CN114452951B - Phenol formaldehyde aerogel rubidium/cesium specific adsorbent and preparation method and application thereof - Google Patents
Phenol formaldehyde aerogel rubidium/cesium specific adsorbent and preparation method and application thereof Download PDFInfo
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- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 61
- 229910052701 rubidium Inorganic materials 0.000 title claims abstract description 61
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 title claims abstract description 61
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000003463 adsorbent Substances 0.000 title claims abstract description 55
- 239000004964 aerogel Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 title abstract description 11
- 229920001568 phenolic resin Polymers 0.000 title abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- 238000000352 supercritical drying Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 239000012267 brine Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 17
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- AZVSIHIBYRHSLB-UHFFFAOYSA-N 3-furaldehyde Chemical compound O=CC=1C=COC=1 AZVSIHIBYRHSLB-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- -1 cesium ions Chemical class 0.000 abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 34
- 238000000926 separation method Methods 0.000 description 9
- 238000002336 sorption--desorption measurement Methods 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000002210 supercritical carbon dioxide drying Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000010410 calcium alginate Nutrition 0.000 description 1
- 239000000648 calcium alginate Substances 0.000 description 1
- 229960002681 calcium alginate Drugs 0.000 description 1
- 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 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002332 oil field water Substances 0.000 description 1
- 229910001744 pollucite Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- 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
- B01J20/28047—Gels
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- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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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
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- B01J20/28054—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 surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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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
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- B01J20/28078—Pore diameter
- B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a phenol formaldehyde aerogel rubidium/cesium specific adsorbent, a preparation method and application thereof, wherein the adsorbent contains a phenol oxygen anion group, and the group has high selectivity on rubidium and cesium ions; the preparation method comprises the following steps: (1) Dissolving a phenolic monomer and an aldehyde monomer in deionized water to obtain a transparent solution, adding a catalyst into the solution, stirring for 0.5-2 h, and standing to obtain phenolic gel; (2) Immersing the phenolic gel obtained in the step (1) in a strong alkali solution for 5-24 hours to convert phenolic hydroxyl functional groups in the phenolic gel into phenolic negative ions, then immersing the phenolic gel in absolute ethyl alcohol for 3-6 times, and finally performing carbon dioxide supercritical drying on the gel to obtain the rubidium/cesium specific adsorbent of the phenolic aerogel. The adsorbent prepared by the invention has a three-dimensional porous network structure, large specific surface area and high adsorption quantity of rubidium and cesium.
Description
Technical Field
The invention belongs to the technical field of adsorbent preparation, relates to preparation of rubidium/cesium adsorbents, and particularly relates to a phenol formaldehyde aerogel rubidium/cesium specific adsorbent, and a preparation method and application thereof.
Background
Rubidium (Rb) and cesium (Cs) are extremely important metal resources and have important applications in numerous fields such as medical treatment, photovoltaic devices, catalysis, and the like. In nature, in addition to solid minerals such as lepidolite and pollucite, rubidium and cesium are also present in liquid resources such as salt lake brine, geothermal water and oilfield water, for example, the average rubidium content in the salt lake brine of the fandard of Qinghai province is 10. mg.L -1 Cesium-containing 0.034 mg.L -1 The total reserve is considerable and the development value is high.
At present, separation and extraction of rubidium and cesium from salt lake brine mainly comprise a precipitation method, an extraction method and an adsorption method. The precipitation method is unsuitable for low concentration Rb in salt lake brine due to poor separation effect, low product purity, low yield and high production cost + 、Cs + Is separated and extracted. Although the extraction method can rapidly separate Rb + 、Cs + However, some of the extractant and diluent may be mixed into the aqueous phase during the extraction process, which is not only highly corrosive to equipment, but also causes environmental pollution.
