CN100464857C - Preparation method of polyantimonic acid ion-exchanger - Google Patents
Preparation method of polyantimonic acid ion-exchanger Download PDFInfo
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- CN100464857C CN100464857C CNB200610169593XA CN200610169593A CN100464857C CN 100464857 C CN100464857 C CN 100464857C CN B200610169593X A CNB200610169593X A CN B200610169593XA CN 200610169593 A CN200610169593 A CN 200610169593A CN 100464857 C CN100464857 C CN 100464857C
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Abstract
The invention discloses a preparation method of poly-antimonic acid ion exchanger. The method of the invention includes the following steps: 1) antimony trioxide oxidation: antimony trioxide is oxygenated under the presence of oxidants and prepares hydrated antimony pentoxide sol; 2) Oxide aging: aging the prepared hydrated antimony pentoxide sol 1- 30 days under constant temperature of 0 ~ 70 degreeC; 3) drying and exploring in order to form particles: drying the aged hydrated antimony pentoxide sol to poly-antimonic acid solid, putting it into thin nitric acid solution to explore particles and prepares poly-antimonic acid ion exchanger. The invention method has the following advantages: 1. mild preparation conditions and short reaction time; 2. simple installations, low requirements to equipment and easy operation process; 3. preparation process avoids the touch of toxic chemicals; 4. low-cost preparation process, less art operating cost and good adsorption properties of ion exchanger; 5. high selective adsorption capacity of the prepared poly-antimonic acid inorganic ion exchanger to Sr2+.
Description
Technical field
The present invention relates to a kind of method for preparing polyantimonic acid ion-exchanger.
Background technology
90Sr is the important radionuclide in the nuclear fission refuse, separates and reclaims
90Sr not only can reduce nuclear waste to be threatened the potential radioactivity of the mankind, but also might turn waste into wealth.That inorganic ion exchanger has is acidproof, high temperature resistant, radiation hardness, selectivity is good, preparation is simple, advantage such as easy and simple to handle, has good application prospects in the separation of radwaste.To Sr
2+Selectivity inorganic ion exchanger preferably is a hydrous antimony pentoxide (HAP)---poly-metaantimmonic acid, it can adsorb radionuclide effectively from acid medium
90Sr.At present, the method for the poly-metaantimmonic acid of the preparation of bibliographical information mainly is to adopt Antimony pentachloride hydrolysis under neutrality or diluted acid condition, ageing at a certain temperature, drying and obtain end product.Yet because Antimony pentachloride shortcomings such as to have toxicity very big, and raw material is expensive and be difficult for obtaining, and the hydrolytic process reaction is comparatively violent.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing polyantimonic acid ion-exchanger.
Preparation method of the present invention comprises the steps:
1) antimony oxide oxidation
Oxidation reaction takes place in antimony oxide in the presence of oxidant, obtain hydrous antimony pentoxide (HAP) colloidal sol;
2) oxide ageing
With the insulation ageing 1～30 day when 0～70 ℃ of the temperature of gained hydrous antimony pentoxide (HAP) colloidal sol;
3) dry, burst and be particle
Hydrous antimony pentoxide (HAP) colloidal sol drying after the ageing must be gathered the metaantimmonic acid solid, drop into to burst in rare nitric acid and be particle, obtain polyantimonic acid ion-exchanger.
Wherein, the described oxidant of step 1) is a hydrogen peroxide.The step 1) oxidation reaction process is as follows:
A) ratio of antimony oxide and water be 1:2～8 (ratio of quality volume g/mL), fully stirs and dropwise adds hydrogen peroxide down, the ratio of hydrogen peroxide and antimony oxide be 1:0.3～5 (ratio of volume mass, mL/g)
B) reaction temperature of oxidation backflow is 30～95 ℃, and the oxidation return time is 0.25～5 hour, obtains hydrous antimony pentoxide (HAP) colloidal sol.
The step 3) baking temperature is 0～100 ℃.The concentration of the rare nitric acid of step 3) is 0.01～12mol/L.
