for avoiding diffusion of radioactive substance <131>I<-> and other radioiodine isotopes, and is widely used for nuclear accident emergency, nuclear facility shielding and medical radioactive wastewater treatment.1g of the novel adsorbent can be used for filtering and purifying 1 ton of radioactive wastewater; and the adsorbent can completely absorb and fix the radioactive substance <131>I<-> in the nuclear wastewater with the radioactive <131>I<-> content of lower than 200 ppm, and thus, is a high-efficiency adsorbing material with directional selectivity.
Description
Technical field
The present invention relates to a kind of Ag
2The preparation method of the Nano titanate adsorbent of O doping is particularly in radioactive wastewater
131I
-The preparation method of high-efficiency adsorbent.
Background technology
The thermal source of nuclear power station be mainly uranium-235 (
235U), when one
235When the atomic nucleus of U is subject to external neutron bombardment, split into two atomic nucleus that quality is less, emit simultaneously 2～3 neutrons.These neutrons continue again to bombard other
235The U atomic nucleus, the chain reaction of nuclear fission that continues thus to carry out can discharge huge energy.
235U more than the 300 kind of nucleic product of fissioning out mainly is distributed in mass number 90～95, between 130～140 peak region in, remove the nucleic that a large amount of yields are few or the half-life is short, the fission product that mainly obtains be iodine-131 (
131I), caesium-137 (
137Cs), Strontium-90 (
90Sr) etc.
131The β decay can occur in I, launches β ray and gamma-rays, and ceiling capacity is respectively 0.6065Mev and 0.364Mev, and the half-life is 8.02 days.
131The boiling point of I is 184.35 ℃, and density is only 4.93g/cm
3, easily distillation, and it is often existed with gas form, and can wide dispersion arrive outside the hundreds of kilometer.Moreover, when nuclear power reactor has an accident,
131I also can be water-soluble rapidly, forms a large amount of
131I
-(as occurring in the Chernobyl in 1986, occurred in pennsylvania, USA Three Mile Island in 1979, occurring in 2011 in the accident of Fukushima, Japan).In 2009, in the major accident of Britain, Germany, U.S. Nuclear Power Station, occured equally
131The leakage of the radioactive substances such as I isotope.Due to the leakage of these high-grade radioactive wastewaters, in waste water, organism and the natural environment of the ionising radiation meeting of fission product harm surrounding area, attract wide attention at world wide.Radioiodine is also in the diagnosis and the treatment that medically are used for thyroid tumors, and radioactive wastewater is also to be directly emitted by medical research department simultaneously.
Effective processing means of radioactive waste are the extensively guarantees used of peace of radio isotope, but existing means are all complicated and extremely expensive (such as the film separation etc.).Need more effective method in time to catch radioiodine, effectively the purified treatment radioactive wastewater.
Summary of the invention
The invention provides a kind of synthetic method of adsorbent of rapidly and efficiently adsorption filtration nuclear pollution waste water.Can be used for preventing and treating radioactive substance iodine-131 and the isotopic diffusion of other radioiodines, can be widely used in Nuclear Accident Emergency, nuclear facilities protection, the processing of medical radiation wastewater etc.
Preparation process of the present invention is simple, does not need expensive device, and products obtained therefrom quality high-performance is good, can be fast, the radioactive substance iodine-131 in efficient, directed absorption nuclear waste water.
The adsorbent cost for preparing in the present invention is low, effective, is a kind of efficient adsorption material with directional selectivity function, can adsorb fast, simply, efficiently immobilization of radioactive material iodine-131.