The adsorption method has the advantages of high recovery rate, low pollution, low energy consumption and the like, and is suitable for separating and extracting low-concentration target ions in salt lake brine. Phosphomolybdates, phosphotungstates, arsenicolybdates, silicomolybdates and the likeThe polyacrylate has a Keggin structure, has high adsorption selectivity to rubidium and cesium, is easy to desorb, and can be completed simultaneously with regeneration. However, heteropolyacid salts are microcrystalline, have poor mechanical properties, and are difficult to mold. Sun et al (C.Y. Sun, F.Zhang, J.F. Cao, J.Colid. Interf. Sci., 2015, 455, 39-45.) use zeolite as carrier, and the composite adsorbent prepared by coating ammonium phosphomolybdate powder in the network structure of zeolite can efficiently separate Cs + But at Na + 、K + In salt lake brine systems with higher concentrations, the zeolite carriers can greatly reduce the concentration of Cs + The adsorption selectivity of the catalyst also leads to the increase of mass transfer resistance in the adsorption and desorption process. Deng et al (H. Deng, Y. X. Li, Y. Huang, X. Ma, L. Wu, T.H. Cheng, chem. Eng. J., 2016, 286, 25-35.) supported ammonium phosphomolybdate powder in silica gel to give a composite adsorbent effective in separating Cs + . Guo et al (T.Guo, S.Yun, L.He, Q.Li, Z.J. Wu, desalin. Water Treat., 2018, 104, 257-262.) prepared a spherical composite adsorbent of calcium alginate gel/ammonium phosphotungstate by sol-gel method. The heteropolyacid salt is only wrapped in the gel, has poor binding force with the gel carrier, and is easy to fall off from the gel carrier, so that the adsorption performance is reduced.
Therefore, in order to realize separation and extraction of rubidium and cesium in salt lake brine, a specific adsorbent which is simple in process, suitable for salt lake brine and has high-efficiency adsorption performance on rubidium and cesium needs to be developed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the phenol formaldehyde aerogel rubidium/cesium specific adsorbent which contains a phenol oxygen anion group, has high selectivity to rubidium and cesium ions and has excellent adsorption performance; meanwhile, the adsorbent has a three-dimensional network porous structure, has large specific surface area and large adsorption capacity to rubidium and cesium; the invention also aims at providing a preparation method and application of the adsorbent.
The invention is realized by the following technical scheme:
a phenol-formaldehyde aerogel rubidium/cesium specific adsorbent containing a phenol oxygen anion group (ph-O - ) Has three-dimensional nano-pore structure with specific surface area exceeding that of600 m 2 And/g, wherein the pore size distribution is 2-200 nm.
The invention further improves the scheme as follows:
the preparation method of the phenol formaldehyde aerogel rubidium/cesium specific adsorbent comprises the following steps:
(1) Dissolving a phenolic monomer and an aldehyde monomer in deionized water to obtain a transparent solution, adding a catalyst into the solution, stirring for 0.5-2 h, and standing to obtain phenolic gel;
(2) Immersing the phenolic gel obtained in the step (1) in a strong alkali solution for 5-24 hours to convert phenolic hydroxyl functional groups in the phenolic gel into phenolic negative ions, then immersing the phenolic gel in absolute ethyl alcohol for 3-6 times, and finally performing carbon dioxide supercritical drying on the gel to obtain the rubidium/cesium specific adsorbent of the phenolic aerogel.
Further, in the step (1), the molar ratio of the phenolic monomer to formaldehyde to the catalyst to deionized water is 1:2-4:0.005-0.01:10-30.
Further, in the step (1), the phenolic monomer is one or more of phenol, o-cresol, p-cresol, m-cresol or resorcinol.
Further, in the step (1), the aldehyde monomer is one or more of formaldehyde, furfural, 5-methylfurfural, 2-furfural or 3-furfural.
Further, in the step (1), the catalyst is one or more of sodium bicarbonate solution, sodium carbonate solution, sodium hydroxide solution or hydrochloric acid solution, and the concentration of each solution is 0.1 mol/L-1.0 mol/L.
Further, in the step (2), the strong alkali solution is one or two of sodium hydroxide solution and potassium hydroxide solution, and the mass percentage concentration of the strong alkali solution is 1% -10%.
The invention further improves the scheme as follows:
application of the phenol formaldehyde aerogel rubidium/cesium specific adsorbent in adsorption extraction of rubidium and cesium in salt lake brine. The adsorption capacity of the adsorbent to rubidium and cesium can reach 240 mg/g, and after more than 10 adsorption-desorption cycles, the adsorption capacity of the adsorbent to rubidium and cesium can reach 220 mg/g.
The beneficial effects of the invention are as follows:
the phenol formaldehyde aerogel rubidium/cesium specific adsorbent contains a phenol oxygen anion group, has high selectivity on rubidium and cesium ions, and is suitable for specific adsorption separation of rubidium and cesium in salt lake brine containing various interference ions.
The phenol formaldehyde aerogel rubidium/cesium specific adsorbent has a three-dimensional porous network structure, large specific surface area and high adsorption quantity of rubidium and cesium; the phenol formaldehyde aerogel rubidium/cesium specific adsorbent belongs to a nano three-dimensional porous solid material, and has no volatility and no pollution to the atmosphere compared with liquid rubidium/cesium extractants.
