CN115155544B - Method for preparing uranium adsorption material containing polypropylene amidoxime multi-layer skeleton sphere based on 3D printing - Google Patents

Method for preparing uranium adsorption material containing polypropylene amidoxime multi-layer skeleton sphere based on 3D printing Download PDF

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CN115155544B
CN115155544B CN202210729047.6A CN202210729047A CN115155544B CN 115155544 B CN115155544 B CN 115155544B CN 202210729047 A CN202210729047 A CN 202210729047A CN 115155544 B CN115155544 B CN 115155544B
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pao
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王志宁
高品
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Shandong University
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Abstract

The invention relates to a method for preparing a multi-layer skeleton sphere uranium adsorption material containing polypropylene amidoxime based on 3D printing, which selects polypropylene amidoxime as a doping material, and performs 3D printing after mixing with polyamino acrylic ester and epoxy acrylic ester.

Description

Method for preparing uranium adsorption material containing polypropylene amidoxime multi-layer skeleton sphere based on 3D printing
Technical Field
The invention relates to a method for preparing a multi-layer skeleton sphere uranium adsorption material containing polypropylene amidoxime based on 3D printing, belonging to the technical field of chemistry and environment.
Background
The stable energy source is the basis of the development of human progress, the non-renewable and environmental pollution shortcomings of the traditional energy source promote the development of new energy sources, in many new energy sources, nuclear energy is expected to replace the traditional energy sources in the future as a clean and efficient stable energy source, the development of the new uranium energy source field plays an irreplaceable role, at present, the worldwide uranium source is mainly uranium ore, as well as the exploitation of the uranium ore, the waste water related to uranium experiments has a large amount of uranium residues, which inevitably has negative influence on the environment and generates a large amount of uranium-containing waste water, and uranium in radioactive waste water mainly comes from uranium ore exploitation/grinding activities, radioactive substances, nuclear accidents, nuclear weapon explosions and the like, so that the worldwide attention has been drawn in recent decades. The high solubility of uranium leads to an expansion of pollution spectrum, and world health organization requires that the maximum uranium content in the forbidden water be 14.4ug/L. The current method for enriching hexavalent uranium in water mainly comprises reduction precipitation, membrane separation, extraction, electrolytic recovery, ion exchange, adsorption and the like. Among them, the adsorption method is considered as one of the most effective treatment methods.
At present, the treatment method of uranium in uranium-containing wastewater mainly comprises chemical precipitation, an ion exchange method, a membrane separation method, an adsorption method and the like. The chemical precipitation method has simple equipment, low cost and high efficiency, but the polymer produced by the reaction needs further treatment; the ion exchange method has good removal effect, but has high price and limited exchange capacity; the membrane separation method is simple to operate and low in energy consumption, but has high requirements on the quality of raw water, and is often used together with other water treatment technologies; the adsorption method is attracting attention because of its high treatment efficiency and the ability to recover uranium. The existing adsorption materials mainly comprise carbon nano materials, such as activated carbon, graphene oxide, biochar, carbon-containing nanotubes, carbon-containing nanofibers and the like, which are widely applied in the adsorption field due to the advantages of large specific surface area, rich functional groups on the surface, stable chemical properties and the like, but the materials have low selectivity to uranium and unsatisfactory adsorption effect when being used independently.
Amidoxime groups (AO) are considered to be the most efficient functional groups for uranium adsorption so far, with good selectivity and adsorptivity. The monomers and polymers can be classified according to the substrate. The polymer has a plurality of adsorption sites, and generally uses polyacrylonitrile Powder (PAN) to generate amidoxime reaction under the action of hydroxylamine hydrochloride to convert nitrile groups into amidoxime groups to prepare the polypropylene amidoxime Powder (PAO), but the powdery material has the problems of difficult recovery and complex operation in adsorption experiments.
Chinese patent document CN109847724 discloses a preparation method of a semi-interpenetrating network hydrogel film material for extracting uranium from seawater, which comprises the steps of dissolving polypropylene amidoxime, a monomer, a photoinitiator and a cross-linking agent in an alkaline aqueous solution according to a certain mass ratio to obtain a precursor solution, and then injecting the precursor solution into a die to perform polymerization reaction under ultraviolet rays or sunlight. The hydrogel film material has small specific surface area, limited adsorption rate and poor mechanical property.