In a kind of nuclear waste water that the present invention proposes
131I
-The preparation method of high-efficiency adsorbent comprises the following steps:
1) with concentrated NaOH solution and TiO
2Particle mixes, ultrasonic being uniformly dispersed after stirring; The concentration of described NaOH solution is the described NaOH solution of 10M and TiO
2The mixing quality ratio of particle is 55～60: 3;
2) mixture use hydrothermal reaction kettle polytetrafluoroethyllining lining packing step 1) carries out hydro-thermal reaction;
3) reacted precipitation use distilled water washing step 2) is carried out drying after cleaning up, obtain matrix Sodium Titanate nanofiber or the nanotube of nano adsorber;
4) the water dispersion steps 3) product, by dripping rare NaOH aqueous solution, the pH value of dispersion liquid is transferred to 11, with the matrix after alkalization by centrifugal collection; The concentration of described rare NaOH aqueous solution is 1mM～1M;
5) matrix after the alkalization use silver nitrate aqueous solution soaking step 4), and vigorous stirring;
6) to step 5) process afterproduct and carry out centrifugally, namely obtain in nuclear waste water after the water cleaning-drying after the collecting precipitation thing
131I
-High-efficiency adsorbent.
Described TiO
2Particle is 325 purpose anatase TiO
2
Described even mixing is ultrasonic dispersion, and ultrasonic power is 30W, and jitter time is 30min.
The hydrothermal condition of described Hydrothermal Synthesis is 130～200 ℃.
Described drying condition is vacuum drying or the oven drying under 80 ℃, and be 12h drying time.
Described nano barium titanate sodium salt matrix is Sodium Titanate Nanotubes or Sodium Titanate nanofiber.
Described alkalization is after the adsorbent matrix mixes with 1: 1000 (mass ratio) with water, pH to be transferred to 11 rear centrifugal collection adsorbent matrixes.
Described silver nitrate aqueous solution concentration is 1 * 10
-2M, the mass ratio of alkalization adsorbent and silver nitrate aqueous solution is 1: 1000.
Described curing deposition is through 300～1000rpm magnetic agitation or mechanical agitation, and mixing time is 24h.
Described collection is centrifugal collection, and centrifugal condition is 5000～13000rpm, and centrifugation time is 5min～10min.
Described drying condition is vacuum drying or the oven drying under 80 ℃, and be 12h drying time.
The present invention has the following advantages:
The raw material that the present invention uses is mainly Ti
2O, wide material sources, environment-friendly and green, safe can not bring pollution to environment.
The adsorbent of the inventive method preparation is high-efficiency adsorbent, and 1g just can process 1t waste water, and in 30min, the clearance of iodine-131 can be up to 80% for high-concentration waste water (content is 125ppm).
The adsorbent of the inventive method preparation has selectively, in the situation that the NaCl existence, still can selective absorption radioactive substance iodine-131 and other radioiodine isotopes.
The adsorbent of the inventive method preparation can also solidify iodine-131, and water rinses 48h only can remove 0.4% iodine-131.
The adsorbent of the inventive method preparation can synthesize in a large number, does not need expensive device, can be widely used in Nuclear Accident Emergency, nuclear facilities protection, the processing of medical radiation wastewater etc.
Description of drawings
Fig. 1 is the Sodium Titanate nanofiber matrix that specific embodiment 1 obtains, and visible fibril under low intensity ultrasound is thicker, is about 100～200nm;
Fig. 2 be specific embodiment 1 obtain deposit a large amount of Ag
2The Fibriform adsorbents material that O is nanocrystalline;
Fig. 3 is the TEM figure of the Sodium Titanate Nanotubes matrix that obtains of specific embodiment 2, has obviously as seen formed tubular structure.The nanotube diameter is no more than 10nm;
Fig. 4 is the specific embodiment 2 a large amount of Ag of deposition
2The tubulose sorbent material that O is nanocrystalline.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
6g 325 order anatase titania particles and the 80mL 10M NaOH aqueous solution are mixed mutually, and mixed suspension makes its Uniform Dispersion with the ultrasonic 30min of 30W.
Dispersion liquid after ultrasonic is poured in the polytetrafluoroethyllining lining of hydrothermal reaction kettle, put into baking oven after water heating kettle is tightened, oven temperature transfers to 180 ℃, and the reaction time is 48h.
Use the distilled water cyclic washing after precipitation after hydro-thermal reaction is collected, obtain the Na of white after 80 ℃ of lower vacuum drying 12h
2Ti
3O
7The Sodium Titanate nanofiber.
2g Sodium Titanate nanofiber and 2L pure water are mixed, and with the titration of 1MNaOH solution, the pH that makes dispersion liquid is 11.
