CN106975470A - A kind of preparation method and applications of porous AMP/CNC PUF sorbing materials - Google Patents
A kind of preparation method and applications of porous AMP/CNC PUF sorbing materials Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 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 claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- -1 cesium ions Chemical class 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 238000005067 remediation Methods 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000003463 adsorbent Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 238000009775 high-speed stirring Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 9
- 239000011609 ammonium molybdate Substances 0.000 claims description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 9
- 210000002421 cell wall Anatomy 0.000 claims description 9
- 238000010907 mechanical stirring Methods 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 9
- 239000011496 polyurethane foam Substances 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical group C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 5
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 238000005187 foaming Methods 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000011109 contamination Methods 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 238000004873 anchoring Methods 0.000 claims 1
- 239000000839 emulsion Substances 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 26
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 abstract description 16
- 230000002285 radioactive effect Effects 0.000 abstract description 6
- 229910052701 rubidium Inorganic materials 0.000 abstract description 5
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 239000002689 soil Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 3
- 239000002775 capsule Substances 0.000 abstract 1
- 230000007812 deficiency Effects 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000648 calcium alginate Substances 0.000 description 4
- 235000010410 calcium alginate Nutrition 0.000 description 4
- 229960002681 calcium alginate Drugs 0.000 description 4
- 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 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 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 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 101100379081 Emericella variicolor andC gene Proteins 0.000 description 1
- XLLACKJGEOHZOV-UHFFFAOYSA-N [O-2].[Ce+3].[Cs+].[O-2] Chemical compound [O-2].[Ce+3].[Cs+].[O-2] XLLACKJGEOHZOV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B01J20/26—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
- B01J20/02—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
- B01J20/0274—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 characterised by the type of anion
- B01J20/0292—Phosphates of compounds other than those provided for in B01J20/048
-
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of preparation method and applications of porous AMP/CNC PUF sorbing materials, belong to nano composite material and repair field with environmental pollution.In order to overcome ammonium phosphomolybdate bad mechanical strength in the prior art, hardly possible shaping is reclaimed, use it for the technical deficiency of complex treatment process during to radioactive element rubidium, caesium absorption, the preparation method and applications of the porous AMP/CNC PUF sorbing materials of offer of the present invention, it is by the way that ammonium phosphomolybdate is carried on nanometer carbon particles, then capsule obtains sorbing material among being loaded on polyurathamc sponge, not only so that the aftertreatment technology of absorption simplifies, and absorption active site can be fully exposed, adsorption efficiency is improved.Prepared composite is used for the reparation that the cesium ions such as water body, soil pollute environment, is had broad application prospects in nuclear pollution environment remediation field.
Description
Technical Field
The invention relates to a preparation method and application of a porous AMP/CNC-PUF adsorbing material, and belongs to the field of nano composite materials and environmental pollution remediation.
Background
With the rapid development of the world economy, the energy crisis gradually emerges. Nuclear energy has become an important component in the world's energy supply due to its unique advantages of economy, cleanliness and high efficiency, making a great contribution to the development of the world's economy, but also bringing about a significant problem of environmental nuclear pollution. Cs-137 and Cs-134 are two isotopes of radioactive cesium with half-lives of 30 years and 2.06 years, respectively. These radioisotopes produce strongly radiating gamma rays during decay, releasing high-energy beta particles, which are the cause of radioactive nuclear contamination. Finding a material and method to selectively remove cesium ions from high concentrations of coexisting ions is a problem that is currently in need of resolution.
Ammonium phosphomolybdate (AMP) is a compound which is cheap, efficient and has high selective adsorption capacity to cesium, and has been used as a enrichment agent for industrial radioactive cesium and rubidium. However, the AMP prepared by the traditional method has a fine powder microcrystalline structure, has poor hydraulic property and is difficult to elute and pack in a column; further, it is very difficult to recover and treat such microcrystals by filtration, centrifugation or the like after they are used for adsorption. The nanocarbon material has an enormous specific surface area, excellent physical/chemical properties, light weight, high tensile strength, coexistence of conductor/semiconductor properties, and other excellent properties, and has been widely noticed and expected by researchers. So far, the synthesis of the nanocarbon loaded ammonium phosphomolybdate encapsulated in polyurethane sponge composite material has not been reported.