Drawings
FIG. 1 is a graph showing the nitrogen adsorption-desorption curve of the adsorbent prepared in example 1;
FIG. 2 is a graph showing pore size distribution of the adsorbent prepared in example 2;
FIG. 3 is a scanning electron microscope image of the adsorbent prepared in example 3;
as can be seen from fig. 1 to 3, the adsorbents prepared according to the present invention have a three-dimensional network porous structure and have a high specific area, and these characteristics can impart excellent adsorption performance to the adsorbents.
Detailed Description
Example 1
Dissolving phenol and formaldehyde in deionized water to obtain a transparent solution, adding sodium bicarbonate into the solution, stirring for 2 h, and standing to obtain phenolic gel, wherein the molar ratio of the phenol to the formaldehyde to the sodium bicarbonate to the deionized water is 1:2:0.005:10.
Immersing the phenolic gel in sodium hydroxide solution for 5 h to convert phenolic hydroxyl functional groups in the phenolic gel into phenolic oxyanions, then immersing the phenolic gel in absolute ethyl alcohol for 3 times, and finally carrying out supercritical carbon dioxide drying on the gel to obtain the specific adsorbent of the phenolic aerogel rubidium and cesium.
Weighing the adsorbent prepared by 2 g into 50 mL salt lake brine, wherein Li is contained in the salt lake brine + 、Na + 、K + 、Rb + 、Cs + 、Mg 2 + 、Ca 2+ The concentrations of (C) were 24.50 g/L, 25.42 g/L, 28.62 g/L, 0.90 g/L, 0.75 g/L, 21.73 g/L, 10.05 g/L, respectively, and static adsorption experiments were performed in a constant temperature water bath shaker at 25 ℃. The specific surface area of the adsorbent is 800 m 2 And/g, wherein the pore size distribution is 2-120 nm, the adsorption capacity of rubidium and cesium is 200 mg/g, and after 10 times of adsorption-desorption separation are carried out to extract rubidium and cesium from salt lake brine, the adsorption capacity of the adsorbent to rubidium and cesium is 190 mg/g.
Example 2
Dissolving resorcinol and formaldehyde in deionized water to obtain a transparent solution, adding sodium carbonate into the solution, stirring for 1 h, and standing to obtain phenolic gel, wherein the mol ratio of resorcinol to formaldehyde to sodium carbonate to deionized water is 1:2.5:0.01:20.
Immersing the phenolic gel in a sodium hydroxide solution for 10 h to convert phenolic hydroxyl functional groups in the phenolic gel into phenolic oxyanions, then immersing the phenolic gel in absolute ethyl alcohol for 3 times, and finally performing supercritical carbon dioxide drying on the gel to obtain the specific adsorbent of the phenolic aerogel rubidium and cesium.
The specific surface area of the prepared adsorbent is 600 m 2 And/g, wherein the pore size distribution is 50-200 nm, the adsorption capacity of rubidium and cesium is 170 mg/g, and after 10 times of cyclic adsorption-desorption separation and extraction of rubidium and cesium in salt lake brine, the adsorption capacity of the adsorbent for rubidium and cesium is 150 mg/g.
Example 3
Dissolving resorcinol and furfural in deionized water to obtain a transparent solution, adding sodium carbonate into the solution, stirring for 1 h, and standing to obtain phenolic gel, wherein the mol ratio of resorcinol to furfural to sodium carbonate to deionized water is 1:4:0.01:30.
Immersing the phenolic gel in a sodium hydroxide solution for 10 h to convert phenolic hydroxyl functional groups in the phenolic gel into phenolic oxyanions, then immersing the phenolic gel in absolute ethyl alcohol for 6 times, and finally performing carbon dioxide supercritical drying on the gel to obtain the specific adsorbent of the phenolic aerogel rubidium and cesium.
The specific surface area of the prepared adsorbent is 1000 m 2 Per g, the pore size distribution is 2-100 nm, the adsorption capacity to rubidium and cesium is 240 mg/g, and 10 times of cyclic adsorption-desorption separation are carried out to extract rubidium from salt lake brineAfter cesium, the adsorption amount of rubidium and cesium by the adsorbent was 220 mg/g.
Example 4
Dissolving o-cresol and 2-furfural in deionized water to obtain a transparent solution, adding hydrochloric acid into the solution, stirring for 0.5: 0.5 h, and standing to obtain phenolic gel, wherein the molar ratio of the o-cresol to 2-furfural to the hydrochloric acid to the deionized water is 1:4:0.01:15.
