CN116532094A - Ammonium phosphomolybdate resin particles, and preparation method and application thereof - Google Patents
Ammonium phosphomolybdate resin particles, and preparation method and application thereof Download PDFInfo
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- CN116532094A CN116532094A CN202310825693.7A CN202310825693A CN116532094A CN 116532094 A CN116532094 A CN 116532094A CN 202310825693 A CN202310825693 A CN 202310825693A CN 116532094 A CN116532094 A CN 116532094A
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- Prior art keywords
- ammonium phosphomolybdate
- resin particles
- mixed solution
- phosphomolybdate
- sodium alginate
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- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 title claims abstract description 146
- 239000002245 particle Substances 0.000 title claims abstract description 96
- 239000011347 resin Substances 0.000 title claims abstract description 96
- 229920005989 resin Polymers 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011259 mixed solution Substances 0.000 claims abstract description 48
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 48
- 239000000661 sodium alginate Substances 0.000 claims abstract description 48
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 48
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 19
- 238000004132 cross linking Methods 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 235000010410 calcium alginate Nutrition 0.000 claims abstract description 11
- 239000000648 calcium alginate Substances 0.000 claims abstract description 11
- 229960002681 calcium alginate Drugs 0.000 claims abstract description 11
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims abstract description 11
- 239000002927 high level radioactive waste Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 51
- 239000007788 liquid Substances 0.000 abstract description 33
- 238000000926 separation method Methods 0.000 abstract description 19
- 230000002378 acidificating effect Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 239000003463 adsorbent Substances 0.000 abstract description 5
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 11
- 238000001035 drying Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 7
- 239000003729 cation exchange resin Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000012265 solid product Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000002285 radioactive effect Effects 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011964 heteropoly acid Chemical class 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- -1 salt cation Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0218—Compounds of Cr, Mo, W
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- 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
- B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of adsorption materials, and provides ammonium phosphomolybdate resin particles, and a preparation method and application thereof. Mixing an orthosilicic acid solution and sodium alginate to obtain a mixed solution; and (3) mixing the mixed solution with ammonium phosphomolybdate, and then dripping the mixed solution into a soluble calcium salt solution for crosslinking to obtain ammonium phosphomolybdate resin particles. According to the invention, ammonium phosphomolybdate is used as an adsorbent, calcium alginate is used as a cross-linking agent, and orthosilicic acid is added to improve the mechanical strength of the material, so that the prepared ammonium phosphomolybdate resin particles have high selectivity of ammonium phosphomolybdate and high adsorption capacity under extremely acidic conditions, and meanwhile, the problem of difficult solid-liquid separation of ammonium phosphomolybdate is solved, and the ammonium phosphomolybdate resin particles have excellent mechanical properties. The results of the examples show that,the maximum bearing capacity of the ammonium phosphomolybdate resin particles prepared by the invention is 18.29N, and the ammonium phosphomolybdate resin particles are 3.75X10 under the condition of 8mol/L of extremely acid ‑4 The adsorption percentage of the mol/L Cs is still higher than 60 percent.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to ammonium phosphomolybdate resin particles, and a preparation method and application thereof.
Background
How to safely and effectively treat a large amount of high-level waste liquid generated by spent fuel post-treatment is one of the bottlenecks limiting the development of the nuclear industry. In the high level waste liquid, cs is mainly used 135 Cs and 137 cs exist in both forms. 135 Cs half-life is as long as 2.3X10 6 Years, there is thus a greater potential for environmental hazards. Although in spite of 137 Cs has a short half-life (30.2 years), but is the primary source of gamma radiation in high level waste, and is considered the most significant heat release hazard for the 1000 years prior to disposal of high level waste. If the radioactive Cs is separated from the high-level radioactive waste liquid, the purposes of reducing the heating value and radioactive toxicity of the high-level radioactive waste liquid and reducing the solidification volume of glass can be achieved, the cooling time of the waste liquid and the storage life of the waste can be shortened, and the disposal cost of the high-level radioactive waste liquid is saved.
At present, the method for separating Cs in the high-level radioactive waste liquid mainly comprises a precipitation method, an ion exchange method and a solvent extraction method. The ion exchange method is attracting attention because of its high adsorption capacity, good ion selectivity and simple process. The adsorbent for radioactive Cs mainly includes zeolite, heteropolyacid salt, polyvalent metal phosphate, metal ferrocyanide, ferricyanide, hydrous oxides and hydroxides of polyvalent metal (transition metal), composite ion exchanger, and the like.
