CN117339250A - Method for selectively separating molybdenum from nitric acid solution containing uranium and splinter elements - Google Patents
Method for selectively separating molybdenum from nitric acid solution containing uranium and splinter elements Download PDFInfo
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- CN117339250A CN117339250A CN202210733403.1A CN202210733403A CN117339250A CN 117339250 A CN117339250 A CN 117339250A CN 202210733403 A CN202210733403 A CN 202210733403A CN 117339250 A CN117339250 A CN 117339250A
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- silica gel
- hydroxyquinoline
- acid solution
- nitric acid
- molybdenum
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 37
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 37
- 239000011733 molybdenum Substances 0.000 title claims abstract description 37
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910017604 nitric acid Inorganic materials 0.000 title claims abstract description 31
- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 30
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 206010041662 Splinter Diseases 0.000 title claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 74
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000741 silica gel Substances 0.000 claims abstract description 52
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 41
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003463 adsorbent Substances 0.000 claims abstract description 28
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims abstract description 15
- 229960003540 oxyquinoline Drugs 0.000 claims abstract description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 25
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 11
- 239000001099 ammonium carbonate Substances 0.000 claims description 11
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010828 elution Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003795 desorption Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- SLBPIHCMXPQAIQ-UHFFFAOYSA-N 8-hydroxyquinoline-2-carbaldehyde Chemical compound C1=C(C=O)N=C2C(O)=CC=CC2=C1 SLBPIHCMXPQAIQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 10
- 239000003446 ligand Substances 0.000 abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 abstract description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 32
- 230000008569 process Effects 0.000 description 12
- 239000008346 aqueous phase Substances 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 231100000987 absorbed dose Toxicity 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Mechanical Engineering (AREA)
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- Manufacturing & Machinery (AREA)
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- Geochemistry & Mineralogy (AREA)
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Abstract
The invention discloses a method for selectively separating molybdenum from a nitric acid solution containing uranium and splinter elements. According to the invention, 8-hydroxyquinoline is chemically grafted onto silica gel through a silane coupling agent to prepare a hydroxyquinoline grafted silica gel material, and then the material is used as an adsorbent to efficiently and selectively adsorb molybdenum from a nitric acid solution containing uranium and splinter elements. The invention breaks through the limitation that the known silica gel graft and the independent quinoline ligand can not well realize the selective separation of molybdenum and other elements, and the 8-hydroxyquinoline ligand is grafted on the silica gel to adjust the space configuration of the 8-hydroxyquinoline ligand, thereby providing the selective adsorption effect of the 8-hydroxyquinoline ligand on the elements such as molybdenum, uranium and the like, and improving the saturated adsorption quantity of the molybdenum.
Description
Technical Field
The invention relates to a separation and purification method of molybdenum, in particular to a method for separating molybdenum, uranium and other splinter elements by utilizing a hydroxyquinoline grafted silica gel material.
Background
Silica gel (SiO) 2 ) Has the characteristics of no toxicity, good mechanical property, low cost, easy chemical modification and the like, is a preferred adsorption material, but is unmodified silica gelThe adsorption capacity and adsorption selectivity of (a) are low. Accordingly, there have been studies focused on grafting organic functional groups on silica gel, providing more stable hybrid or composite materials through chemical bonds between the silica gel material and organic molecules, and using them for adsorption of metal ions. However, the existing known silica gel graft can not well separate molybdenum from uranium and various split elements, and the saturated adsorption quantity of molybdenum needs to be further improved.
Under acidic conditions, 8-hydroxyquinoline has a good coordination effect on Mo (VI) and has great potential in the adsorption of Mo (VI) (Ramkumar, J.; maiti, B.Transport of molybdenum across a bulk liquid membrane using8-hydroxy quinoline as a carrier.Sep.Sci.technology.2004, 39, 449-457). However, the independent 8-hydroxyquinoline can coordinate with uranium and other splinter elements and even be extracted or adsorbed, so that the selective separation of molybdenum and uranium and other elements cannot be realized by only relying on the 8-hydroxyquinoline.
Disclosure of Invention
The invention aims to provide a method for selectively separating molybdenum, uranium and other split elements.