Immersing phenolic gel in sodium hydroxide solution for 8 h to convert phenolic hydroxyl functional groups in the phenolic gel into phenolic oxyanions, then immersing the phenolic gel in absolute ethyl alcohol for 6 times, and finally performing supercritical carbon dioxide drying on the gel to obtain the specific adsorbent of the phenolic aerogel rubidium and cesium.
The specific surface area of the prepared adsorbent is 850 m 2 And/g, wherein the pore size distribution is 10-100 nm, the adsorption capacity of rubidium and cesium is 210 mg/g, and after 10 times of cyclic adsorption-desorption separation are carried out to extract rubidium and cesium from salt lake brine, the adsorption capacity of the adsorbent to rubidium and cesium is 200 mg/g.
Example 5
Dissolving resorcinol and 5-methylfurfural in deionized water to obtain a transparent solution, adding sodium hydroxide into the solution, stirring for 0.8: 0.8 h, and standing to obtain phenolic gel, wherein the mol ratio of resorcinol to 5-methylfurfural to sodium hydroxide to deionized water is 1:4:0.005:20.
Immersing the phenolic gel in a sodium hydroxide solution for 10 h to convert phenolic hydroxyl functional groups in the phenolic gel into phenolic oxyanions, then immersing the phenolic gel in absolute ethyl alcohol for 5 times, and finally performing carbon dioxide supercritical drying on the gel to obtain the specific adsorbent of the phenolic aerogel rubidium and cesium.
The prepared adsorbent has specific surface area of 700 m 2 And/g, wherein the pore size distribution is 2-150 nm, the adsorption capacity of rubidium and cesium is 185-mg/g, and the adsorption capacity of the adsorbent to rubidium and cesium is 170-mg/g after 10 times of cyclic adsorption-desorption separation and extraction of rubidium and cesium in salt lake brine.
Claims (7)
1. The preparation method of the phenolic aerogel rubidium/cesium adsorbent is characterized by comprising the following steps of:
(1) Dissolving a phenolic monomer and an aldehyde monomer in deionized water to obtain a transparent solution, adding a catalyst into the solution, stirring for 0.5-2 h, and standing to obtain phenolic gel;
(2) Immersing the phenolic gel obtained in the step (1) in a strong alkali solution for 5-24 hours to convert phenolic hydroxyl functional groups in the phenolic gel into phenolic negative ions, then immersing the phenolic gel in absolute ethyl alcohol for 3-6 times, and finally performing carbon dioxide supercritical drying on the gel to obtain a rubidium/cesium adsorbent of the phenolic aerogel;
the prepared adsorbent contains phenolic oxygen anion groups and has a three-dimensional nano-pore structure, and the specific surface area exceeds 600 m 2 And/g, wherein the pore size distribution is 2-200 nm.
2. The method for preparing the phenolic aerogel rubidium/cesium adsorbent according to claim 1, wherein the method comprises the following steps: in the step (1), the molar ratio of the phenolic monomer to formaldehyde to the catalyst to the deionized water is 1:2-4:0.005-0.01:10-30.
3. The method for preparing the phenolic aerogel rubidium/cesium adsorbent according to any one of claims 1 or 2, wherein the method comprises the following steps: in the step (1), the phenolic monomer is one or more than two of phenol, o-cresol, p-cresol, m-cresol or resorcinol.
4. The method for preparing the phenolic aerogel rubidium/cesium adsorbent according to claim 1, wherein the method comprises the following steps: in the step (1), the aldehyde monomer is one or more than two of formaldehyde, furfural, 5-methylfurfural or 3-furfural.
5. The method for preparing the phenolic aerogel rubidium/cesium adsorbent according to any one of claims 1 or 2, wherein the method comprises the following steps: in the step (1), the catalyst is one or more than two of sodium bicarbonate solution, sodium carbonate solution, sodium hydroxide solution or hydrochloric acid solution, and the concentration of each solution is 0.1 mol/L-1.0 mol/L.
6. The method for preparing the phenolic aerogel rubidium/cesium adsorbent according to claim 1, wherein the method comprises the following steps: in the step (2), the strong alkali solution is one or two of sodium hydroxide solution and potassium hydroxide solution, and the mass percentage concentration of the strong alkali solution is 1% -10%.
7. The use of the phenolic aerogel rubidium/cesium adsorbent prepared by the method of claim 1 in adsorption extraction of rubidium and cesium in salt lake brine.
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