Ammonium phosphomolybdate (AMP) is a heteropolyacid salt cation exchanger, which is a yellow crystalline inorganic compound of the formula (NH) 4 ) 3 P(Mo 3 O 10 ) 4 Consists of dodecamolybdenum phosphoheteropolyacid anions [ P (MO) with Keggin skeleton structure 12 O 40 )] 3- And NH 4 + Composition is prepared. AMP has the advantages of good adsorption selectivity, large adsorption capacity and easy desorption on Cs, and has better acid resistance and irradiation resistance stability. However, the method is thatHowever, the powder crystallite structure of AMP makes it inferior in hydrodynamic properties, low in mechanical strength, and unsuitable for continuous operation of column experiments; and the solid-liquid separation is difficult, the recycling is difficult, and the secondary pollution is easy to cause.
Disclosure of Invention
The invention aims to provide ammonium phosphomolybdate resin particles, a preparation method and application thereof, and the ammonium phosphomolybdate resin particles prepared by the preparation method provided by the invention have high selectivity of ammonium phosphomolybdate and high adsorption capacity under extremely acidic conditions, solve the problem of difficult solid-liquid separation of ammonium phosphomolybdate, and have excellent mechanical strength.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of ammonium phosphomolybdate resin particles, which comprises the following steps:
(1) Mixing an orthosilicic acid solution and sodium alginate to obtain a mixed solution; the mass ratio of the orthosilicic acid and the sodium alginate in the mixed solution in the step (1) is (4.5-11.2): (0.4 to 0.8);
(2) And (3) mixing the mixed solution obtained in the step (1) with ammonium phosphomolybdate, and then dripping the mixed solution into a soluble calcium salt solution for crosslinking to obtain ammonium phosphomolybdate resin particles.
Preferably, the mass concentration of sodium alginate in the mixed solution in the step (1) is 0.5% -2%.
Preferably, the mode of mixing the orthosilicic acid solution and the sodium alginate in the step (1) is stirring; the stirring speed is 400-600 r/min, and the stirring time is 3-6 h.
Preferably, the mass ratio of the sodium alginate in the step (1) to the ammonium phosphomolybdate in the step (2) is (0.4-0.8): (0.4 to 2.0).
Preferably, the dropping speed in the step (2) is 0.8-1.0 mL/min.
Preferably, the concentration of the soluble calcium salt solution in the step (2) is 0.1-0.2 mol/L; the soluble calcium salt in the soluble calcium salt solution comprises calcium chloride, calcium nitrate or emulsified calcium.
Preferably, the time of crosslinking in the step (2) is 24-48 h.
The invention provides the ammonium phosphomolybdate resin particles prepared by the preparation method in the technical proposal, and the ammonium phosphomolybdate resin particles comprise ammonium phosphomolybdate, calcium alginate and SiO 2 。
The invention also provides application of the ammonium phosphomolybdate resin particles in separating cesium in high-level radioactive waste liquid.
The beneficial effects are that:
the invention provides a preparation method of ammonium phosphomolybdate resin particles, which comprises the following steps: (1) Mixing an orthosilicic acid solution and sodium alginate to obtain a mixed solution; the mass ratio of the orthosilicic acid and the sodium alginate in the mixed solution in the step (1) is (4.5-11.2): (0.4 to 0.8); (2) And (3) mixing the mixed solution obtained in the step (1) with ammonium phosphomolybdate, and then dripping the mixed solution into a soluble calcium salt solution for crosslinking to obtain ammonium phosphomolybdate resin particles. According to the invention, ammonium phosphomolybdate is used as an adsorbent, calcium alginate is used as a cross-linking agent, and orthosilicic acid is added to improve the mechanical strength of the material, so that the prepared ammonium phosphomolybdate resin particles have high selectivity of ammonium phosphomolybdate and high adsorption capacity under extremely acidic conditions, and meanwhile, the problem of difficult solid-liquid separation of ammonium phosphomolybdate is solved, and the ammonium phosphomolybdate resin particles have excellent mechanical properties. The results of the examples show that the maximum tolerance of the ammonium phosphomolybdate resin particles prepared according to the invention is 18.29N for 3.75X10 s under extremely acidic conditions of 8mol/L -4 The adsorption percentage of the Cs is still higher than 60 percent, and the Cs is 3mol/L H + The separation factor for other cations is greater than 145.