To achieve the above object, the present invention has found cis-MoO by grafting 8-hydroxyquinoline onto silica gel 2 2+ Can form a stable complex structure with grafted hydroxyquinoline at the pH of about 1.0, so as to be adsorbed on a grafted silica gel material; for uranium and other elements, a plurality of quinoline groups need to be twisted to a specific angle to form a stable complex structure. The quinoline group is fixed on the silica gel and cannot move freely, so that the quinoline group is difficult to coordinate with elements such as uranium, and finally, the selective separation effect of the elements such as molybdenum and uranium is achieved. The invention breaks through the limitation that the known silica gel graft and the single quinoline ligand can not well realize the selective separation of molybdenum from other elements, and obtains unexpected molybdenum separation effect.
The technical scheme provided by the invention is as follows: a method for selectively separating molybdenum from nitric acid solution containing uranium and splinter elements comprises the steps of firstly chemically grafting 8-hydroxyquinoline onto silica gel through a silane coupling agent to prepare a hydroxyquinoline grafted silica gel material, and then efficiently and selectively adsorbing molybdenum from the nitric acid solution containing uranium and splinter elements by utilizing the material.
Preferably, the specific surface area of the silica gel is 150-1500 m 2 /g。
Preferably, the hydroxyquinoline grafted silica gel material is prepared by two-step chemical grafting of (3-Aminoalkyl) trialkoxysilane (AATAS) and 8-hydroxyquinoline (Quin) having a high selective coordination to Mo (VI) using inorganic silica gel as a base material, as shown in FIG. 1, to obtain a hydroxyquinoline grafted silica gel material (designated as SiO 2 -AATAS-Quin)。
The chemical structure of the hydroxyquinoline grafted silica gel material prepared by the method is shown as a formula I:
wherein a is an integer of 1 to 12, and b is an integer of 1 to 12. Preferably, a=3 and b=2, i.e. using (3-aminopropyl) triethoxysilane (APTES) as grafting coupling agent.
Hydroxyquinoline grafted silica gel adsorption material (SiO) shown in formula I 2 -AATAS-Quin) is prepared by: silica gel (SiO) 2 ) Adding the silica gel into hydrochloric acid solution, heating and refluxing overnight to activate the surface of the silica gel; separating the activated silica gel by filtration and drying; adding AATAS into the suspension of activated silica gel, heating and refluxing under the protection of argon gas for reaction, cooling to room temperature after the reaction is completed, filtering, washing and drying to obtain SiO 2 AATAS; siO is made of 2 Reflux-reacting AATAS and 8-hydroxyquinoline-2-formaldehyde in organic solvent (such as DMF), cooling to room temperature after reaction, filtering, washing, and drying to obtain SiO 2 -AATAS-Quin。
The hydroxyquinoline grafted silica gel material can be used for efficiently and selectively separating and purifying molybdenum from nitric acid solution containing uranium, zirconium, ruthenium, iodine, cesium and/or cerium and other split elements, wherein the nitric acid solution is usually nitric acid solution of a uranium target after irradiation.
Specifically, the method for separating and purifying molybdenum from nitric acid solution containing uranium and fissile elements such as zirconium, ruthenium, iodine, cesium and/or cerium comprises the following steps:
(1) The silica gel material grafted by the hydroxyquinoline is used as an adsorbent to adsorb molybdenum in nitric acid solution containing molybdenum, uranium and other split elements, while uranium and other split elements (such as zirconium, ruthenium, iodine, cesium, cerium and the like) are not adsorbed;
(2) Desorbing the adsorbent subjected to the step (1) to obtain an elution solution containing molybdenum.
The adsorbent desorbed in the step (2) can be recycled.
In the above step (1), the amount of the hydroxyquinoline grafted silica gel material adsorbent is not particularly limited, and in general, 0.01 to 1.5g/L of adsorbent per liter of the nitric acid solution is used. When the concentration of molybdenum in the nitric acid solution is higher, the quality of the adsorbent can be correspondingly improved to realize efficient adsorption. The adsorption temperature may be 5 ℃ to 100 ℃, and there is no particular limitation on the adsorption process and equipment.
Preferably, the pH of the nitric acid solution in step (1) is 1.0 to 2.0. The adsorption operation can be to add the hydroxyquinoline grafted silica gel material into the nitric acid solution, shake and mix the materials uniformly and then stand the materials for a period of time, or to enable the nitric acid solution to flow through an adsorption column filled with the hydroxyquinoline grafted silica gel material.
