CN118515830A - Preparation method of heteroatom doped phenolic resin nano adsorbent and application of heteroatom doped phenolic resin nano adsorbent in selective separation of palladium - Google Patents
Preparation method of heteroatom doped phenolic resin nano adsorbent and application of heteroatom doped phenolic resin nano adsorbent in selective separation of palladium Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 65
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 42
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 25
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 11
- 238000000926 separation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 16
- -1 palladium ions Chemical class 0.000 claims abstract description 14
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 40
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- KIKDXUSFMAWUGW-UHFFFAOYSA-N 4-(4-hydroxyphenyl)selanylphenol Chemical compound C1=CC(O)=CC=C1[Se]C1=CC=C(O)C=C1 KIKDXUSFMAWUGW-UHFFFAOYSA-N 0.000 claims description 12
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 10
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 5
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- 239000008098 formaldehyde solution Substances 0.000 claims 2
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- 238000001179 sorption measurement Methods 0.000 abstract description 55
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 14
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- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 6
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Abstract
The invention belongs to the technical field of adsorption separation functional materials, and discloses a preparation method of a heteroatom doped phenolic resin nano adsorbent and application of selective palladium separation. The method takes nitrogen element in ammonia water as a key condition for rapid forming, and takes selenium compound as a core monomer. By means of the strong affinity between nitrogen and selenium and noble metal ions and high-speed stirring technology, the controllable and rapid preparation of the nitrogen-doped (RF-H) and nitrogen and selenium co-doped (Se-RF-H) phenolic resin adsorbent is realized. The method not only remarkably improves the adsorption efficiency of palladium ions, but also realizes the rapid preparation of the novel adsorbent by adjusting the reaction conditions and time, thereby reducing the cost and promoting the conversion to industrial application. The invention has important economic value in the field of noble metal recovery, can effectively solve the problems of noble metal resource waste and environmental pollution in electronic garbage, and simultaneously provides a new thought for designing low-cost high-performance adsorbents.
Description
Technical Field
The invention belongs to the technical field of adsorption separation functional materials, relates to preparation of a heteroatom doped phenolic resin adsorbent for selectively separating palladium, and particularly relates to a rapid and controllable preparation method based on high-speed stirring assistance and application of the method in selective adsorption separation of palladium ions.
Background
Noble metal palladium is widely applied to the fields of jewelry, finance, electronics, aerospace, military, catalysis, medical treatment and the like due to the excellent physical and chemical properties, and is an extremely important economic resource and strategic resource. With the rapid growth of noble metal demands and the limited ore resources, the contradiction between supply and demand is increasingly significant. Electronic waste, due to its high content of precious metals, is an attractive recycling source, however, most electronic waste is not properly recycled, resulting in waste of resources and environmental pollution. Studies have shown that: palladium resources are extremely scarce in nature (only 0.015ppm concentration in the crust), while the palladium content in waste electronic equipment (300 g t -1) is much higher than in natural ores (< 10g t -1). This makes the electronic waste a "urban mine" that remains to be exploited.
At present, main methods for extracting noble metals from electronic waste include precipitation, ion exchange, extraction, membrane separation, electrolysis, adsorption and the like. Among these methods, adsorption is considered as a very potential technique because of its low cost, high extraction yield and easy continuous operation. However, current adsorption techniques remain challenging in the face of low concentrations of precious metals, complex competing ions, and extremely acidic environments.
Although the general resorcinol-formaldehyde resin (phenolic resin) has been widely used in industry, there are still some limitations of this conventional material in a specific field, especially in terms of precious metal recovery. First, conventional phenolic resins often exhibit lower adsorption capacity and selectivity when adsorbing noble metals, particularly palladium. Due to their chemical structure limitations, these resins tend to be difficult to achieve effective identification and selective adsorption of specific noble metal ions when dealing with complex systems containing multiple metal ions. Therefore, there is an urgent need to develop a novel adsorbent capable of rapidly and selectively extracting noble metal palladium from electronic waste leachate under the premise of environmental friendliness and high selectivity.