The present invention with antimony oxide in the presence of oxidant, carry out the oxidation back flow reaction at a certain temperature, the gained oxide after the low temperature drying, places dilute nitric acid solution to burst into granule through ageing, washing is to neutral, low temperature drying is through repeatedly bursting washing, drying, the product of getting certain particle size is as inorganic ion exchanger.The inventive method has following advantage: 1. preparation condition gentleness, and the reaction time is short; 2. device is simple, and low for equipment requirements, technological operation is easy; 3. preparation process has been avoided the contact toxic chemical substance; 4. preparation process is with low cost, and the process operation expense is few, and the absorption property of gained ion-exchanger is good, in nitric acid medium to Sr
2+-Y
3+The exchange adsorption capacity of strontium reaches 0.52～0.80mmol/g in the mixed solution, is 0.002～0.04mmol/g to the exchange adsorption capacity of yttrium; 5. prepared poly-metaantimmonic acid inorganic ion exchanger is to Sr
2+Selective absorption capacity height, realized Sr
2+-Y
3+Efficient separation, can reach 5.6 * 10 to the separation maximum of strontium and yttrium
6
The specific embodiment
Embodiment 1: the preparation of polyantimonic acid ion-exchanger
Get antimony oxide 10g, add 30mL water, stirring to pulp is warming up to 90 ℃, adds hydrogen peroxide 6mL, continues insulation reaction 90min.After being cooled to room temperature after reaction finishes, inclining reacted colloidal sol, in ageing under the room temperature after 3 days, with the ageing product place 70 ℃ baking oven dry the blocks of solid product.The blocks of solid that drying is obtained is poured into while hot in rare nitric acid and is made solid burst into granule then, is washed till neutrality, through repeatedly dry and burst, wash and drying after to get 40～100 purpose particles be final poly-metaantimmonic acid inorganic ion exchanger product.
Embodiment 2: the preparation of polyantimonic acid ion-exchanger
Get antimony oxide 10g, add 60mL water, stirring to pulp is warming up to 60 ℃, adds hydrogen peroxide 9mL, continues insulation reaction 90min.After being cooled to room temperature after reaction finishes, inclining reacted solution, after 5 days, the ageing product is placed the blocks of solid product of 70 ℃ baking oven drying in ageing under the room temperature.Pour the blocks of solid that is dried to into rare nitric acid while hot then and make blocks of solid burst into granule, be washed till neutrality, through repeatedly dry and burst that finally to get 40～100 purpose particles be final poly-metaantimmonic acid inorganic ion exchanger product.
Embodiment 3: the preparation of polyantimonic acid ion-exchanger
Get antimony oxide 10g, add 40mL water, stirring to pulp is warming up to 70 ℃, adds hydrogen peroxide 12mL, continues insulation reaction 120min.After being cooled to room temperature after reaction finishes, inclining reacted solution, after 2 days, the ageing product is placed the blocks of solid product of 40 ℃ baking oven drying in ageing under the room temperature.Pour the blocks of solid that is dried to into rare nitric acid while hot then and make blocks of solid burst into granule, be washed till neutrality, through repeatedly dry and burst that finally to get 40～100 purpose particles be final poly-metaantimmonic acid inorganic ion exchanger product.
Embodiment 4: the preparation of polyantimonic acid ion-exchanger
Get antimony oxide 10g, add 30mL water, stirring to pulp is warming up to 80 ℃, adds hydrogen peroxide 12mL, continues insulation reaction 60min.After being cooled to room temperature after reaction finishes, inclining reacted solution, after 10 days, the ageing product is placed the blocks of solid product of 50 ℃ baking oven drying in ageing under the room temperature.Pour the blocks of solid that is dried to into rare nitric acid while hot then and make blocks of solid burst into granule, be washed till neutrality, through repeatedly dry and burst that finally to get 40～100 purpose particles be final poly-metaantimmonic acid inorganic ion exchanger product.
Embodiment 5: the preparation of polyantimonic acid ion-exchanger
Get antimony oxide 10g, add 50mL water, stirring to pulp is warming up to 70 ℃, adds hydrogen peroxide 12mL, continues insulation reaction 90min.After being cooled to room temperature after reaction finishes, inclining reacted solution, after 7 days, the ageing product is placed the blocks of solid product of 60 ℃ baking oven drying in ageing under the room temperature.Pour the blocks of solid that is dried to into rare nitric acid while hot then and make blocks of solid burst into granule, be washed till neutrality, through repeatedly dry and burst that finally to get 40～100 purpose particles be final poly-metaantimmonic acid inorganic ion exchanger product.