In the step (2), the desorption solution after the hydroxyquinoline grafted silica gel material adsorbs molybdenum can be an ammonia water solution of ammonium carbonate, a guanidine carbonate solution and an ammonium carbonate solution. Preferably, the desorption solution used in step (2) is an aqueous ammonia solution containing 0.05M ammonium carbonate.
The hydroxyquinoline grafted silica gel material adsorbent used in the invention has good irradiation stability and thermal stability, and can maintain high adsorption efficiency when the total irradiation dose is lower than 800kGy and the temperature is lower than 300 ℃.
The invention provides a method for adsorbing and separating molybdenum from nitric acid solution containing uranium, molybdenum, zirconium, ruthenium, iodine, cesium and cerium. The method takes the silica gel material grafted with the hydroxyquinoline as the adsorbent, breaks through the known silica gel graft and the independent quinoline ligand, and can not realize molybdenum wellThe selective separation limit with other elements regulates the spatial configuration of the 8-hydroxyquinoline ligand by grafting the 8-hydroxyquinoline on silica gel, provides the selective adsorption effect of the 8-hydroxyquinoline ligand on elements such as molybdenum, uranium and the like, and improves the saturated adsorption quantity of the molybdenum. The invention discovers through experiments that SiO 2 The adsorption process of the APTES-Quin to Mo (VI) accords with the isothermal adsorption formula of Langmuir and is single-layer chemical adsorption. SiO (SiO) 2 The saturated adsorption quantity of the APTES-Quin adsorbent to Mo (VI) is 203mg/g, which is more than 5 times of that of commercial alumina. SiO (SiO) 2 The adsorption process of APTES-Quin to Mo (VI) conforms to the quasi-second order kinetics, indicating that the adsorption process is controlled by chemical interactions. Mo (VI) can be eluted close to 100% at a time by an aqueous ammonia solution of 0.05M ammonium carbonate. At a temperature below 300 ℃, siO 2 APTES-Quin meets the thermal stability requirement. When the radiation absorption dose reaches 800kGy, siO 2 The adsorption percentage of APTES-Quin to Mo (VI) is reduced by not more than 1%, so that the irradiation stability can be better met.
Drawings
FIG. 1 is a SiO of the present invention 2 -AATAS-Quin adsorbent synthesis route.
FIG. 2 shows SiO at different pH values 2 Distribution ratio of APTES-Quin to Mo (VI), wherein the inner graph shows adsorption distribution ratio at higher acidity (adsorbent mass: 30.0mg; initial Mo (VI) concentration: 1.0mM; aqueous phase volume: 0.5mL; adsorption time: 2 h).
FIG. 3 shows SiO 2 APTES-Quin adsorbent was fitted to (a) adsorption kinetics and (b) quasi-second order kinetics models of Mo (VI) (adsorbent mass: 10.0mg; aqueous phase volume: 5mL; nitric acid concentration: 0.10M; mo (VI) initial concentration: 1300 ppm).
FIG. 4 shows SiO 2 APTES-Quin adsorbent was linearly fitted to Mo (VI) by (a) adsorption isotherms and (b) Langmuir adsorption isotherms (adsorbent mass: 10.0mg; aqueous phase volume: 10mL; nitric acid concentration: 0.10M; adsorption time: 2 h).
FIG. 5 is a graph of SiO at various absorbed doses 2 Percentage adsorption of Mo (VI) by APTES-Quin (adsorbent mass: 30.0mg; initial Mo (VI) concentration: 1.0mM; aqueous phase volume: 1.0mL; nitric acid concentration):0.10M; adsorption time: 2h) A. The invention relates to a method for producing a fibre-reinforced plastic composite
FIG. 6 is SiO 2 Column chromatography flow Curve of APTES-Quin (aqueous phase: 0.50mL of 0.10M nitric acid solution containing 125.0mg/L U (VI), 18.1mg/L Mo (VI), 27.1mg/L Zr (IV), 13.4mg/L Ru (III), 20.3mg/L Sr (II) and 26.1mg/L Ce (III; stationary phase: 0.200g SiO) 2 -APTES-Quin)
Detailed Description
The invention is illustrated in detail below by means of specific experiments, but in no way limits the scope of the invention.