In the development of adsorption technology, there is an increasing demand for efficient controllable preparation of adsorbents. The ideal adsorbent should have high adsorption capacity, excellent selectivity, good chemical stability, and be capable of stable operation in complex environments. However, conventional methods of adsorbent preparation are often limited by long synthesis times, complicated steps, low cost effectiveness, and the like. Therefore, developing a rapid and controllable adsorbent preparation method is an important subject in the industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the problems of complicated steps, low adsorption capacity and selectivity and the like in the preparation of the conventional palladium ion adsorbent, and provides a method for preparing a novel phenolic resin adsorbent based on heteroatom doping fast and controllable. The N-doped phenolic resin adsorbent (RF-H) and the N, se co-doped phenolic resin adsorbent (Se-RF-H) are prepared rapidly and controllably by taking nitrogen element in ammonia water as a necessary condition for rapid forming, taking selenium compounds as key monomers and utilizing the strong affinity between the selenium compounds and noble metal ions through high-speed stirring.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of an N-doped phenolic resin nano adsorbent comprises the following steps:
step A1: adding ammonia water into ethanol-water solution with a certain proportion, adding resorcinol, performing ultrasonic dispersion, then adding formaldehyde water solution, then inserting into a high-speed stirrer, stirring and reacting for a certain time t 2 at a certain rotating speed r 1, centrifugally separating the obtained solid, washing with water and ethanol for several times to obtain the product N-doped phenolic resin nano adsorbent RF-H, and placing into a vacuum oven for full drying.
In the step A1, the dosage ratio of the ammonia water, the ethanol, the deionized water, the resorcinol and the formaldehyde aqueous solution is 35-150 mu L:1-6mL:1-6mL:10-70mg: 35-150. Mu.L;
wherein the mass percentage concentration of the formaldehyde aqueous solution is 37.0-40.0%,
The rotation speed r 1 of the high-speed stirrer is 5000-15000rpm, and the reaction time t 2 is 3-7min.
A preparation method of an N, se co-doped phenolic resin nano adsorbent comprises the following steps:
step B1: preparation of bis (4-hydroxyphenyl) selenide monomer
Firstly, adding selenium powder into chloroform A, dispersing the selenium powder by magnetic stirring, then adding a mixture of sulfonyl chloride and chloroform B, uniformly stirring, then adding a mixture of phenol and anhydrous diethyl ether, stirring to be clear and transparent, continuously reacting for a period of time t 1 at room temperature, dropwise adding Na 2CO3 solution with a certain concentration until no bubbles are generated, separating an organic phase by using a separating funnel, removing an organic solvent by using rotary evaporation, purifying by using a column chromatography, and finally obtaining golden yellow solid, namely a bis (4-hydroxyphenyl) selenide monomer;
Step B2: preparation of N, se co-doped phenolic resin nano adsorbent
Adding ammonia water into ethanol-water solution with a certain proportion, adding resorcinol and the bis (4-hydroxyphenyl) selenide monomer synthesized in the step B1, performing ultrasonic dispersion, then adding a certain amount of formaldehyde water solution, then inserting into a high-speed stirrer, stirring and reacting for a certain time t 3 at a certain rotating speed r 2, performing centrifugal separation on the obtained solid, washing with water and ethanol for several times to obtain the product N, se co-doped phenolic resin nano adsorbent (Se-RF-H), and placing into a vacuum oven for full drying.
In the step B1, the dosage ratio of the selenium powder to the chloroform A to the sulfonyl chloride to the chloroform B to the phenol to the anhydrous diethyl ether is 1.98-7.90g:50-200mL:3.38-13.50g:50-200mL:4.70-18.80g:50-200mL; the reaction time t 1 is 2-4h, and the mass concentration of Na 2CO3 solution is 10.50-42.00wt%.
In the step B2, the dosage ratio of the ammonia water, the ethanol, the deionized water, the resorcinol, the formaldehyde aqueous solution and the bis (4-hydroxyphenyl) selenide is 35-150 mu L:1-6mL:1-6mL:5-20mg:35-150 μl:12-50mg;
Wherein the mass percentage concentration of the formaldehyde aqueous solution is 37.0-40.0%, the rotating speed r 2 of the high-speed stirrer is 5000-15000rpm, and the reaction time t 3 is 3-7min.
The N-doped phenolic resin nano-adsorbent or the N, se co-doped phenolic resin nano-adsorbent prepared by the invention is used for adsorbing palladium ions.
The invention has the beneficial effects that:
solves the problems in noble metal recovery: because the content of noble metal palladium in the electronic waste is relatively high, the adsorbent disclosed by the invention is designed and prepared for noble metals in the electronic waste. The method is favorable for efficiently recycling the noble metals in the electronic waste, and meets the requirement for efficient recycling of resources.