Chinese patent application 2009100218782 provides a calcium alginate embedded ammonium phosphomolybdate composite adsorbent, which is prepared by dissolving ammonium phosphomolybdate in water to form ammonium phosphomolybdate suspension with the mass percent of 2-4%; adding sodium alginate with the mass of 0.3-2 times that of the ammonium phosphomolybdate, and stirring to fully mix; then, dripping the mixture into a calcium chloride solution with the mass percentage of 3-10%, and reacting for 12-48 hours to obtain a spherical product; separating, washing with distilled water, and drying to obtain the calcium alginate embedded ammonium phosphomolybdate composite adsorbent. The composite adsorbent is structurally characterized in that ammonium phosphomolybdate is used as a core substance, calcium alginate is used as an embedded egg-shaped sphere with the diameter of 2-5 mm, the mass ratio of the calcium alginate to the ammonium phosphomolybdate is 1: 2-3: 1, the water content is 90-97%, and the density is 0.4-0.6 g/ml < -1 >. The composite adsorbent has good adsorption performance on rubidium and cesium in an alkali metal ion mixed solution, and can be applied to adsorption separation and removal of rubidium and cesium ions from various solution systems.
According to the preparation method, the AMP is controllably anchored on the surface of the nano-carbon material (AMP/CNC) by utilizing the ultra-large specific surface area and the stable chemical/physical characteristics of the nano-carbon material, and the powdery AMP/CNC is compounded with the foamed polyurethane to prepare the three-dimensional high-performance cesium adsorption material for the foamed polyurethane sponge (PUF). The encapsulation technology of gradual assembly integrates the characteristic of high selective adsorption of the nano ammonium phosphomolybdate to cesium ions and the characteristic of easy recovery of macroscopic materials, and has wide application prospect in the fields of nuclear pollution treatment and the like.
Disclosure of Invention
In order to overcome the technical defects that ammonium phosphomolybdate in the prior art is poor in mechanical strength and difficult to form and recycle, and the treatment process is complex when the ammonium phosphomolybdate is used for adsorbing radioactive elements rubidium and cesium, the invention provides a preparation method of a three-dimensional high-performance cesium adsorption material which is prepared by loading ammonium phosphomolybdate nano particles on the nano carbon particles and encapsulating the nano particles in foamed polyurethane sponge.
The invention realizes the technical effects through the following technical scheme:
the invention provides a nano-carbon loaded ammonium phosphomolybdate composite material encapsulated in foamed polyurethane sponge, namely a porous AMP/CNC-PUF adsorbing material.
Specifically, the preparation method of the porous AMP/CNC-PUF adsorbing material comprises the following steps:
1) preparing an ammonium phosphomolybdate nano carbon composite material: ultrasonically dispersing nano carbon particles into deionized water to obtain a nano carbon suspension; adding ammonium molybdate aqueous solution into the nano carbon suspension under mechanical stirring, continuing to perform ultrasonic stirring for 20-30min, adding phosphoric acid, and adjusting the pH of the mixed solution to 0.5-1.5 by using concentrated nitric acid; continuously stirring for 1-2 h at room temperature, aging for 18-22 h at room temperature, performing centrifugal separation, washing for 2-4 times by using 1 mol/L nitric acid, washing for 2-4 times by using deionized water, and drying for 5-7h at 40-50 ℃ to obtain an ammonium phosphomolybdate nano-carbon composite material;
2) preparation of porous AMP/CNC-PUF adsorbing material: and (2) carrying out foaming polymerization on the ammonium phosphomolybdate nano-carbon composite material, the polyurethane prepolymer and the foam stabilizer according to the volume ratio of 8-12:100:1 under the condition of high-speed stirring, so that the ammonium phosphomolybdate nano-carbon composite material is fixed on the cell wall of polyurethane foam, washing for 2-4 times by using deionized water, and drying for 5-7h at the temperature of 40-50 ℃ to obtain the porous AMP/CNC-PUF adsorbing material.
Preferably, in the preparation method of the porous AMP/CNC-PUF adsorbing material, the nano-carbon particles are graphene oxide or carbon nanotubes.