The 3D printing technology is widely paid attention to in recent years, and has the characteristics of controllable printing shape, simple material preparation and large-scale operation. The 3D printing is of a variety including photo-curing printers (SLA), fused deposition rapid prototyping printers (FDM), selective Laser Sintering (SLS), etc. Wherein the SLA adopts light-cured resin as raw material, FDM mainly adopts thermoplastic materials such as wax, ABS, PC, nylon and the like, and adopts filiform feeding, and SLS adopts powder, usually nylon/polyamide as raw material.
Therefore, aiming at the problem of difficult enrichment of hexavalent uranium in the current water body, a uranium adsorbing material with high uranium selectivity, large adsorption capacity and recycling capability is needed.
Disclosure of Invention
Aiming at the defects of the prior art, in particular to a method for preparing a multi-layer skeleton sphere uranium adsorption material containing polypropylene amidoxime based on 3D printing, which has the advantages of small adsorption quantity, poor mechanical property and poor recycling property of the existing uranium adsorption material.
The multi-layer skeleton sphere uranium adsorption material prepared by the invention has the advantages of large uranium adsorption capacity, strong mechanical property, high uranium selectivity, easy recovery, strong recycling property, simple manufacture and large-scale production.
Summary of the invention:
according to the invention, the polyacrylamide oxime powder prepared from the polyacrylonitrile powder is used as a doping material, the mixture resin of the polyamino acrylic ester and the epoxy acrylic ester is used as a printing raw material, and the uranium adsorption material (3D-PAO) containing the polyacrylamide oxime multi-layer skeleton sphere is prepared through SLA 3D printing.
Detailed description of the invention:
in order to solve the problems, the invention is realized by the following technical scheme:
the uranium adsorbing material is prepared by directly doping polypropylene amidoxime PAO powder into a mixed resin of polyamino acrylic ester and epoxy acrylic ester, so as to obtain the uranium adsorbing material (3D-PAO) containing the polypropylene amidoxime multi-layer skeleton sphere.
The method for preparing the uranium adsorption material containing the polypropylene amidoxime multi-layer skeleton sphere based on 3D printing comprises the following steps:
the preparation method of the polypropylene amidoxime PAO powder comprises the following steps:
and adding the polypropylene amidoxime PAO into the mixed resin of the polyamino acrylic ester and the epoxy acrylic ester to obtain a mixture, and printing the mixture into a sphere with a multi-layer skeleton by adopting an SLA photo-curing 3D printer to obtain a uranium adsorbing material (3D-PAO) containing the polypropylene amidoxime multi-layer skeleton sphere.
The preparation method of the polypropylene amidoxime PAO powder comprises the following steps:
and dissolving polyacrylonitrile PAN and hydroxylamine hydrochloride in methanol to obtain a mixed solution, dissolving sodium hydroxide in deionized water, adding the mixed solution into the mixed solution, condensing and refluxing at 70-90 ℃, reacting for 12-36h, centrifugally collecting samples after the reaction, washing the samples with ethanol and deionized water respectively, and freeze-drying to obtain the polypropylene amidoxime PAO.
According to the invention, the mass ratio of hydroxylamine hydrochloride to PAN is preferably 1-3:1.
according to the invention, the mass ratio of deionized water to sodium hydroxide is preferably 1: (0.4-0.8).
According to the invention, the mass ratio of sodium hydroxide to hydroxylamine hydrochloride is preferably 1: (1-3).
According to the invention, the preferred volume ratio of PAN mass to methanol is 1: (30-40), units g/mL.
According to a preferred embodiment of the invention, the methanol is anhydrous methanol.
According to the invention, the reaction temperature is preferably 75℃and the reaction time is 24 hours.
According to the invention, the mass ratio of the polypropylene amidoxime PAO to the mixed resin of the polyamino acrylate and the epoxy acrylate is preferably 15-25%.
In the polyaminoacrylate and epoxy acrylate mixture resin, the mixing ratio of the two is not limited.
According to the invention, the shape of the uranium adsorption material of the multi-layer skeleton sphere is a multi-layer sphere, the layers are connected through fulcra, the uranium adsorption material is of a hollowed-out structure, and the specification of the whole sphere is 23:47:52, unit mm, skeleton size 0.19mm.