The selectivity and the adsorption capacity of the adsorbent are improved: the traditional phenolic resin may show lower adsorption capacity and selectivity when adsorbing noble metals, but the invention introduces selenium compounds as key monomers, and realizes the high selectivity and the improvement of the adsorption capacity of palladium through the strong affinity between the selenium compounds and noble metal ions.
Using heteroatom doping techniques: the invention adopts a heteroatom doping method, namely, nitrogen element and selenium element are introduced in the process of preparing the phenolic resin adsorbent, thereby enhancing the performance of the adsorbent. The doping technology is helpful for regulating and controlling the physicochemical properties of the adsorbent and improving the adsorption capacity of the adsorbent to palladium ions under specific conditions.
The rapid and controllable preparation method comprises the following steps: the invention uses a rapid and controllable preparation method assisted by high-speed stirring, and realizes the rapid preparation of the novel adsorbent by adjusting the reaction conditions and time. This contributes to an improvement in production efficiency, a reduction in cost, and promotion of industrial production.
Is suitable for complex environment and low-concentration noble metals: conventional adsorption techniques present challenges in facing low concentrations of precious metals, complex competing ions, and extremely acidic environments. The adsorbent provided by the invention still has excellent performance under the conditions and better stability and adaptability.
In combination, the invention has remarkable economic benefit in the field of noble metal recovery, and can effectively solve the problems of noble metal resource waste and environmental pollution in electronic garbage. Meanwhile, by introducing a novel adsorbent and a rapid preparation method, the invention has important innovative significance in the technical field of adsorption.
Drawings
FIG. 1 is a scanning electron micrograph and a particle size distribution plot of RF-H prepared at different rotational speeds in example 1.
In FIG. 2, a-b are the scanning electron microscope image and the transmission electron microscope image of RF-H obtained at 10000rpm in example 1, and d-e are the scanning electron microscope image and the transmission electron microscope image of Se-RF-H obtained at 10000 rpm.
FIG. 3 is a graph showing nitrogen adsorption-desorption of Se-RF-H adsorbent prepared in example 1.
FIG. 4 is an infrared spectrum of the RF-H and Se-RF-H adsorbents prepared in example 1.
FIG. 5 shows the effect of pH on the adsorption capacity of palladium ions by Se-RF-H adsorbent prepared in example 1.
FIG. 6 is a graph showing the adsorption kinetics of Se-RF-H adsorbent to palladium ions and model fitting thereof prepared in example 1.
FIG. 7 is a graph showing the effect of temperature on the adsorption balance of palladium ions by the Se-RF-H adsorbent prepared in example 1 and its model fitting.
FIG. 8 shows the adsorption selectivity of Se-RF-H adsorbent prepared in example 1.
FIG. 9 shows the adsorption regeneration performance of Se-RF-H adsorbent prepared in example 1.
Detailed Description
In the specific embodiment of the invention, the identification performance evaluation is carried out according to the following method: the static adsorption experiment was used. Testing the adsorption capacity of 2.0mg Se-RF-H for palladium ions within the pH range of 1.0-4.0, measuring the content of the palladium ions after adsorption by using an inductively coupled plasma emission spectrometer, and determining the optimal adsorption pH according to the result; secondly, researching the influence of adsorption time on Se-RF-H adsorption capacity, and performing fitting calculation and analysis on data by using a Pseudo first-order model, a Pseudo second-order model and the like; in order to study the maximum adsorption capacity of Se-RF-H, an adsorption balance test is carried out within the range of 100-500ppm of palladium ion concentration, a Langmuir model and a Freundlich model are adopted to fit adsorption data, and the adsorption capacity is calculated according to the result; and the common metal ions in other electronic wastes are selected as competitive adsorbates to study the selective adsorption performance of Se-RF-H; and finally, testing the adsorption regeneration performance of the catalyst.
The invention will be further described with reference to specific examples.
Example 1:
(1) Preparation of N-doped phenolic resin nano adsorbent
70 Μl of ammonia was added to 1mL: to 6mL of ethanol-water solution, 70mg of resorcinol was added, followed by ultrasonic dispersion, then 70. Mu.L of formaldehyde water solution was added, followed by insertion into a high-speed stirrer, stirring at 10000rpm for 5min, the obtained solid was separated by centrifugation, and after washing with water and ethanol several times, the product N-doped phenol resin nano adsorbent (RF-H) was obtained, and was placed in a vacuum oven to be sufficiently dried.