Embodiment 6: the preparation of polyantimonic acid ion-exchanger
Get antimony oxide 20g, add 60mL water, stirring to pulp is warming up to 90 ℃, adds hydrogen peroxide 12mL, continues insulation reaction 90min.After being cooled to room temperature after reaction finishes, inclining reacted solution, after 15 days, the ageing product is placed the blocks of solid product of 30 ℃ baking oven drying in ageing under the room temperature.Pour the blocks of solid that is dried to into rare nitric acid while hot then and make blocks of solid burst into granule, be washed till neutrality, through repeatedly dry and burst that finally to get 40～100 purpose particles be final poly-metaantimmonic acid inorganic ion exchanger product.
Embodiment 7: the preparation of polyantimonic acid ion-exchanger
Get antimony oxide 50g, add 200mL water, stirring to pulp is warming up to 60 ℃, adds hydrogen peroxide 60mL, continues insulation reaction 120min.After being cooled to room temperature after reaction finishes, inclining reacted solution, after 25 days, the ageing product is placed the blocks of solid product of 50 ℃ baking oven drying in ageing under the room temperature.Pour the blocks of solid that is dried to into rare nitric acid while hot then and make blocks of solid burst into granule, be washed till neutrality, through repeatedly dry and burst that finally to get 40～100 purpose particles be final poly-metaantimmonic acid inorganic ion exchanger product.
Embodiment 8, polyantimonic acid ion-exchanger absorption Sr
2+
Adsorption separation process does not have special requirement to equipment, if the Sr that is adsorbed
2+Initial concentration is bigger, can adjust the size and the quantity of absorber, in the hope of material balance according to adsorption rate and adsorbance.Pack in absorber and gather the metaantimmonic acid inorganic ion exchanger, pending liquid can be removed Sr from top adding from lower part outlet
2+Solution.When this absorber reached the control terminal point, pending liquid can switch to another absorber.
To contain Sr
2+Initial concentration be the acid solution (medium is a nitric acid, and concentration is 0.2mol/L) of 445mg/L by the 5cm adsorption column, diameter is 3mm, the poly-metaantimmonic acid inorganic ion exchanger of dress dry weight 0.4g in the post (embodiment 1 preparation), flow velocity is 0.0017m/min.When elution volume reached 18.7mL, the concentration of strontium was 0 in the outlet liquid.When the concentration of strontium in the outlet liquid reaches 0.01%, can switch absorber.Can be made into adsorption volume-concentration curve, come to determine the switching time of absorber as required.
Embodiment 9: polyantimonic acid ion-exchanger adsorbing separation Sr
2+-Y
3+
Be examination Sr
2+-Y
3+Exist simultaneously down, polyantimonic acid ion-exchanger will contain Sr to the separation case of strontium and yttrium
2+-Y
3+Mixed solution (Sr wherein
2+Concentration be Y
3+10～100 times of concentration) by ion exchange column, diameter is 3～5mm, adorns the polyantimonic acid ion-exchanger of certain dry weight in the post, the control certain flow rate.Collect outflow liquid and measure wherein Sr
2+And Y
3+Concentration.