The invention also provides application of the multi-layer skeleton sphere uranium adsorption material containing the polypropylene amidoxime, and the multi-layer skeleton sphere uranium adsorption material containing the polypropylene amidoxime is added into a water body to carry out adsorption enrichment of hexavalent uranium.
The preferred specific application method according to the invention is as follows: the method comprises the steps of adding a multi-layer skeleton sphere uranium adsorption material containing the polypropylene amidoxime into a water body, carrying out adsorption enrichment on hexavalent uranium for 20-24 hours, wherein the adding amount is 0.21-0.23g per 150mL of water body, the pH value of the water body is 3-10, and the adsorption temperature is 25 ℃.
According to the invention, the adsorption material after adsorbing and enriching hexavalent uranium adopts H 2 O 2 Eluting uranium adsorbed on the surface of 3D-PAO by mixed solution of NaOH and H 2 O 2 The concentration of (C) was 0.1mol/L, and the concentration of NaOH was 0.1mol/L.
The beneficial effects of the invention are as follows:
1. according to the invention, polypropylene amidoxime is selected as a doping material, 3D printing is carried out after the polypropylene amidoxime is mixed with the mixture of polyamino acrylic ester and epoxy acrylic ester, on one hand, amidoxime groups are introduced to serve as an adsorption material of hexavalent uranium, on the other hand, PAO is stably fixed on the surface of the material in a 3D printing mode, so that the problems of uneven mixing, easy sedimentation and recycling difficulty of powdery materials in solution are avoided.
2. According to the invention, the polypropylene amidoxime is selected as a doping material, 3D printing is carried out after the polypropylene amidoxime is mixed with the polyamino acrylic ester and the epoxy acrylic ester, and the multi-layer skeleton sphere uranium adsorption material containing the polypropylene amidoxime is obtained, the multi-layer sphere is used as a skeleton structure, and a bionic sponge structure is selected on the surface of the sphere, so that the strength of the material is improved; meanwhile, the surface of the sphere is adopted, so that the 3D-PAO is uniformly contacted with the fluid when being adsorbed in the water body.
3. According to the invention, the polypropylene amidoxime is selected as the doping material, 3D printing is carried out after the polypropylene amidoxime is mixed with the polyamino acrylic ester and the epoxy acrylic ester, the multilayer skeleton sphere uranium adsorption material with a customizable shape can be prepared by the method, the effect of comprehensive and uniform adsorption of the multilayer skeleton sphere uranium adsorption material can be realized, the adsorption quantity is large, the efficiency is high, the cost of the used material is low, the preparation method is simple, the mass preparation can be carried out, the material preparation is uniform, and the error is small.
4. The multi-layer skeleton sphere uranium adsorption material prepared by the invention has the advantages of large uranium adsorption capacity, strong mechanical property, high uranium selectivity, easiness in recovery and recycling, environment-friendly product and long recycling service life, and is used for treating hexavalent uranium.
5. The uranium adsorption material prepared by the invention has the advantages of large adsorption capacity, strong mechanical property, high uranium selectivity, easy recovery, strong recycling property, simple manufacture and mass production.
Drawings
FIG. 1 is a SEM comparative view of the materials prepared in example 1 and comparative example 2 of the present invention, the left hand drawing is comparative example 2, and the right hand drawing is example 1;
FIG. 2 is a graph showing the water contact angle of the materials prepared in example 1 and comparative example 2 according to the present invention; the left figure is comparative example 2 and the right figure is example 1;
FIG. 3 is a graph showing the comparison of contact angles of the underwater oils (a pump oil, b mineral oil, c simethicone, d 1, 2-dichloroethane) of the materials prepared in example 1 and comparative example 2 according to the present invention; the left hand figure is comparative example 2 and the right hand figure is example 1.
FIG. 4 is a simulation of the adsorption of example 1 and comparative example 1 of the present invention.
FIG. 5 is a graph showing the variation of mechanical strength with PAO doping amount for the materials of the present invention.
FIG. 6 is a bar graph showing the adsorption amounts of the materials prepared in example 1 and comparative example 2 according to the present invention.