(2) Preparation of bis (4-hydroxyphenyl) selenide monomer
First, 3.96g of selenium powder was added to 100mL of chloroform and dispersed by magnetic stirring. Then, a mixture of 6.75g of sulfonyl chloride and 100mL of chloroform was added, and after stirring uniformly, a mixture of 9.4g of phenol and 100mL of anhydrous diethyl ether was added, and stirring was continued at room temperature for 3 hours, after which a 21wt% Na 2CO3 solution was added dropwise until no bubbles were generated, and the organic phase was separated using a separating funnel, and the organic solvent was removed by rotary evaporation. Purifying by column chromatography to obtain golden yellow solid.
(3) Preparation of N, se co-doped phenolic resin nano adsorbent
70 Μl of ammonia was added to 1mL: to 6mL of ethanol-water solution, 10mg of resorcinol and 25mg of the monomer synthesized in (1) were added, and the mixture was subjected to ultrasonic dispersion, followed by adding 70. Mu.L of formaldehyde water solution, followed by inserting the mixture into a high-speed stirrer, stirring at 10000rpm for 5min, and washing the obtained solid with water and ethanol several times to obtain a product of N, se-co-doped phenolic resin nano-adsorbent (Se-RF-H), and placing the product in a vacuum oven for sufficient drying.
FIG. 1 shows a scanning electron microscope image of RF-H produced at different stirring speeds, and by comparison, it was found that the particle size of the resulting product was not uniform and the production time required was longer without stirring. When the rotation speed is 10000rpm, the particle size of the obtained product is most uniform, the rotation speed is increased or reduced, and the particle size distribution range is enlarged.
FIG. 2 shows a scanning electron microscope image and a transmission electron microscope image of RF-H (a, b) and Se-RF-H (c, d) prepared in example 1, from which it can be seen that the Se-RF-H has a distinct core unlike the RF-H.
FIG. 3 shows a nitrogen adsorption-desorption graph of Se-RF-H prepared in example 1, and the specific surface area thereof is about 25.41m 2·g-1.
FIG. 4 shows the infrared spectra of RF-H and Se-RF-H prepared in example 1, which have similar structures without great difference, except that Se-RF-H has increased the absorption peak of C-Se at 2900cm -1, confirming the successful introduction of Se element.
Example 2:
(1) Preparation of N-doped phenolic resin nano adsorbent
35 Μl of ammonia was added to 2mL: to 5mL of ethanol-water solution, 10mg of resorcinol was added, followed by ultrasonic dispersion, and then 35. Mu.L of formaldehyde water solution was added, followed by insertion into a high-speed stirrer, stirring at 5000rpm for 3min, and the obtained solid was separated by centrifugation, washed several times with water and ethanol to obtain the product N-doped phenol resin nanosorbent (RF-H), and then placed in a vacuum oven for sufficient drying.
(2) Preparation of bis (4-hydroxyphenyl) selenide monomer
First, 1.98g of selenium powder was added to 50mL of chloroform and dispersed by magnetic stirring. Then, a mixture of 3.38g of sulfonyl chloride and 50mL of chloroform was added, and after stirring uniformly, a mixture of 4.7g of phenol and 50mL of anhydrous diethyl ether was added, and stirring was continued at room temperature for 2 hours, and after further reaction, a Na 2CO3 solution having a concentration of 10.5wt% was added dropwise until no bubbles were generated, and the organic phase was separated using a separating funnel, and the organic solvent was removed by rotary evaporation. Purifying by column chromatography to obtain golden yellow solid.
(3) Preparation of N, se co-doped phenolic resin nano adsorbent
35 Μl of ammonia was added to 2mL:5mL of ethanol-water solution is added with 5mg of resorcinol and 12mg of monomer synthesized in (1), ultrasonic dispersion is carried out, then 35 mu L of formaldehyde water solution is added, a high-speed stirrer is inserted, stirring is carried out for 3min at 5000rpm, the obtained solid is separated by centrifugation, the obtained solid is washed with water and ethanol for several times, and the product N, se co-doped phenolic resin nano adsorbent (Se-RF-H) is obtained, and is placed in a vacuum oven for full drying.
Example 3:
(1) Preparation of N-doped phenolic resin nano adsorbent
150 Μl of ammonia was added to 3mL: to 4mL of ethanol-water solution, 70mg of resorcinol was added, followed by ultrasonic dispersion, followed by addition of 150. Mu.L of formaldehyde water solution, followed by insertion into a high-speed stirrer, stirring at 15000rpm for 7min, and the obtained solid was separated by centrifugation, washed several times with water and ethanol to obtain the product N-doped phenol resin nanosorbent (RF-H), and then placed in a vacuum oven for sufficient drying.