To contain Sr
2+Initial concentration be 390mg/L, the initial concentration of yttrium is that the acid solution (medium is a nitric acid, and concentration is 0.2mol/L) of 24.46mg/L passes through the 3.5cm adsorption column, and diameter is 3mm, the poly-metaantimmonic acid inorganic ion exchanger of dress dry weight 0.5g in the post (embodiment 2 preparations), flow velocity is 0.0017m/min.When the volume that flows out liquid was 1mL, the concentration of strontium was 0 in the outlet solution, and the concentration of yttrium is 0.16% of entrance concentration.When the volume that flows out liquid was 13mL, the concentration of strontium still was 0 in the outlet solution, and the concentration of yttrium reaches more than 80% of entrance concentration, and when the volume that flows out liquid reached 32mL, the concentration of strontium still was 0 in the outlet solution, and the concentration of yttrium then is 100% of entrance concentration.When the concentration of strontium in the outlet liquid reaches 0.01%, can switch absorber, come to determine the switching time of absorber as required.Like this, Sr
2+With Y
3+Obtain separating, separation is 2.6 * 10
4
Embodiment 10: polyantimonic acid ion-exchanger adsorbing separation Sr
2+-Y
3+
Be examination Sr
2+-Y
3+Exist simultaneously down, polyantimonic acid ion-exchanger will contain Sr to the absorption of strontium and yttrium and to the desorb separation case of yttrium
2+-Y
3+Mixed solution (Sr wherein
2+Concentration be Y
3+10～100 times of concentration) by ion exchange column, diameter is 3～4mm, adorns the polyantimonic acid ion-exchanger of certain dry weight in the post, the control certain flow rate.Collect outflow liquid and measure wherein Sr
2+And Y
3+Concentration.
To contain Sr
2+Initial concentration be 467mg/L, the initial concentration of yttrium is that the acid solution (medium is a nitric acid, and concentration is 0.2mol/L) of 3.82mg/L passes through the 5cm adsorption column, and diameter is 3mm, the poly-metaantimmonic acid inorganic ion exchanger of dress dry weight 0.40g in the post (embodiment 3 preparations), flow velocity is 0.0017m/min.After mixed solution flows through the ion exchange column certain hour, in the time of in flowing out liquid, can't detecting strontium, with strippant the yttrium on the ion exchange column is carried out desorb, used strippant is that concentration is the EDTA solution (solvent is hydrochloric acid or the nitric acid of 0.01-1mol/L) of 0.005-0.1mol/L, this strippant can be separated sucking-off and be adsorbed on yttrium on the ion exchange column, and can not separate the sucking-off strontium substantially, and like this, Sr
2+With Y
3+Obtain separating, separation is 500.
Embodiment 11: polyantimonic acid ion-exchanger adsorbing separation Sr
2+-Y
3+
Be examination Sr
2+-Y
3+Exist simultaneously down, polyantimonic acid ion-exchanger will contain Sr to the absorption of strontium and yttrium and to the desorb separation case of yttrium
2+-Y
3+Mixed solution (Sr wherein
2+Concentration be Y
3+4000 times of concentration) by ion exchange column, diameter is 3～4mm, adorns the polyantimonic acid ion-exchanger of certain dry weight in the post, the control certain flow rate.Collect outflow liquid and measure wherein Sr
2+And Y
3+Concentration.
To contain Sr
2+Initial concentration be 487mg/L, the initial concentration of yttrium is that the acid solution (medium is a nitric acid, and concentration is 0.1mol/L) of 3.17mg/L passes through the 5cm adsorption column, and diameter is 3mm, the poly-metaantimmonic acid inorganic ion exchanger of dress dry weight 0.40g in the post (embodiment 4 preparations), flow velocity is 0.0017m/min.After mixed solution flows through the ion exchange column certain hour, in the time of in flowing out liquid, can't detecting strontium, with strippant the yttrium on the ion exchange column is carried out desorb, used strippant is that concentration is the hydrochloric acid of 0.5mol/L, this strippant can be separated sucking-off and be adsorbed on yttrium on the ion exchange column, and can not separate the sucking-off strontium, and like this, Sr
2+With Y
3+Obtain separating, separation is 9.5 * 10
5
Embodiment 12: polyantimonic acid ion-exchanger adsorbing separation Sr
2+-Y
3+
Be examination Sr
2+-Y
3+Exist simultaneously down, polyantimonic acid ion-exchanger will contain Sr to the absorption of strontium and yttrium and to the desorb separation case of yttrium
2+-Y
3+Mixed solution (Sr wherein
2+Concentration be Y
3+4000 times of concentration) by ion exchange column, diameter is 3～4mm, adorns the polyantimonic acid ion-exchanger of certain dry weight in the post, the control certain flow rate.Collect outflow liquid and measure wherein Sr
2+And Y
3+Concentration.