Drawings
FIG. 1 is a physical view of ammonium phosphomolybdate resin particles prepared in example 1 of the present invention;
FIG. 2 is an SEM image of ammonium phosphomolybdate resin particles prepared according to example 1 of the invention;
FIG. 3 is a surface morphology graph of ammonium phosphomolybdate resin particles prepared in example 1 of the present invention;
FIG. 4 is an XRD pattern of ammonium phosphomolybdate resin particles and commercially available ammonium phosphomolybdate powder prepared in example 1 of the present invention;
FIG. 5 is an infrared spectrum of ammonium phosphomolybdate resin particles prepared in example 1 of the present invention;
FIG. 6 is an EDS spectrum of ammonium phosphomolybdate resin particles prepared in example 1 of the present invention;
FIG. 7 is a graph showing the effect of ammonium phosphomolybdate resin particles prepared in example 1 of the present invention on the adsorption of Cs during various time periods;
FIG. 8 shows the ammonium phosphomolybdate resin particles prepared in example 1 of the present invention at various H' s + Adsorption percentage graph of Cs at concentration;
FIG. 9 shows the reaction of the ammonium phosphomolybdate resin particles prepared in example 1 of the present invention in H + A dot plot of the amount of adsorbed Cs with Cs concentration at concentrations of 3mol/L and 5 mol/L;
FIG. 10 is a bar graph showing the adsorption percentage of Cs by the ammonium phosphomolybdate resin particles prepared in examples 1 to 4 and comparative example 1 of the present invention;
FIG. 11 is a bar graph showing the adsorption effect of ammonium phosphomolybdate resin particles prepared in example 1 of the present invention on each ion in a simulated high level waste liquid;
FIG. 12 is a bar graph showing the mechanical properties of the ammonium phosphomolybdate resin particles prepared in examples 1 to 4 and comparative example 1 according to the present invention.
Detailed Description
The invention provides a preparation method of ammonium phosphomolybdate resin particles, which comprises the following steps:
(1) Mixing an orthosilicic acid solution and sodium alginate to obtain a mixed solution; the mass ratio of the orthosilicic acid and the sodium alginate in the mixed solution in the step (1) is (4.5-11.2): (0.4 to 0.8);
(2) And (3) mixing the mixed solution obtained in the step (1) with ammonium phosphomolybdate, and then dripping the mixed solution into a soluble calcium salt solution for crosslinking to obtain ammonium phosphomolybdate resin particles.
The invention mixes the orthosilicic acid solution and sodium alginate to obtain the mixed solution. According to the invention, the sodium alginate is dissolved in the orthosilicic acid solution by mixing the orthosilicic acid solution and the sodium alginate.
The method of mixing the orthosilicic acid solution and sodium alginate is not particularly limited, and a mixing method well known to those skilled in the art may be adopted. In the present invention, the means for mixing the orthosilicic acid solution and sodium alginate is preferably stirring. In the invention, the stirring speed is preferably 400-600 r/min; the stirring time is preferably 3-6 hours. In the present invention, the temperature at which the orthosilicic acid solution and sodium alginate are mixed is preferably room temperature.
In the present invention, the preparation method of the orthosilicic acid solution preferably comprises: na is mixed with 2 SiO 3 ·5H 2 O is dissolved in water and then exchanged by cation exchange resin to obtain an orthosilicic acid solution. In the present invention, the Na 2 SiO 3 ·5H 2 The mass of O and the volume ratio of water are preferably 7.07g:20.0mL; the water is preferably deionized water. In the present invention, the cation exchange resin is preferably a 732 type strongly acidic cation exchange resin.
In the invention, the mass concentration of sodium alginate in the mixed solution is preferably 0.5% -2%, more preferably 0.8% -1.6%. The invention preferably controls the mass concentration of the sodium alginate in the mixed solution within the above range, which is beneficial to improving the regularity of ammonium phosphomolybdate resin particles. The source of the sodium alginate is not particularly limited, and commercially available products known to those skilled in the art can be used.