(2) Preparation of bis (4-hydroxyphenyl) selenide monomer
First, 7.9g of selenium powder was added to 200mL of chloroform and dispersed by magnetic stirring. Then, a mixture of 13.5g of sulfonyl chloride and 200mL of chloroform was added, and after stirring uniformly, a mixture of 18.8g of phenol and 200mL of anhydrous diethyl ether was added, and stirring was continued at room temperature for 4 hours, after which a solution of Na 2CO3 having a concentration of 42wt% was added dropwise until no bubbles were generated, the organic phase was separated using a separating funnel, and the organic solvent was removed by rotary evaporation. Purifying by column chromatography to obtain golden yellow solid.
(3) Preparation of N, se co-doped phenolic resin nano adsorbent
150 Μl of ammonia was added to 3mL: to 4mL of ethanol-water solution, 20mg of resorcinol and 50mg of the monomer synthesized in (1) were added, and the mixture was subjected to ultrasonic dispersion, followed by addition of 150. Mu.L of formaldehyde water solution, followed by insertion into a high-speed stirrer, stirring at 15000rpm for 7min, and washing the obtained solid with water and ethanol several times to obtain the product N, se-co-doped phenolic resin nano-adsorbent (Se-RF-H), which was placed in a vacuum oven and dried sufficiently.
Example 4:
4 parts of 2mg of Se-RF-H prepared under the conditions described in example 1 were accurately weighed, added to 5mL of palladium ion solution with pH value of 1,2,3,4 and concentration of 100mg/L, placed on a shaking table at 25 ℃ for adsorption for 2 hours, and the supernatant was collected. The concentration of remaining palladium ions in the solution was measured by inductively coupled plasma emission spectroscopy (ICP), and three groups were performed in parallel. As shown in FIG. 5, at pH 2, the adsorption capacity of Se-RF-H prepared in example 1 reached the maximum value, which was determined by the presence of Pd (II) and the charge properties of the adsorbent surface.
Example 5:
8 parts of 2mg of RF-H and 9 parts of 2mg of Se-RF-H are respectively and accurately weighed, respectively added into 5mL of palladium ion solution with the concentration of 100mg/L and the pH value of 2, placed on a shaking table at 25 ℃ to be respectively adsorbed for 5, 10, 15, 20, 30, 60, 120, 240 and 360min, and supernatant is collected. The concentration of remaining palladium ions in the solution was measured by inductively coupled plasma emission spectroscopy (ICP), and three groups were performed in parallel. The adsorption kinetics of Se-RF-H and RF-H to Pd (II) prepared in example 1 shown in FIG. 6, RF-H reached adsorption equilibrium within 120min, se-RF-H reached adsorption equilibrium only within 60min, and Se-RF-H equilibrium adsorption capacity was significantly higher than that of RF-H, and fitting calculation and analysis were performed on the data using a Pseudo first-order model and a Pseudo second-order model, respectively.
Example 6:
Accurately weighing 6 parts of 2mg Se-RF-H, respectively adding into 5mL palladium ion solutions (pH is 2) with the concentration of 100, 200, 300, 400 and 500mg/L in sequence, respectively placing on a shaking table at 25 ℃ for adsorption for 1H, and collecting supernatant; placing on a shaking table at 35 ℃ for adsorption for 1h, and collecting supernatant; placed on a shaking table at 45 ℃ for adsorption for 1h, and the supernatant is collected. The concentration of remaining palladium ions in the solution was measured by inductively coupled plasma emission spectroscopy (ICP), and three groups were performed in parallel. FIG. 7 shows adsorption isotherms of Se-RF-H to Pd (II) prepared in example 1, fitting adsorption data using Langmuir model, freundlich model, and exploring the effect of temperature on adsorption capacity. The adsorption capacity increases with increasing temperature over the test temperature range.