Carry out the dispersion liquid of alkalization centrifugal, centrifugation rate is 10000rpm, and centrifugation time is 10min.Remove supernatant, the collecting precipitation thing.
Joining 2L concentration is 1 * 10
-2The silver nitrate aqueous solution of M will be collected good sediment rapid dispersion in silver nitrate aqueous solution, and magnetic agitation speed is 500rpm, continues to stir 24h, and silver oxide fully is deposited on nanofiber.
The centrifugal sediment of having collected again, centrifugal 5min under 13000rpm uses washed with de-ionized water 3 times after centrifugal, again at 80 ℃ of lower vacuum drying 12h.Obtain the Ag that deposits of grizzle this moment
2The superpower absorption nanofiber that O is nanocrystalline.
The adsorbent that 1mg is synthetic adds the NaI of 1L to
125In the aqueous solution, (concentration is 100ppm), at room temperature rotate this dispersion liquid with 1000rpm.Can adsorb iodide ion fully after 30min, this moment, the adsorbent color became faint yellow
Embodiment 2
12g 325 order anatase titania particles and the 160mL 10M NaOH aqueous solution are mixed mutually, and mixed suspension makes its Uniform Dispersion with the ultrasonic 30min of 30W.
Dispersion liquid after ultrasonic is poured in the polytetrafluoroethyllining lining of hydrothermal reaction kettle, put into baking oven after water heating kettle is tightened, oven temperature transfers to 150 ℃, and the reaction time is 48h.
Use the distilled water cyclic washing after precipitation after hydro-thermal reaction is collected, obtain the Na of white after 80 ℃ of lower baking oven convection drying 12h
2Ti
3O
7Sodium Titanate Nanotubes.
1g Sodium Titanate nanofiber and 1L pure water are mixed, and with the NaOH solution titration of 0.1M, the pH that makes dispersion liquid is 10.5.
Carry out the dispersion liquid of alkalization centrifugal, centrifugation rate is 12000rpm, and centrifugation time is 6min.Remove supernatant, the collecting precipitation thing.
Joining 1L concentration is 1 * 10
-2The silver nitrate aqueous solution of M will be collected good sediment rapid dispersion in silver nitrate aqueous solution, and magnetic agitation speed is 1000rpm, continues to stir 24h, and silver oxide fully is deposited on nanotube.
The centrifugal sediment of having collected again, centrifugal 10min under 13000rpm uses washed with de-ionized water 3 times after centrifugal, again at 80 ℃ of lower oven drying 12h.Obtain the Ag that deposits of grizzle this moment
2The superpower absorption nanotube that O is nanocrystalline.
The adsorbent that 1mg is synthetic adds the NaI of 1L to
131In the aqueous solution, (concentration is 200ppm), at room temperature rotate this dispersion liquid with 800rpm.Can adsorb the radioiodine ion fully after 30min, this moment, the adsorbent color became faint yellow.
Should be understood that, for those of ordinary skills, can be improved according to the above description or conversion, and all these improve and conversion all should belong to the protection domain of claims of the present invention.
Claims (10)
1. in a nuclear waste water
131I
-The preparation method of high-efficiency adsorbent is characterized in that, the method comprises the following steps:
1) with concentrated NaOH solution and TiO
2Particle mixes, ultrasonic being uniformly dispersed after stirring; The concentration of described NaOH solution is the described NaOH solution of 10M and TiO
2The mixing quality ratio of particle is 55～60: 3;
2) mixture use hydrothermal reaction kettle polytetrafluoroethyllining lining packing step 1) carries out hydro-thermal reaction;
3) reacted precipitation use distilled water washing step 2) is carried out drying after cleaning up, obtain matrix Sodium Titanate nanofiber or the nanotube of nano adsorber;
4) the water dispersion steps 3) product, by dripping rare NaOH aqueous solution, the pH value of dispersion liquid is transferred to 11, with the matrix after alkalization by centrifugal collection; The concentration of described rare NaOH aqueous solution is 1mM～1M;
5) matrix after the alkalization use silver nitrate aqueous solution soaking step 4), and vigorous stirring;
6) to step 5) process afterproduct and carry out centrifugally, namely obtain in nuclear waste water after the water cleaning-drying after the collecting precipitation thing
131I
-High-efficiency adsorbent.