In the invention, the mass ratio of the orthosilicic acid to the sodium alginate in the mixed solution is (4.5-11.2): (0.4-0.8), preferably (4.5-5.6): (0.6-0.8). In the invention, the mass ratio of the orthosilicic acid and the sodium alginate in the mixed solution is preferably controlled within the range, so that the mechanical strength of the ammonium phosphomolybdate resin particles is improved.
After the mixed solution is obtained, the mixed solution and the ammonium phosphomolybdate are mixed, and then dripped into a soluble calcium salt solution for crosslinking, so that the ammonium phosphomolybdate resin particles are obtained. The invention drops the mixed solution containing sodium alginate into the soluble calcium salt solution for crosslinking, wherein the sodium alginate reacts with the soluble calcium salt to generate water-insoluble calcium alginate, and then a crosslinked gel system which wraps orthosilicic acid and ammonium phosphomolybdate is formed. According to the invention, the orthosilicic acid solution and the sodium alginate are mixed firstly and then are mixed with the ammonium phosphomolybdate, so that the problem that the orthosilicic acid solution is aggregated into silica gel and cannot be molded due to the fact that the molecular weight of the ammonium phosphomolybdate is large is avoided.
The mode of mixing the mixed solution and ammonium phosphomolybdate in the present invention is not particularly limited, and a mixing mode well known to those skilled in the art may be adopted. The invention does not limit the mixing time of the mixed solution and the ammonium phosphomolybdate, and the mixed solution and the ammonium phosphomolybdate are fully and uniformly mixed.
In the invention, the mass ratio of the sodium alginate to the ammonium phosphomolybdate is preferably (0.4-0.8): (0.4 to 2.0), more preferably (0.6 to 0.8): (0.4 to 2.0). The mass ratio of the sodium alginate to the ammonium phosphomolybdate is preferably controlled within the range, so that the adsorption efficiency of the ammonium phosphomolybdate resin particles is improved. The source of the ammonium phosphomolybdate is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
The operation of the dropping is not particularly limited, and the dropping method can be adopted by a technical scheme well known to those skilled in the art.
In the present invention, the dropping speed is preferably 0.8 to 1.0mL/min, more preferably 0.8 to 0.9mL/min.
In the present invention, the dropping device is preferably a syringe pump; the needle hole diameter of the syringe pump is preferably 0.7-1.0 mm, more preferably 0.7-0.9 mm.
In the invention, the concentration of the soluble calcium salt solution is preferably 0.1-0.2 mol/L; the soluble calcium salt in the soluble calcium salt solution preferably includes calcium chloride, calcium nitrate or emulsified calcium, more preferably calcium chloride. The source of the soluble calcium salt solution is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the invention, the use amount of the soluble calcium salt solution is preferably 300-500 mL.
In the present invention, the time for crosslinking is preferably 24 to 48 hours, more preferably 24 hours.
After the crosslinking is completed, the crosslinked product is preferably washed, stood and dried in sequence. The washing, standing and drying operations are not particularly limited, and the washing, standing and drying technical schemes well known to those skilled in the art can be adopted. In the present invention, the washing reagent is preferably deionized water. In the invention, the temperature of the drying is preferably 50-60 ℃; the drying equipment is preferably an oven.
According to the invention, ammonium phosphomolybdate is used as an adsorbent, calcium alginate is used as a cross-linking agent, and orthosilicic acid is added to improve the mechanical strength of the material, so that the prepared ammonium phosphomolybdate resin particles have high selectivity of ammonium phosphomolybdate and high adsorption capacity under extremely acidic conditions, and meanwhile, the problem of difficult solid-liquid separation of ammonium phosphomolybdate is solved, and the ammonium phosphomolybdate resin particles have excellent mechanical properties.
The ammonium phosphomolybdate resin particles prepared by the preparation method provided by the invention comprise ammonium phosphomolybdate, calcium alginate and SiO 2 。
The ammonium phosphomolybdate resin particles provided by the invention have excellent mechanical properties, and have high selectivity and high adsorption capacity for cesium.
The invention also provides application of the ammonium phosphomolybdate resin particles in separating cesium in high-level radioactive waste liquid.
The application of the ammonium phosphomolybdate resin particles in separating cesium in the high-level waste liquid is not particularly limited, and the method of separating cesium in the high-level waste liquid by using an adsorbent well known to those skilled in the art can be adopted.
In the present invention, the concentration of cesium in the high-level radioactive waste liquid is preferably 7.50X10 -5 ~9.40×10 -3 mol/L; h in the high-level radioactive waste liquid + The concentration of (C) is preferably 1-8 mol/L.