To contain Sr
2+Initial concentration be 8000mg/L, the initial concentration of yttrium is that the acid solution (medium is a nitric acid, and concentration is 0.02mol/L) of 2mg/L passes through the 5cm adsorption column, and diameter is 4mm, the poly-metaantimmonic acid inorganic ion exchanger of dress dry weight 0.60g in the post (embodiment 5 preparations), flow velocity is 0.0017m/min.After getting the 1.00mL mixed solution and flowing through ion exchange column, with strippant the yttrium on the ion exchange column is carried out desorb, used strippant is that concentration is the nitric acid of 0.5mol/L, this strippant can be separated sucking-off and be adsorbed on yttrium on the ion exchange column, and can not separate the sucking-off strontium substantially, and like this, Sr
2+With Y
3+Obtain separating, separation is 5.6 * 10
6
Claims (4)
1, a kind of method for preparing polyantimonic acid ion-exchanger comprises the steps:
1) antimony oxide oxidation
Oxidation reaction takes place in antimony oxide in the presence of oxidant hydrogen peroxide, obtain hydrous antimony pentoxide (HAP) colloidal sol;
2) oxide ageing
With the insulation ageing 1～30 day when 0～70 ℃ of the temperature of gained hydrous antimony pentoxide (HAP) colloidal sol;
3) dry, burst and be particle
Hydrous antimony pentoxide (HAP) colloidal sol drying after the ageing must be gathered the metaantimmonic acid solid, drop into to burst in rare nitric acid and be particle, obtain polyantimonic acid ion-exchanger.
2, method according to claim 1 is characterized in that: the described oxidation reaction process of step 1) is as follows:
A) ratio of antimony oxide and water be 1:2～8 (ratio of quality volume g/mL), fully stirs and dropwise adds hydrogen peroxide down, the ratio of hydrogen peroxide and antimony oxide be 1:0.3～5 (ratio of volume mass, mL/g)
B) reaction temperature of oxidation backflow is 30～95 ℃, and the oxidation return time is 0.25～5 hour, obtains hydrous antimony pentoxide (HAP) colloidal sol.
3, method according to claim 1 and 2 is characterized in that: the baking temperature described in the step 3) is 0～100 ℃.
4, method according to claim 1 and 2 is characterized in that: the concentration of the rare nitric acid described in the step 3) is 0.01～12mol/L.
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|---|---|---|---|
| CNB200610169593XA CN100464857C (en) | 2006-12-22 | 2006-12-22 | Preparation method of polyantimonic acid ion-exchanger |
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| CNB200610169593XA CN100464857C (en) | 2006-12-22 | 2006-12-22 | Preparation method of polyantimonic acid ion-exchanger |
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| CN100464857C true CN100464857C (en) | 2009-03-04 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106140108B (en) * | 2015-03-27 | 2020-10-23 | 中国科学院上海应用物理研究所 | Polyantimonic acid/polyacrylonitrile composite ion exchanger and preparation method and application thereof |
| CN110540240A (en) * | 2019-08-20 | 2019-12-06 | 包头钢铁（集团）有限责任公司 | preparation method of poly-antimonic acid |
| CN114669269B (en) * | 2022-02-15 | 2023-06-09 | 天津理工大学 | Cs (cell lines) + 、Sr 2+ Co-adsorption-separation dual-function ion exchanger and preparation method and application thereof |
| CN114804202B (en) * | 2022-05-31 | 2023-06-23 | 中国核动力研究设计院 | Inorganic adsorbent of poly antimonic acid, preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1129039A (en) * | 1966-01-05 | 1968-10-02 | Commissariat Energie Atomique | Process for separating strontium values from a solution containing strontium |
| US4859343A (en) * | 1987-12-02 | 1989-08-22 | Lithium Corporation Of America | Sodium removal from brines |
-
2006
- 2006-12-22 CN CNB200610169593XA patent/CN100464857C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1129039A (en) * | 1966-01-05 | 1968-10-02 | Commissariat Energie Atomique | Process for separating strontium values from a solution containing strontium |
| US4859343A (en) * | 1987-12-02 | 1989-08-22 | Lithium Corporation Of America | Sodium removal from brines |
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