Preferably, in the preparation method of the porous AMP/CNC-PUF adsorbing material, the mass ratio of the nano-carbon particles to the deionized water in the nano-carbon ultra-biological dispersion process in the step 1) is 1: 2000.
Preferably, in the preparation method of the porous AMP/CNC-PUF adsorbing material, the ultrasonic power in the ultrasonic dispersion and ultrasonic stirring processes in the step 1) is 360-630W, and more preferably 450-540W.
Preferably, in the preparation method of the porous AMP/CNC-PUF adsorbing material, the polyurethane prepolymer is obtained by reacting polyisocyanate and polyol, the foam stabilizer is one or more of emulsified silicone oil, a higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane, more preferably, the polyurethane prepolymer is NB-9000B, and the foam stabilizer is Pluronic L-62.
Preferably, in the preparation method of the porous AMP/CNC-PUF adsorbing material, the rotation speed of the high-speed stirring in the step 2) is 2000-.
As a preferred embodiment of the present invention, the preparation method of the porous AMP/CNC-PUF adsorption material specifically comprises the following steps:
1) ultrasonically dispersing 50 mg of nano graphene oxide or carbon nano tube into 100 mL of deionized water; rapidly adding an aqueous solution dissolved with 3 mmol of ammonium molybdate into the graphene oxide suspension under mechanical stirring, continuously stirring and ultrasonically treating for 20 min, adding 2.5 mmol of phosphoric acid, and adjusting the pH value of the mixed solution to 1 by using concentrated nitric acid; stirring the mixed solution at room temperature for 1.5 h, then aging at room temperature for 20h, performing centrifugal separation, washing with 1 mol/L nitric acid for 3 times, then washing with deionized water for 3 times, and drying at 40 ℃ for 6h to obtain the composite material AMP/CNC;
2) AMP/CNC, NB-9000B and Pluronic L-62 were foam-polymerized (> 2000 r/min) at a volume ratio of 10:100:1 under high-speed stirring, AMP/CNC was immobilized on the cell walls of the polyurethane foam, washed 3 times with deionized water, and dried at 40 ℃ for 6 hours to obtain a porous AMP/CNC-PUF adsorbing material.
The ammonium phosphomolybdate nano carbon polyurethane sponge composite material prepared by the invention is used for repairing cesium ion polluted environments such as water, soil and atmosphere, and the removal rate of cesium in the polluted environments with medium and low concentration can reach more than 97%. Based on the method, the invention also requests to protect the application of the composite adsorption material in the remediation of the environmental pollution caused by cesium ions.
The ammonium phosphomolybdate nano carbon polyurethane sponge composite material provided by the invention is different from the materials reported before, has a large specific surface, and has a three-dimensional network structure with good permeability in water. The method adopts a self-assembly technology, and the ammonium phosphomolybdate nano particles are anchored on the carbon nano material with the oversized specific surface in situ, so that the bonding force is strong and the ammonium phosphomolybdate nano particles are not easy to fall off; the nano-material is encapsulated in the vesicle of the foaming polyurethane sponge, so that the macroscopic view of the microscopic nano-material is realized, and the nano-material is easy to put in and recycle; has the advantages of easily available raw materials, simple and rapid method and suitability for popularization and application. Due to the large specific surface, high cesium selectivity and good liquid permeability, the cesium cerium oxide has a good application.
Detailed Description
The invention is further described below by means of specific examples, which are known to the person skilled in the art and which do not limit the scope of protection of the patent in any way.
Embodiment 1 preparation method of porous AMP/CNC-PUF adsorbing material
Ultrasonically dispersing 50 mg of nano graphene oxide into 100 mL of deionized water; rapidly adding an aqueous solution dissolved with 3 mmol of ammonium molybdate into the graphene oxide suspension under mechanical stirring, continuously stirring and ultrasonically treating for 20 min, adding 2.5 mmol of phosphoric acid, and adjusting the pH value of the mixed solution to 1 by using concentrated nitric acid; and stirring the mixed solution at room temperature for 1.5 h, then aging at room temperature for 20h, performing centrifugal separation, washing with 1 mol/L nitric acid for 3 times, then washing with deionized water for 3 times, and drying at 40 ℃ for 6h to obtain the composite material AMP/CNC.