In the present invention, the amount of the ammonium phosphomolybdate resin particles is preferably 10g/L.
In the present invention, the temperature of the separation is preferably normal temperature; the separation time is preferably 14-48 h.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) 7.07g of Na at room temperature 2 SiO 3 ·5H 2 O is dissolved in 20mL of deionized water, and then the solution is exchanged by 732 type strong acid cation exchange resin to obtain an orthosilicic acid solution; then adding 0.8g of sodium alginate into the orthosilicic acid solution, and stirring for 4 hours at the speed of 550r/min to obtain a mixed solution; wherein the mass concentration of sodium alginate in the mixed solution is 1.6%, and the mass ratio of the orthosilicic acid and the sodium alginate in the mixed solution is 4.5:0.8;
(2) Adding 2.0g of ammonium phosphomolybdate (the mass ratio of sodium alginate to ammonium phosphomolybdate is 0.8:2.0) into the mixed solution obtained in the step (1), fully mixing, adding into a syringe pump with the pinhole diameter of 0.7mm, dripping 300mL of 0.1mol/L calcium chloride solution at the speed of 0.9mL/min, crosslinking for 24 hours, carrying out solid-liquid separation, washing a solid product with deionized water, standing, and drying at 50 ℃ to obtain ammonium phosphomolybdate resin particles, and N 2 Specific surface area measured by BET method of 84.64m 2 /g。
FIG. 1 is a physical view of ammonium phosphomolybdate resin particles prepared in this example. As can be seen from FIG. 1, the ammonium phosphomolybdate resin particles prepared in this example are regular in shape, uniform in size and about 1-2 mm in diameter.
Fig. 2 is an SEM image of the ammonium phosphomolybdate resin particles prepared in this example. As can be seen from FIG. 2, the diameter of the ammonium phosphomolybdate resin particles was about 1.3mm.
The surface morphology of the ammonium phosphomolybdate resin particles prepared in this example was observed by a scanning electron microscope, and the result is shown in fig. 3. As can be seen from fig. 3, the surface of the ammonium phosphomolybdate resin particles is roughened.
FIG. 4 is an XRD pattern of the ammonium phosphomolybdate resin particles prepared in this example and of a commercially available ammonium phosphomolybdate powder. As can be seen from fig. 4, the XRD pattern diffraction peaks of the ammonium phosphomolybdate resin particles prepared in this example are almost identical to those of the commercial ammonium phosphomolybdate powder, and since both of the orthosilicic acid and the calcium alginate are amorphous materials, there is no significant diffraction peak in the XRD pattern.
FIG. 5 is an infrared spectrum of ammonium phosphomolybdate resin particles prepared in this example. In FIG. 5, 790cm -1 And 869cm -1 The absorption peak corresponds to the Mo-O-Mo functional group, 961cm -1 Characteristic absorption peak for mo=o, 961cm -1 And 869cm -1 Is a characteristic peak of Keggin structure. 1064cm -1 The characteristic absorption peak of P-O bond is 3446cm -1 And 1636cm -1 The nearby peaks correspond to the-OH symmetrical stretching vibration peak and the H-O-H bending vibration of water respectively, which indicates that the ammonium phosphomolybdate resin particles have crystal water or surface adsorbed water. 1404cm -1 The nearby peaks correspond to the bending vibration peak and the stretching vibration peak of N-H respectively, which proves that NH exists in the resin particles 4 + 。
FIG. 6 is an EDS spectrum of ammonium phosphomolybdate resin particles prepared in this example. As can be seen from FIG. 6, si, cl, ca, mo, P, N and other elements are present in the ammonium phosphomolybdate resin particles prepared in this example, which proves that the material is composed of ammonium phosphomolybdate, calcium alginate and SiO 2 Composite material is formed.