Example 1
Materials and methods
(1)SiO 2 Synthesis method of-APTES-Quin adsorbent
20.0g of commercially available silica gel (SiO 2 ) To 200mL of hydrochloric acid solution (18.5%) was added, and the mixture was heated under reflux overnight to activate the silica gel surface. The silica gel was isolated by filtration and dried overnight in a vacuum oven. To a 100mL toluene suspension of 4.0g activated silica gel was added 4mL (3-aminopropyl) triethoxysilane (APTES), and the mixture was heated under reflux under argon for 72 hours to functionalize the silica gel surface to give SiO 2 APTES. Cooling to room temperature, filtering, and collecting SiO 2 APTES is washed sequentially with toluene, methanol, diethyl ether. Placing into a vacuum drying oven, and drying overnight. 2.0g of SiO 2 APTES was added to a solution of 3.0g of 8-hydroxyquinoline-2-carbaldehyde in DMF and refluxed at 135℃for 12 hours. After cooling to room temperature, filtration was performed. Washing the solid with DMF, methanol and diethyl ether sequentially, and drying overnight in a vacuum drying oven to obtain SiO 2 APTES-Quin adsorbent. The synthetic route is schematically shown in FIG. 1.
(2)SiO 2 APTES-Quin adsorption Effect test
At 25℃0.5mL of an aqueous phase containing uranium (1.0 mmol/L), molybdenum (1.0 mmol/L) and other split element ions (0.5 mmol/L) and 30mg of SiO were oscillated 2 The adsorption experiments were performed with APTES-Quin adsorbent. The adsorption time was about 1h to ensure adsorption equilibrium. Centrifuging at 4500rpm for 5min after adsorption, diluting the separated water phase to proper concentration, measuring the concentration of corresponding element by ICP-OES or ICP-MS, 131 the change in I concentration was measured by gamma counter.
(3) Distribution ratio K d (mL·g -1 ) Adsorption percentage E (%), selectivity factor SF
Calculated according to the following formula:
wherein C is 0 (mg·L -1 ) Is the concentration of metal ions in the aqueous solution before separation, C (mg.L -1 ) The concentration of metal ions in the separated aqueous solution is that V is the volume of water phase (mL), W is the mass of adsorbent (g), K d (M) and K d (N) represents the distribution ratio of M and N elements, respectively. Each experiment was repeated more than 4 times.
(II) results
(1) Acidity influence
Determination of SiO by varying the acidity of the aqueous phase 2 APTES-Quin has optimal adsorption effect on Mo (VI) under different acidity conditions. After changing the nitric acid concentration, the adsorption partition ratio (K) of Mo (VI) was measured d ) As shown in fig. 2. Experiments have found that as the pH increases from 0.3 to 8.0, the partitioning ratio of mo (VI) increases and then decreases, an optimum acidity condition occurs. Near ph=1.0 and 2.0, with the highest partition ratio, up to 10 4 On the order of magnitude.
(2) Adsorption kinetics and thermodynamics
Testing SiO at different time points 2 The adsorption amount of APTES-Quin to Mo (VI). The adsorption kinetics results are shown in FIG. 3. SiO (SiO) 2 The adsorption process rate of the APTES-Quin to Mo (VI) is faster, and the adsorption equilibrium can be reached in about 1 hour. Using quasi-first order kinetic models and quasi-The second order kinetic model fits the adsorption kinetic data. As shown in fig. 3, the adsorption kinetics conform to a quasi-secondary kinetics model (correlation coefficient R 2 =0.999), indicating that the adsorption process is mainly controlled by chemical action, not mass transfer action.
As shown in FIG. 4, siO was tested by varying the Mo (IV) concentration in the mother liquor 2 Adsorption isotherm of APTES-Quin to Mo (VI). And fitting a Langmuir adsorption model and a Freundlich adsorption model on the adsorption isothermal process, wherein the fitting result shows that the adsorption process is more in accordance with a Langmuir adsorption isothermal formula, and the adsorption process is single-layer chemical adsorption. The saturated adsorption amount was calculated by the amount of grafting to be about 228 mg.g -1 Langmuir adsorption isothermal predicted saturation adsorption amount was 243 mg.g -1 The saturated adsorption amount was found to be 203 mg.g -1 。SiO 2 The adsorption saturation quantity of the APTES-Quin to Mo (VI) is more than 5 times of that of commercial alumina, and the adsorption capacity requirement of the adsorbent can be better met.