AMP/CNC, NB-9000B and Pluronic L-62 were foam-polymerized at a volume ratio of 10:100:1 (3000 r/min) under high-speed stirring, AMP/CNC was fixed to the cell walls of the polyurethane foam, washed 3 times with deionized water, and dried at 40 ℃ for 6 hours to obtain a porous AMP/CNC-PUF adsorbing material. Wherein the ultrasonic power in the ultrasonic dispersion and ultrasonic stirring processes in the step 1) is 480W,
embodiment 2 preparation method of porous AMP/CNC-PUF adsorbing material
Ultrasonically dispersing 50 mg of carbon nano tubes into 100 mL of deionized water; rapidly adding the aqueous solution dissolved with 3 mmol of ammonium molybdate into the carbon nano tube suspension under mechanical stirring, continuously stirring and ultrasonically treating for 25 min, adding 2.5 mmol of phosphoric acid, and adjusting the pH value of the mixed solution to 0.5 by using concentrated nitric acid; and stirring the mixed solution at room temperature for 1 h, then aging at room temperature for 18 h, performing centrifugal separation, washing with 1 mol/L nitric acid for 2 times, then washing with deionized water for 2 times, and drying at 40 ℃ for 5h to obtain the composite material AMP/CNC.
AMP/CNC, NB-9000B and polyoxypropylene glycerol ether were subjected to foam polymerization (2000 r/min) at a volume ratio of 9:100:1 with high-speed stirring, AMP/CNC was immobilized on cell walls of the polyurethane foam, washed 2 times with deionized water, and dried at 40 ℃ for 5 hours to obtain a porous AMP/CNC-PUF adsorbing material.
Embodiment 3 preparation method of porous AMP/CNC-PUF adsorbing material
Ultrasonically dispersing 50 mg of nano graphene oxide into 100 mL of deionized water; rapidly adding an aqueous solution dissolved with 3 mmol of ammonium molybdate into the graphene oxide suspension under mechanical stirring, continuously stirring and ultrasonically treating for 30min, adding 2.5 mmol of phosphoric acid, and adjusting the pH value of the mixed solution to 1.5 by using concentrated nitric acid; and stirring the mixed solution at room temperature for 2 h, then aging at room temperature for 22 h, performing centrifugal separation, washing with 1 mol/L nitric acid for 4 times, then washing with deionized water for 4 times, and drying at 50 ℃ for 5h to obtain the composite material AMP/CNC.
AMP/CNC, NB-9000B and polyoxyethylene polyoxypropylene ether were foam-polymerized at a volume ratio of 11:100:1 (5000 r/min) with high-speed stirring, AMP/CNC was immobilized on cell walls of the polyurethane foam, washed 4 times with deionized water, and dried at 50 ℃ for 5 hours to obtain a porous AMP/CNC-PUF adsorbing material.
Embodiment 4 preparation method of porous AMP/CNC-PUF adsorbing material
Ultrasonically dispersing 50 mg of nano graphene oxide into 100 mL of deionized water; rapidly adding an aqueous solution dissolved with 3 mmol of ammonium molybdate into the graphene oxide suspension under mechanical stirring, continuously stirring and ultrasonically treating for 20 min, adding 2.5 mmol of phosphoric acid, and adjusting the pH value of the mixed solution to 1.5 by using concentrated nitric acid; and stirring the mixed solution at room temperature for 1 h, then aging at room temperature for 22 h, performing centrifugal separation, washing with 1 mol/L nitric acid for 3 times, then washing with deionized water for 3 times, and drying at 50 ℃ for 7h to obtain the composite material AMP/CNC.
AMP/CNC, NB-9000B and polyoxyethylene polyoxypropylene pentaerythritol ether were foam-polymerized at a volume ratio of 8:100:1 (4000 r/min) with high-speed stirring, AMP/CNC was fixed to cell walls of the polyurethane foam, washed 4 times with deionized water, and dried at 50 ℃ for 5 hours to obtain a porous AMP/CNC-PUF adsorbing material.