Example 2
(1) 7.07g of Na at room temperature 2 SiO 3 ·5H 2 O is dissolved in 20mL of deionized water, and then the solution is exchanged by 732 type strong acid cation exchange resin to obtain an orthosilicic acid solution; then adding 0.8g of sodium alginate into the orthosilicic acid solution, and stirring for 4 hours at the speed of 550r/min to obtain a mixed solution; wherein the mass concentration of sodium alginate in the mixed solution is 1.6%, and the mass ratio of the orthosilicic acid and the sodium alginate in the mixed solution is 4.5:0.8;
(2) Adding 0.4g of ammonium phosphomolybdate (the mass ratio of sodium alginate to ammonium phosphomolybdate is 0.8:0.4) into the mixed solution obtained in the step (1), fully mixing, adding into a syringe pump with the pinhole diameter of 0.7mm, dripping 300mL of 0.1mol/L calcium chloride solution at the speed of 0.9mL/min, crosslinking for 24 hours, carrying out solid-liquid separation, washing a solid product with deionized water, standing, and drying at 50 ℃ to obtain ammonium phosphomolybdate resin particles.
Example 3
(1) 7.07g of Na at room temperature 2 SiO 3 ·5H 2 O is dissolved in 20mL of deionized water, and then the solution is exchanged by 732 type strong acid cation exchange resin to obtain an orthosilicic acid solution; then adding 0.4g of sodium alginate into the orthosilicic acid solution, and stirring for 4 hours at the speed of 550r/min to obtain a mixed solution; wherein the mass concentration of sodium alginate in the mixed solution is 0.8%, and the mass ratio of the orthosilicic acid and the sodium alginate in the mixed solution is 4.5:0.4;
(2) Adding 2.0g of ammonium phosphomolybdate (the mass ratio of sodium alginate to ammonium phosphomolybdate is 0.4:2.0) into the mixed solution obtained in the step (1), fully mixing, adding into a syringe pump with the pinhole diameter of 0.7mm, dripping 300mL of 0.1mol/L calcium chloride solution at the speed of 0.9mL/min, crosslinking for 24 hours, carrying out solid-liquid separation, washing a solid product with deionized water, standing, and drying at 50 ℃ to obtain ammonium phosphomolybdate resin particles.
Example 4
(1) 7.07g of Na at room temperature 2 SiO 3 ·5H 2 O is dissolved in 20mL of deionized water, and then the solution is exchanged by 732 type strong acid cation exchange resin to obtain an orthosilicic acid solution; then adding 0.6g of sodium alginate into the orthosilicic acid solution, and stirring for 4 hours at the speed of 550r/min to obtain a mixed solution; wherein the mass concentration of sodium alginate in the mixed solution is 1.2%, and the mass ratio of the orthosilicic acid and the sodium alginate in the mixed solution is 4.5:0.6;
(2) Adding 2.0g of ammonium phosphomolybdate (the mass ratio of sodium alginate to ammonium phosphomolybdate is 0.6:2.0) into the mixed solution obtained in the step (1), fully mixing, adding into a syringe pump with the pinhole diameter of 0.7mm, dripping 300mL of 0.1mol/L calcium chloride solution at the speed of 0.9mL/min, crosslinking for 24 hours, carrying out solid-liquid separation, washing a solid product with deionized water, standing, and drying at 50 ℃ to obtain ammonium phosphomolybdate resin particles.
Comparative example 1
Adding 0.8g of sodium alginate into 40mL of deionized water solution, stirring for 4 hours at the speed of 550r/min, adding 2.0g of ammonium phosphomolybdate, fully mixing, adding into a syringe pump with the pinhole diameter of 0.7mm, dripping 300mL of 0.1mol/L of calcium chloride solution at the speed of 0.9mL/min, crosslinking for 24 hours, performing solid-liquid separation, washing a solid product with deionized water, standing, and drying at 50 ℃ to obtain ammonium phosphomolybdate resin particles.
Performance test:
1. adsorption performance
(1) At normal temperature, adding ammonium phosphomolybdate resin particles into the mixture according to the dosage of 10g/L, wherein the concentration of Cs is 0-1.00 multiplied by 10 - 2 mol/L，H + Placing the high-level waste liquid with the concentration of 1-8 mol/L in a constant temperature oscillator, oscillating for 0-48 h, taking supernatant, passing through a 0.22 mu m membrane, measuring the concentration of Cs in the adsorption equilibrium supernatant by using ICP-OES, and calculating the adsorption percentage (S%) and the adsorption quantity (q);
the adsorption percentage (S%) and the adsorption amount (q) were calculated according to the following formulas, respectively:
wherein C is 0 The unit is mol/L for the initial concentration of ions; c (C) e The unit is mol/L for the equilibrium liquid phase concentration of ions; v is the volume of the high-level waste liquid, and the unit is L; m is the mass of the ammonium phosphomolybdate resin particles, and the unit is g.