Based on the experimental data, the optimized relevant flow parameters are as follows:
(1)SiO 2 nitric acid solution with optimal acidity of pH=1.0-2.0 when APTES-Quin adsorbs Mo (VI), and distribution ratio reaches 10 4 On the order of magnitude.
(2) SiO is actually observed 2 The saturated adsorption amount of APTES-Quin to Mo (VI) is 203 mg.g -1 Is more than 5 times of commercial alumina.
(3)SiO 2 The adsorption process rate of the APTES-Quin to Mo (VI) is faster, and the adsorption balance can be achieved for 1 hour at most.
Example 2
Materials and methods
(1) The materials and adsorption process were the same as in example 1;
(2) In desorption, 30.0mg of SiO after Mo (VI) was adsorbed 2 To the APTES-Quin adsorbent, 2.0mL of eluent was added and the mixture was shaken for 30 minutes. After shaking, the mixture was centrifuged to obtain 1.0mL of an aqueous phase, the organic matters were removed by nitro-lysis, and then the volume was set to 5mL for ICP-OES test. The aqueous phase containing ammonia water needs to be volatilized to dry the ammonia water, and then the nitrolysis is carried out to constant volume.
(II) results
To realize SiO 2 Elution of APTES-Quin adsorbed Mo (VI) A number of elution conditions were tested as shown in Table 1. In addition to adjusting the acidity and alkalinity, it is still necessary to increase the salinity or complexation of the eluate to increase the desorption capacity. The ammonium carbonate aqueous ammonia solution has the best eluting effect, and Mo (VI) is eluted almost once. The elution effect of the aqueous ammonium carbonate solution and the aqueous guanidine carbonate solution is inferior.
TABLE 1 SiO under different conditions 2 Elution Effect of APTES-Quin adsorption of Mo (VI)
Example 3
Materials and methods
(1) The material was the same as in example 1;
(2) In the irradiation experiment, the adsorbent and the water phase are jointly accepted 60 Co source irradiation, the irradiation dose is 200-800 kGy, adsorption experiment is carried out after irradiation, and the operation of the adsorption experiment is the same as that described above.
(II) results
To test SiO 2 Irradiation stability of APTES-Quin 30.0mg SiO 2 APTES-Quin with 1.0mL of 0.1M HNO containing 1.0mM Mo (VI) 3 The solutions are put together 60 And (5) Co source irradiation. After different doses are absorbed, siO 2 The decrease in adsorption effect of APTES-Quin on Mo (VI) was not significant, as shown in FIG. 5. At an absorbed dose of 800kGy, the adsorption percentage was only reduced by about 1%. In addition, the aqueous phase remained colorless and transparent after absorption of the higher dose radiation (400 kGy). The adsorption material has good irradiation stability and has potential to be used for the separation and purification of Mo (VI) in an actual strong irradiation environment.
Example 4
Materials and methods
(1) The material was the same as in example 1;
(2) Column test for simulating uranium target dissolution liquid, taking 0.200g SiO 2 APTES-Quin adsorbent, to which 0.1M HNO was added 3 After the solution, the chromatographic column is filled. The column was a glass column with a tap having an inner diameter of about 6 mm. 500. Mu.L of the simulated dissolution solution was taken and put on a column. Wherein, 0.10M HNO 3 The simulated uranium target dissolution liquid of (1) contains 125.0mg/L U (VI), 18.1mg/LMo (VI), 27.1mg/L Zr (IV), 13.4mg/L Ru (III), 20.3mg/L Sr (II) and 26.1mg/L Ce (III). After loading, the sample was taken up in 0.1M HNO 3 The solution is a mobile phase, and various impurity element ions are eluted. Then, mo (VI) was eluted with an aqueous ammonia solution of 0.05M ammonium carbonate as an eluent. The flow rate of the mobile phase is about 0.35 mL/min -1 。
(II) results
To further explore SiO 2 Dynamic separation and purification effect of APTES-Quin on Mo (VI), we performed a column separation test, as shown in FIG. 6. After loading, 0.10M HNO was used first 3 The solution was used as the mobile phase, where Mo (VI) was substantially completely adsorbed on the column, while U (VI) and Sr (II), ru (III) and Ce (III) rapidly flowed out with the effluent in large amounts. About 8.0mL of 0.10M HNO was used 3 After the eluent, the metal ions of U (VI), sr (II), ru (III) and Ce (III) are completely eluted, and no metal ions exist in the eluent.