FIG. 7 is a Langmuir adsorption curve fitted to the adsorption data of hexavalent uranium for 3D-PAO of example 1, resulting in a maximum adsorption of 78.01 μg/mg.
Fig. 8 is a print structure diagram and a post-print split diagram of embodiment 1 and comparative example of the present invention.
FIG. 9 is a diagram showing adsorption of uranium solutions of different concentrations to the material prepared in example 1 of the present invention.
FIG. 10 shows the selective adsorption effect of the material prepared in example 1 of the present invention on different metal elements.
FIG. 11 is a graph showing the effect of the material circulation test in example 1 of the present invention.
Detailed Description
Example 1:
the method for preparing the uranium adsorption material containing the polypropylene amidoxime multi-layer skeleton sphere based on 3D printing comprises the following steps:
(1) Dissolving hydroxylamine hydrochloride and PAO in methanol, wherein the mass ratio of the hydroxylamine hydrochloride to the PAO is 1.5:1, the mass volume ratio of PAO to absolute methanol is 1g to 30mL, and a mixed solution is obtained; 3g of sodium hydroxide particles are dissolved in 5mL of deionized water to obtain sodium hydroxide solution; mixing sodium hydroxide solution and the mixed solution into a three-necked flask, condensing and refluxing in an oil bath mode, wherein the reaction temperature is 75 ℃, the reaction time is 24 hours, light yellow powder is obtained, centrifugally collecting samples, washing the samples with ethanol and water respectively, and then freeze-drying the samples to obtain polypropylene amidoxime powder;
(2) Stirring 80g of PAO and 400g of mixed resin of polyamino acrylic ester and epoxy acrylic ester under a high-speed oscillator until the PAO is completely and uniformly mixed to obtain 20% PAO doped printing resin;
(3) Pouring the doped resin in the step (2) into a resin tank of a photo-curing printer Form lab 3, setting parameters to print and Form a sphere with a multi-layer framework, connecting layers through fulcrums, and adopting a hollow structure, wherein the specification of the whole sphere is that the diameter ratio is 23:47:52, unit mm, and framework size of 0.19mm to obtain a cured material with a multi-layer spherical framework structure; repeatedly cleaning in ethanol and aqueous solution until the surface of the material is free of liquid resin; and (3) drying the printed and cured material in a baking oven at 40 ℃ to obtain the uranium adsorption material containing the polypropylene amidoxime multi-layer skeleton sphere.
EXAMPLE 2,
The method for preparing a multi-layered skeletal sphere uranium adsorption material containing a polypropylene amidoxime, based on 3D printing, as described in example 1, was different in that,
in step (2), the PAO addition was 60g, yielding a 15% PAO doped print resin. The rest of the procedure and the amount are exactly the same as in example 1.
EXAMPLE 3,
The method for preparing a multi-layered skeletal sphere uranium adsorption material containing a polypropylene amidoxime, based on 3D printing, as described in example 1, was different in that,
in step (2), PAO was added at 100g. 25% PAO doped print resin was obtained. The rest of the procedure and the amount are exactly the same as in example 1.
Comparative example 1,
The method for preparing a multi-layered skeletal sphere uranium adsorption material containing a polypropylene amidoxime, based on 3D printing, as described in example 1, was different in that,
in step (3), the doped resin is printed into a square skeleton structure.
Comparative example 2,
The preparation method of the multilayer skeleton sphere uranium adsorption material comprises the steps of pouring a polyamino acrylic ester and epoxy acrylic ester mixed resin into a resin groove of a photo-curing printer Form lab 3, setting parameters to print and print the polyurethane resin into a sphere with a multilayer skeleton, connecting layers through fulcrums, and forming a hollow structure, wherein the specification of the whole sphere is that the diameter ratio is 23:47:52, unit mm, and framework size of 0.19mm to obtain a cured material with a multi-layer spherical framework structure; repeatedly cleaning in ethanol and aqueous solution until the surface of the material is free of liquid resin; and (3) drying the printed and cured material in a baking oven at 40 ℃ to obtain the multi-layer skeleton sphere uranium adsorption material.
The following is a characterization of the adsorption material and adsorption experiment for hexavalent uranium manufactured under different conditions.