FIG. 7 is a graph showing the effect of ammonium phosphomolybdate resin particles prepared in example 1 on adsorption of Cs during various time periods; wherein H is + The concentration is 3mol/L, and the concentration of Cs is 3.75X10 -4 mol/L. As can be seen from fig. 7, as the time of action increases, the adsorption capacity of the ammonium phosphomolybdate resin particles prepared in example 1 to Cs increases significantly, and adsorption equilibrium is reached after 14 hours. The calculation found that the adsorption data of Cs on ammonium phosphomolybdate resin particles can be quantitatively described using a quasi-second order kinetic equation (R 2 =0.96). In the figure, the solid line is the quasi-second-level dynamics fitting result, R 2 Representing the correlation coefficient.
FIG. 8 shows the ammonium phosphomolybdate resin particles prepared in example 1 at different H' s + Concentration of Cs adsorption percentage graph. As can be seen from fig. 8, H + The concentration is in the range of 1-8 mol/L, and the adsorption of ammonium phosphomolybdate resin particles to Cs with different concentrations is kept at a higher level; in particular, under the condition of 8mol/L extremely acidity, the ammonium phosphomolybdate resin particle pair is 3.75X10 -4 The adsorption percentage of the mol/L Cs is still higher than 60 percent.
FIG. 9 shows the ammonium phosphomolybdate resin particles prepared in example 1 at H + And a dot plot of the amount of adsorbed Cs with the concentration of Cs at concentrations of 3mol/L and 5 mol/L. As can be seen from fig. 9, as the Cs concentration increases, the Cs adsorption amount increases rapidly and then remains unchanged. When the adsorption does not reach saturation, as the concentration of Cs increases, cs bound by the adsorption sites of the ammonium phosphomolybdate resin particles gradually increases, and thus the amount of Cs adsorbed increases. When the concentration of Cs is increased to a certain degree, the adsorption sites of the ammonium phosphomolybdate resin particles can reach saturation, the concentration of Cs is continuously increased, and the adsorption capacity is not obviously increased. At the same Cs concentration, the ammonium phosphomolybdate resin particles are in the H state + The adsorption amount of Cs is higher than H at the concentration of 3mol/L + Adsorption amount at a concentration of 5 mol/L.
FIG. 10 is a bar graph showing the adsorption percentage of Cs by the ammonium phosphomolybdate resin particles prepared in examples 1 to 4 and comparative example 1; wherein H is + The concentration is 3mol/L, and the concentration of Cs is 3.76X10 -4 mol/L. As can be seen from fig. 10, the adsorption performance of the ammonium phosphomolybdate resin particles is affected by the amount of ammonium phosphomolybdate, the more the amount of ammonium phosphomolybdate, the higher the adsorption percentage, while the change in calcium alginate content has a negligible effect on the adsorption percentage of Cs.
(2) Simulation of adsorption experiments of Cs in high level waste liquid: at normal temperature, the ammonium phosphomolybdate resin particles prepared in example 1 were added at a rate of 10g/L to Cs-containing + 、Al 3+ 、Cr 3+ 、Fe 3+ 、K + 、Na + 、Nd 3+ 、Ni 2+ 、Sr 2+ ，H + Placing in high-level waste liquid with concentration of 3mol/L, oscillating in a constant temperature oscillator for 48 hr, collecting supernatant, passing through 0.22 μm membrane, measuring the concentration of each ion in the adsorption balance supernatant by ICP-OES, and calculating the adsorption distribution ratio and separation factor of each ionThe results are shown in Table 1.
Adsorption partition ratio (K) d ) And a Separation Factor (SF) are calculated according to the following formulas, respectively:
wherein C is 0 The unit is mol/L for the initial concentration of ions; c (C) e The unit is mol/L for the equilibrium liquid phase concentration of ions; v is the volume of the high-level waste liquid, and the unit is L; m is the mass of ammonium phosphomolybdate resin particles, and the unit is g; m refers to ions other than Cs.
FIG. 11 is a bar graph showing the adsorption effect of ammonium phosphomolybdate resin particles prepared in example 1 on each ion in a simulated high level waste liquid. As can be seen from FIG. 11, the adsorption percentage of the ammonium phosphomolybdate resin particles prepared in example 1 to Cs in the simulated high level waste liquid is significantly higher than that of other ions, which indicates that the ammonium phosphomolybdate resin particles have specific adsorption capacity to Cs and are expected to be used for the selective separation of Cs in the high level waste liquid.