Mo (VI) was then eluted using an aqueous ammonia solution of 0.05M ammonium carbonate. Zr (IV) is not eluted during the whole process. The main reason is that the silica gel can efficiently adsorb Zr (IV) under the acidic condition, the Zr (IV) is extremely easy to hydrolyze, and the Zr (IV) is easy to precipitate under the alkaline condition and can not be eluted and dissolved effectively.
It should be noted that the purpose of the disclosed embodiments is to aid further understanding of the present invention, but those skilled in the art will appreciate that: various alternatives and modifications are possible without departing from the spirit and scope of the invention and the appended claims. Therefore, the invention should not be limited to the disclosed embodiments, but rather the scope of the invention is defined by the appended claims.
Claims (10)
1. A method for separating molybdenum from nitric acid solution containing uranium and splinter elements comprises the steps of firstly chemically grafting 8-hydroxyquinoline onto silica gel through a silane coupling agent to prepare a hydroxyquinoline grafted silica gel material, and then selectively adsorbing molybdenum from the nitric acid solution containing uranium and splinter elements by utilizing the material.
2. The method according to claim 1, wherein the silica gel has a specific surface area of 150 to 1500m 2 /g。
3. The method according to claim 1, wherein the hydroxyquinoline grafted silica gel material, designated as SiO, is prepared by two-step chemical grafting of a (3-aminoalkyl) trialkoxysilane and 8-hydroxyquinoline using an inorganic silica gel as a substrate material 2 AATAS-Quin, the chemical structure of which is shown in formula I:
in the formula I, a is an integer of 1-12, and b is an integer of 1-12.
4. A method according to claim 3, wherein the (3-aminoalkyl) trialkoxysilane is (3-aminopropyl) triethoxysilane.
5. The method of claim 3, wherein the preparation of the hydroxyquinoline grafted silica gel material of formula I is: adding silica gel into hydrochloric acid solution, heating and refluxing overnight to activate the surface of the silica gel; separating the activated silica gel by filtration and drying; adding (3-aminoalkyl) trialkoxysilane into the suspension of activated silica gel, heating and refluxing under the protection of argon gas for reaction, cooling to room temperature after the reaction is finished, filtering, washing and drying to obtain a graft SiO 2 AATAS; to be grafted with SiO 2 Reflux reaction of AATAS and 8-hydroxyquinoline-2-formaldehyde in organic solvent, cooling to room temperature after the reaction, filtering, washing and drying to obtain the hydroxyquinoline grafted silica gel material shown in the formula I.
6. The method of claim 5, wherein the suspension of activated silica gel is activated silica gelToluene suspension; graft SiO 2 The reflux reaction of AATAS and 8-hydroxyquinoline-2-carbaldehyde in N, N-dimethylformamide.
7. The method of claim 1, wherein separating molybdenum from the uranium and fissile element-containing nitric acid solution using a hydroxyquinoline grafted silica gel material comprises the steps of:
1) The silica gel material grafted by the hydroxyquinoline is used as an adsorbent to adsorb molybdenum in nitric acid solution containing uranium and splinter elements, while the uranium and other splinter elements are not adsorbed;
2) Desorbing the adsorbent obtained in the step 1) to obtain an elution solution containing molybdenum.
8. The method according to claim 7, wherein in step 1), 0.01 to 1.5g/L of adsorbent is used per liter of the nitric acid solution, and the pH of the nitric acid solution is 1.0 to 2.0.
9. The method of claim 7, wherein the adsorption operation of step 1) is to add the hydroxyquinoline grafted silica gel material to the nitric acid solution, shake mix and then stand for a period of time, or to flow the nitric acid solution through an adsorption column filled with the hydroxyquinoline grafted silica gel material.
10. The method according to claim 7, wherein the desorption solution of step 2) is an aqueous ammonia solution of ammonium carbonate, a guanidine carbonate solution or an ammonium carbonate solution, preferably an aqueous ammonia solution containing 0.05M ammonium carbonate.
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