Embodiment 5 preparation method of porous AMP/CNC-PUF adsorbing material
Ultrasonically dispersing 50 mg of carbon nano tubes into 100 mL of deionized water; rapidly adding the aqueous solution dissolved with 3 mmol of ammonium molybdate into the carbon nano tube suspension under mechanical stirring, continuously stirring and ultrasonically treating for 30min, adding 2.5 mmol of phosphoric acid, and adjusting the pH value of the mixed solution to 0.5 by using concentrated nitric acid; and stirring the mixed solution at room temperature for 2 h, then aging at room temperature for 18 h, performing centrifugal separation, washing with 1 mol/L nitric acid for 2 times, then washing with deionized water for 4 times, and drying at 40 ℃ for 5h to obtain the composite material AMP/CNC.
AMP/CNC, NB-9000B and emulsified silicone oil were subjected to foam polymerization (3500 r/min) at a volume ratio of 12:100:1 under high-speed stirring, AMP/CNC was immobilized on the cell walls of polyurethane foam, washed 3 times with deionized water, and dried at 50 ℃ for 7 hours to obtain a porous AMP/CNC-PUF adsorbing material.
Test example:
adsorption experiment: adsorption experiments were performed with stabilized cesium, based on the same chemistry of stabilized cesium (Cs-133) as radioactive cesium. Weighing about 0.05 g of the prepared cesium adsorbent, adding the cesium adsorbent into a centrifuge tube filled with 25 mL of cesium-contaminated aqueous solution, placing the centrifuge tube on a shaking table at the rotation speed of 200 rpm for 24 h at room temperature, then filtering and separating the adsorbent and the adsorbed liquid, measuring the concentration of the cesium ions remaining in the adsorbed liquid, and calculating the corresponding cesium ion removal rate (E%) and equilibrium adsorption capacity (q) by using the following formulae）：
Wherein,C 0 andC e respectively being Cs in the adsorbed liquid+Initial and equilibrium concentrations (mg/L);Vis the volume of adsorbed liquid (L);mis the mass (g) of the dried adsorbent.
The above experiment was carried out using the adsorbent materials prepared in examples 1 to 5, and E and q were measuredeThe measurement results are shown in table 1. Comparative example 1 was prepared as in 2009100218782 example 1 and comparative example 2 was phosphomolybdic acidAmmonium.
Table 1 adsorption materials of the invention for cesium ion removal (E%) and equilibrium adsorption capacity (q)e）
| Adsorbent material | Cesium ion removal rate E (%) | Equilibrium adsorption capacity qe（mg/g） | Separation characteristics |
| Example 1 | 99.3**## | 102.8**## | Is easy to separate and recycle |
| Example 2 | 98.5*## | 101.4**## | Is easy to separate and recycle |
| Example 3 | 97.4*## | 100.2**## | Is easy to separate and recycle |
| Example 4 | 98.2*## | 100.8**## | Is easy to separate and recycle |
| Example 5 | 98.3*## | 100.9**## | Is easy to separate and recycle |
| Comparative example 1 | 81.5## | 48.6## | Is easy to separate and recycle |
| Comparative example 2 | 45.6 | 12.7 | Is coagulated and is not easy to separate |
In comparison with the comparative example 1, the present inventors have conducted a study,*P＜0.05，**p is less than 0.01; in comparison with the comparative example 2, the present inventors have conducted a study,##P＜0.01；
as can be seen from the data results of table 1, the composite absorbent prepared according to the present invention has a cesium ion removal rate and an equilibrium adsorption capacity superior to those of comparative example 2, and also superior to those of comparative example 1 in terms of the equilibrium adsorption capacity. This indicates that:
1) ammonium phosphomolybdate is easy to agglomerate, the adsorption performance of the ammonium phosphomolybdate is greatly reduced when the ammonium phosphomolybdate is directly used for cesium ions, the process is complex, and the adsorbent is difficult to recycle.
2) The adsorption performance of the composite adsorption material prepared by the invention is superior to that of comparative example 1, which shows that the adsorption material prepared by the invention can expose the adsorption sites of ammonium phosphomolybdate more repeatedly, the dosage of the adsorption material is less, and the adsorption efficiency is higher.
3) The adsorbent according to example 1 is more excellent in adsorption performance, and is the most preferred example of the present invention.
Claims (10)
1. A preparation method of a porous AMP/CNC-PUF adsorbing material is characterized in that a composite material is formed by anchoring ammonium phosphomolybdate nano-particles in situ by using a nano-carbon material as a substrate and utilizing an in-situ growth self-assembly technology, and encapsulating the ammonium phosphomolybdate nano-particles in foamed polyurethane sponge.