As can be seen from Table 1, at 3mol/L H + Under the conditions of (1), the separation factors of the ammonium phosphomolybdate resin particles prepared in example 1 on other cations are all larger than 145. From this, it is found that the ammonium phosphomolybdate resin particles have specific adsorption capacity for Cs, and are expected to be used for selective separation of Cs in high level radioactive waste liquid.
2. Mechanical properties
And (3) taking one sample of ammonium phosphomolybdate resin particles to be detected, placing the sample in the middle of two steel sheets with the length of 2cm multiplied by 5mm, then placing the sample on a pressing head of a universal material testing machine, performing compressive strength test to obtain a pressure-strain curve, recording from the position with the pressure of 0.04N to the position with the maximum bearing, measuring once for each group of samples, and recording the maximum force value, wherein the descending speed of the pressing head is 1 mm/min.
Fig. 12 is a bar graph of mechanical properties of ammonium phosphomolybdate resin particles prepared in examples 1 to 4 and comparative example 1. The results of comparative example 1 and comparative example 1 revealed that the maximum tolerance of the ammonium phosphomolybdate resin particles to which no orthosilicate was added during the preparation was 3.31N, whereas the maximum tolerance of the ammonium phosphomolybdate resin particles to which orthosilicate was added during the preparation was increased to 18.29N, indicating a significant improvement in the mechanical properties of the material. As a result of comparing the mechanical properties of the ammonium phosphomolybdate resin particles obtained in the various examples, it was found that the initial amounts of ammonium phosphomolybdate, calcium alginate and orthosilicic acid all had a certain effect on the mechanical strength of the ammonium phosphomolybdate resin particles.
As can be seen from the above examples, the ammonium phosphomolybdate resin particles prepared according to the present invention have excellent mechanical properties, and have high selectivity for Cs and high adsorption capacity under extremely acidic conditions, with a maximum tolerance of 18.29N, under 8mol/L extremely acidic conditions of 3.75X10 -4 The adsorption percentage of the Cs is still higher than 60 percent, and the Cs is 3mol/L H + The separation factor for other cations is greater than 145.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A method for preparing ammonium phosphomolybdate resin particles, comprising the steps of:
(1) Mixing an orthosilicic acid solution and sodium alginate to obtain a mixed solution; the mass ratio of the orthosilicic acid and the sodium alginate in the mixed solution in the step (1) is (4.5-11.2): (0.4 to 0.8);
(2) And (3) mixing the mixed solution obtained in the step (1) with ammonium phosphomolybdate, and then dripping the mixed solution into a soluble calcium salt solution for crosslinking to obtain ammonium phosphomolybdate resin particles.
2. The preparation method of claim 1, wherein the mass concentration of sodium alginate in the mixed solution in the step (1) is 0.5% -2%.
3. The method according to claim 1, wherein the method of mixing the raw silicic acid solution and sodium alginate in step (1) is stirring; the stirring speed is 400-600 r/min, and the stirring time is 3-6 h.
4. The preparation method according to claim 1, wherein the mass ratio of the sodium alginate in the step (1) to the ammonium phosphomolybdate in the step (2) is (0.4-0.8): (0.4 to 2.0).
5. The method according to claim 1, wherein the dropping speed in the step (2) is 0.8 to 1.0ml/min.
6. The preparation method according to claim 1, wherein the concentration of the soluble calcium salt solution in the step (2) is 0.1 to 0.2mol/L; the soluble calcium salt in the soluble calcium salt solution comprises calcium chloride, calcium nitrate or emulsified calcium.
7. The method according to claim 1, wherein the time of crosslinking in the step (2) is 24 to 48 hours.
8. The ammonium phosphomolybdate resin particles prepared by the method of any of claims 1 to 7, comprising ammonium phosphomolybdate, calcium alginate and SiO 2 。
9. Use of the ammonium phosphomolybdate resin particles according to claim 8 for separating cesium in high level radioactive waste.
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| CN116713039A (en) * | 2023-08-10 | 2023-09-08 | 兰州大学 | Zirconium phosphate inorganic ion exchange resin and preparation method thereof |
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