Experimental example 1,
SEM tests were performed on example 1 and comparative example 2, and the results are shown in fig. 1. It can be seen from fig. 1 that the surface of the examples is covered with a large amount of granular material, which shows that the invention successfully embeds the polypropylene amidoxime uniformly and firmly in the material.
Experimental example 2,
The water contact angle test is performed on the embodiment 1 and the comparative example 2, the experimental results are shown in fig. 2, and as can be seen from fig. 2, the adsorption material of the embodiment 1 has a small contact angle, and the 3D printing material doped with PAO has good hydrophilicity. This is because PAN material has abundant amino and hydroxyl groups on the surface, and belongs to hydrophilic oleophobic functional groups.
Experimental example 3,
The experimental results of the underwater different oil contact angle tests of the example 1 and the comparative example 2 are shown in fig. 3, and it can be seen from fig. 3 that the 3D printing material doped with PAO of the example 1 has good oil stain resistance.
Experimental example 4,
For the adsorption experiments of example 1 and comparative example 1, the adsorption image results were simulated as fig. 4, and the shades of the colors represent the intensity of adsorption for clear illustration. It can be seen that the cubic structure material is mainly concentrated on the ribs during the adsorption process, which is unfavorable for the uniform adsorption effect. The uranium adsorbing material with the multi-layer skeleton sphere of the embodiment 1 is comprehensively and uniformly adsorbed, and has large adsorption capacity and high efficiency.
Experimental example 5,
The mechanical strength test was performed on the examples, and the results are shown in fig. 5. It can be seen that the mechanical strength of the material gradually decreases with increasing addition of the PAO powder, and the PAO doped with 25% has both high mechanical strength and adsorption effect.
Example 6
As shown in fig. 6, it can be seen from fig. 6 that the 3D printing material of example 1 has good adsorption performance on uranium, because PAO surfaces contain rich amidoxime groups, and can be used for adsorption of uranyl ions in water, and the adsorption amount increases with increasing PAO doping amount.
EXAMPLE 7,
The multi-layer skeleton sphere uranium adsorption material of example 1 is used for adsorbing uranium solutions with different concentrations, the adsorption conditions are measured, experimental results are shown, and as can be seen from fig. 7, the adsorption data of 3D-PAO of example 1 of the present invention on hexavalent uranium is fitted with Langmuir adsorption curve, and the maximum adsorption amount is 78.01 μg/mg, which indicates that the multi-layer skeleton sphere uranium adsorption material of the present invention has large adsorption amount and high efficiency on uranium.
Experimental example 8,
As can be seen from fig. 1, even PAO particles are embedded on the surface of the 3D material after PAO doping, and the adsorption experiment of uranium adsorption materials with different concentrations of uranium in the multi-layer skeleton sphere of example 1 can be used for gradually changing the particles on the surface of 3D-PAO from white to orange according to the increase of the adsorption amount. As shown in fig. 9, it is obvious that the colors of the surfaces after the 3D-PAO adsorption are different when the uranium solution concentration is different, so that the uranium adsorption condition can be determined by the state of the dark and light colors of the surfaces of the materials.
Experimental example 9,
The selective adsorption experiment is carried out on the multi-layer skeleton sphere uranium adsorption material of the embodiment 1, the adsorption condition of the multi-layer skeleton sphere uranium adsorption material on different elements is measured, and an experimental result is shown in a graph 10, so that the 3D-PAO of the embodiment 1 of the invention has specific adsorption on hexavalent uranium, and the binding force between the 3D-PAO and uranium is 10 other heavy metal elements.
Experimental example 10,
The uranium adsorbent material of example 1 was subjected to a cyclic adsorption test using 0.1mol/L H as shown in FIG. 11 2 O 2 The effect of the mixed solution of 0.1mol/L NaOH as the eluent is relatively good, and after the repeated 5 times of adsorption test, the adsorption effect respectively reaches that the first adsorption surface is covered with a large amount of granular materials, namely PAO.
97.26%, 97.36%, 94.92%, 75.78% and 71.63% of the experiments show that 3D-PAO still has a better regeneration effect within a certain number of cycles.