2. The method for preparing a porous AMP/CNC-PUF adsorbing material according to claim 1, characterized in that it comprises in particular the following steps:
1) preparing an ammonium phosphomolybdate nano carbon composite material: ultrasonically dispersing nano carbon particles into deionized water to obtain a nano carbon suspension; adding ammonium molybdate aqueous solution into the nano carbon suspension under mechanical stirring, continuing to perform ultrasonic stirring for 20-30min, adding phosphoric acid, and adjusting the pH of the mixed solution to 0.5-1.5 by using concentrated nitric acid; continuously stirring for 1-2 h at room temperature, aging for 18-22 h at room temperature, performing centrifugal separation, washing for 2-4 times by using 1 mol/L nitric acid, washing for 2-4 times by using deionized water, and drying for 5-7h at 40-50 ℃ to obtain an ammonium phosphomolybdate nano-carbon composite material;
2) preparation of porous AMP/CNC-PUF adsorbing material: and (2) carrying out foaming polymerization on the ammonium phosphomolybdate nano-carbon composite material, the polyurethane prepolymer and the foam stabilizer according to the volume ratio of 8-12:100:1 under the condition of high-speed stirring, so that the ammonium phosphomolybdate nano-carbon composite material is fixed on the cell wall of polyurethane foam, washing for 2-4 times by using deionized water, and drying for 5-7h at the temperature of 40-50 ℃ to obtain the porous AMP/CNC-PUF adsorbing material.
3. The method for preparing the porous AMP/CNC-PUF adsorbing material as recited in claim 2, wherein the nano-carbon particles are graphene oxide or carbon nanotubes.
4. The method for preparing the porous AMP/CNC-PUF adsorbing material according to claim 2, wherein the mass ratio of the nano-carbon particles to the deionized water in the nano-carbon ultra-biological dispersion process of the step 1) is 1: 2000.
5. The method for preparing a porous AMP/CNC-PUF adsorbing material according to claim 2, wherein the ultrasonic power during the ultrasonic dispersion and the ultrasonic agitation in the step 1) is 360W to 630W, preferably 450W to 540W.
6. The method for preparing the porous AMP/CNC-PUF adsorbing material as recited in claim 2, wherein the polyurethane prepolymer is obtained by reacting polyisocyanate and polyol, and the foam stabilizer is one or more of silicone emulsion, higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, and polydimethylsiloxane.
7. The method of claim 6, wherein the polyurethane prepolymer is NB-9000B and the foam stabilizer is Pluronic L-62.
8. The method for preparing the porous AMP/CNC-PUF adsorbing material as recited in claim 2, wherein the rotation speed of the high-speed stirring in the step 2) is 2000-5000 r/min.
9. The method for preparing the porous AMP/CNC-PUF adsorbing material according to claim 2, wherein the method for preparing the porous AMP/CNC-PUF adsorbing material comprises the following steps:
1) ultrasonically dispersing 50 mg of nano graphene oxide or carbon nano tube into 100 mL of deionized water; rapidly adding an aqueous solution dissolved with 3 mmol of ammonium molybdate into the graphene oxide suspension under mechanical stirring, continuously stirring and ultrasonically treating for 20 min, adding 2.5 mmol of phosphoric acid, and adjusting the pH value of the mixed solution to 1 by using concentrated nitric acid; stirring the mixed solution at room temperature for 1.5 h, then aging at room temperature for 20h, performing centrifugal separation, washing with 1 mol/L nitric acid for 3 times, then washing with deionized water for 3 times, and drying at 40 ℃ for 6h to obtain the composite material AMP/CNC;
2) AMP/CNC, NB-9000B and Pluronic L-62 were foam-polymerized at a volume ratio of 10:100:1 under high-speed stirring, AMP/CNC was fixed on the cell walls of the polyurethane foam, washed 3 times with deionized water, and dried at 40 ℃ for 6 hours to obtain a porous AMP/CNC-PUF adsorbing material.
10. Use of the porous AMP/CNC-PUF adsorbent material according to any one of claims 1 to 9 in the remediation of environmental contamination with cesium ions.
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