2. preparation method according to claim 1, is characterized in that step 1) described in TiO
2Particle is 325 purpose anatase TiO
2
3. preparation method according to claim 1, is characterized in that step 1) described in ultrasonic dispersion be that ultrasonic power is 30W, jitter time is 30min.
4. preparation method according to claim 1, is characterized in that step 2) described in hydrothermal condition be 130～200 ℃, the reaction time is 48h.
5. preparation method according to claim 1, is characterized in that step 3) described in drying condition be vacuum drying or oven drying under 80 ℃, be 12h drying time.
6. preparation method according to claim 1, is characterized in that step 4) described in the mass ratio that mixes with water of adsorbent matrix be 1: 1000.
7. preparation method according to claim 1, is characterized in that step 4) described in centrifugal condition be 5000～13000rpm, centrifugation time is 5min～10min.
8. preparation method according to claim 1, is characterized in that step 5) described in silver nitrate aqueous solution concentration be 1 * 10
-2Matrix after the M alkalization and the mass ratio of silver nitrate aqueous solution are 1: 1000.
9. preparation method according to claim 1, is characterized in that step 5) described in intense agitation be magnetic agitation or the mechanical agitation of 300～1000rpm, mixing time is 24h.
10. preparation method according to claim 1, is characterized in that step 6) described in centrifugal condition be 5000～13000rpm, centrifugation time is 5min～10min; Described drying condition is vacuum drying or the oven drying under 80 ℃, and be 12h drying time.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016187914A1 (en) * | 2015-05-26 | 2016-12-01 | 清华大学 | Activation agent for deep treatment of radioactive waste water and application thereof |
| CN109569535A (en) * | 2018-12-11 | 2019-04-05 | 华东师范大学 | The adsorbent material and preparation method of radioiodine in a kind of enriching seawater |
| CN109999758A (en) * | 2019-04-18 | 2019-07-12 | 浙江农林大学 | A kind of timber aeroge and preparation method and application capturing radioactivity zwitterion altogether |
| CN113019312A (en) * | 2021-03-03 | 2021-06-25 | 中国科学院地球化学研究所 | Halloysite-based composite material for removing radioactive iodide ions and preparation method thereof |
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| US20060226081A1 (en) * | 2005-04-12 | 2006-10-12 | Honeywell International Inc. | Water purification system and modes of operation |
| CN101003385A (en) * | 2006-01-17 | 2007-07-25 | 河南大学 | Method for preparing Nano tube of titanate |
| CN101546805A (en) * | 2009-03-04 | 2009-09-30 | 中国科学院广州能源研究所 | Preparation method of high-quality-factor low-dimensional-oxide nanometer thermoelectric new material |
| CN101564688A (en) * | 2009-02-24 | 2009-10-28 | 福建工程学院 | Method for preparing titanic oxide nano composited tube |
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Patent Citations (8)
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| CN1378977A (en) * | 2002-05-24 | 2002-11-13 | 清华大学 | Process for preparing hydrated sodium titanate and nano titanate tube series |
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| CN101766540A (en) * | 2010-01-01 | 2010-07-07 | 东南大学 | Antibacterial artificial tooth root with bioactivity and preparation method thereof |
| WO2011086567A1 (en) * | 2010-01-12 | 2011-07-21 | Council Of Scientific & Industrial Research | Magnetic dye-adsorbent catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016187914A1 (en) * | 2015-05-26 | 2016-12-01 | 清华大学 | Activation agent for deep treatment of radioactive waste water and application thereof |
| CN109569535A (en) * | 2018-12-11 | 2019-04-05 | 华东师范大学 | The adsorbent material and preparation method of radioiodine in a kind of enriching seawater |
| CN109999758A (en) * | 2019-04-18 | 2019-07-12 | 浙江农林大学 | A kind of timber aeroge and preparation method and application capturing radioactivity zwitterion altogether |
| CN113019312A (en) * | 2021-03-03 | 2021-06-25 | 中国科学院地球化学研究所 | Halloysite-based composite material for removing radioactive iodide ions and preparation method thereof |
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