Claims (8)

1. The uranium adsorbing material comprises a polypropylene amidoxime-containing multi-layer skeleton sphere, wherein polypropylene amidoxime PAO powder is directly doped into a mixed resin of polyamino acrylic ester and epoxy acrylic ester to obtain a polypropylene amidoxime-containing multi-layer skeleton sphere uranium adsorbing material 3D-PAO;
the uranium adsorption material containing the polypropylene amidoxime multi-layer skeleton sphere is prepared by the following method:
the preparation method of the polypropylene amidoxime PAO powder comprises the following steps: dissolving polyacrylonitrile PAN and hydroxylamine hydrochloride in methanol to obtain a mixed solution, dissolving sodium hydroxide in deionized water, adding the solution into the mixed solution, condensing and refluxing at 70-90 ℃, reacting 12-36h, centrifugally collecting samples after the reaction, washing the samples with ethanol and deionized water respectively, and freeze-drying to obtain polypropylene amidoxime PAO;
adding polypropylene amidoxime PAO into a mixed resin of polyamino acrylic ester and epoxy acrylic ester to obtain a mixture, and printing the mixture into a sphere with a multi-layer skeleton by adopting an SLA photo-curing 3D printer to obtain a uranium adsorption material 3D-PAO containing the polypropylene amidoxime multi-layer skeleton sphere; the mass ratio of the polypropylene amidoxime PAO to the mixed resin of the polyamino acrylic ester and the epoxy acrylic ester is 15-25%.
2. The method for preparing the uranium adsorption material containing the polypropylene amidoxime multi-layer skeleton sphere of claim 1, which comprises the following steps:
the preparation method of the polypropylene amidoxime PAO powder comprises the following steps: dissolving polyacrylonitrile PAN and hydroxylamine hydrochloride in methanol to obtain a mixed solution, dissolving sodium hydroxide in deionized water, adding the solution into the mixed solution, condensing and refluxing at 70-90 ℃, reacting 12-36h, centrifugally collecting samples after the reaction, washing the samples with ethanol and deionized water respectively, and freeze-drying to obtain polypropylene amidoxime PAO;
adding polypropylene amidoxime PAO into a mixed resin of polyamino acrylic ester and epoxy acrylic ester to obtain a mixture, printing the mixture into a sphere with a multi-layer skeleton by adopting an SLA photo-curing 3D printer to obtain a uranium adsorption material 3D-PAO containing the polypropylene amidoxime multi-layer skeleton sphere, wherein the mass ratio of the polypropylene amidoxime PAO to the mixed resin of polyamino acrylic ester and epoxy acrylic ester is 15-25%.
3. The preparation method according to claim 2, wherein the mass ratio of hydroxylamine hydrochloride to PAN is 1-3:1, the mass ratio of deionized water to sodium hydroxide is 1: (0.4-0.8), the mass ratio of sodium hydroxide to hydroxylamine hydrochloride is 1: (1-3).
4. The preparation method according to claim 2, wherein the volume ratio of PAN mass to methanol is 1: (30-40), unit g/mL, methanol is anhydrous methanol.
5. The method according to claim 2, wherein the reaction temperature is 75 ℃ and the reaction time is 24h.
6. The preparation method of claim 2, wherein the uranium adsorbing material of the multi-layer skeleton sphere is in the shape of a multi-layer sphere, the layers are connected through fulcrums, the hollow structure is formed, and the specification of the whole sphere is that the diameter ratio is 23:47:52, unit mm, skeleton size 0.19mm.
7. The application of the uranium adsorption material containing the polypropylene amidoxime multi-layer skeleton spheres, which is disclosed in claim 1, wherein the uranium adsorption material containing the polypropylene amidoxime multi-layer skeleton spheres is added into a water body to carry out adsorption enrichment of hexavalent uranium.
8. The use according to claim 7, characterized in that the specific application method is as follows: adding a multi-layer skeleton sphere uranium adsorption material containing the polypropylene amidoxime into a water body, carrying out adsorption enrichment on hexavalent uranium for 20-24 hours, wherein the adding amount is 0.21-0.23g in each 150mL water body, the pH value of the water body is 3-10, and the adsorption temperature is 25 ℃; the adsorption material after adsorbing and enriching hexavalent uranium adopts H 2 O 2 Eluting uranium adsorbed on the surface of 3D-PAO by mixed solution of NaOH and H 2 O 2 The concentration of (C) was 0.1mol/L, and the concentration of NaOH was 0.1mol/L.
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