Example 7:
2Mg of RF-H and Se-RF-H are accurately weighed, 5mL of mixed solution which contains 50Mg/L of Pd (II), ca (II), cu (II), fe (III), K (I), mg (II), na (I), ni (II) and Zn (II) and is leached by simulated electronic wastes is added, the mixed solution is placed on a shaking table at 25 ℃ to be adsorbed for 1H, supernatant is collected, the residual concentration of various ions in the solution is detected by an inductively coupled plasma emission spectrometer (ICP), and three groups of experiments are carried out in parallel. As shown in FIG. 8, the RF-H and Se-RF-H prepared in example 1 still have the highest adsorption capacity to Pd (II) in the presence of numerous interfering ions, which is far greater than the adsorption capacity to Ca (II), cu (II), fe (III), K (I), mg (II), na (I), ni (II), zn (II) and the like metal ions, and the adsorption selectivity to Pd (II) of Se-RF-H is also significantly better than that of RF-H.
Example 8:
Accurately weighing 2mg of Se-RF-H, adding 5mL of palladium ion solution with the concentration of 100mg/L and the pH value of 2, placing on a shaking table at 25 ℃ for adsorption for 1H, taking supernatant, removing the solution, washing with deionized water, adding 5mL of eluent prepared from 1mol/L thiourea and 0.1mol/L hydrochloric acid, continuing to place on the shaking table for desorption for 1H, centrifuging to collect the adsorbent, removing the solution, washing with deionized water and drying, performing five cycles, detecting the concentration of residual palladium ions in the solution by an inductively coupled plasma emission spectrometer (ICP), and performing three groups of parallel experiments. As shown in FIG. 9, se-RF-H prepared in example 1 still has higher adsorption capacity after 5 adsorption-desorption cycle experiments, which indicates that the Se-RF-H has better adsorption regeneration performance and can keep good adsorption capacity to Pd (II) in the recycling process.
Description: the above embodiments are only for illustrating the present invention and not for limiting the technical solution described in the present invention; thus, while the invention has been described in detail with reference to the various embodiments described above, it will be understood by those skilled in the art that the invention may be modified or equivalents; all technical solutions and modifications thereof that do not depart from the spirit and scope of the present invention are intended to be included in the scope of the appended claims.
Claims (10)
1. A method for preparing a heteroatom doped phenolic resin nano adsorbent is characterized in that,
The heteroatom doped phenolic resin nano-adsorbent comprises an N doped phenolic resin nano-adsorbent RF-H or an N, se co-doped phenolic resin nano-adsorbent Se-RF-H;
Wherein,
The N-doped phenolic resin nano adsorbent RF-H is prepared by taking ammonia water and resorcinol as main raw materials and adopting a high-speed stirring method;
The N, se co-doped phenolic resin nano adsorbent Se-RF-H is prepared by taking ammonia water, resorcinol and bis (4-hydroxyphenyl) selenide monomer as main raw materials and adopting a high-speed stirring method;
The rotation speed of high-speed stirring is not lower than 5000rpm.
2. The preparation method of claim 1, wherein the preparation steps of the N-doped phenolic resin nano-adsorbent specifically include:
step A1: adding ammonia water into ethanol-water solution with a certain proportion, adding resorcinol, performing ultrasonic dispersion, then adding formaldehyde water solution, then inserting into a high-speed stirrer, stirring and reacting for a certain time t 2 at a certain rotating speed r 1, centrifugally separating the obtained solid, washing with water and ethanol for several times to obtain the product N-doped phenolic resin nano adsorbent RF-H, and placing into a vacuum oven for full drying.
3. The method according to claim 2, wherein in step A1, the aqueous ammonia, ethanol, deionized water, resorcinol and formaldehyde solution are used in an amount ratio of 35 to 150 μl:1-6mL:1-6mL:10-70mg: 35-150. Mu.L; wherein the mass percentage concentration of the formaldehyde aqueous solution is 37.0-40.0%.
4. The process according to claim 2, wherein in step A1, the rotation speed r 1 of the high-speed stirrer is 5000 to 15000rpm and the reaction time t 2 is 3 to 7min.
5. The preparation method of claim 1, wherein the preparation steps of the N, se co-doped phenolic resin nano adsorbent specifically include:
step B1: preparation of bis (4-hydroxyphenyl) selenide monomer
Firstly, adding selenium powder into chloroform A, dispersing the selenium powder by magnetic stirring, then adding a mixture of sulfonyl chloride and chloroform B, uniformly stirring, then adding a mixture of phenol and anhydrous diethyl ether, stirring to be clear and transparent, continuously reacting for a period of time t 1 at room temperature, dropwise adding Na 2CO3 solution with a certain concentration until no bubbles are generated, separating an organic phase by using a separating funnel, removing an organic solvent by using rotary evaporation, purifying by using a column chromatography, and finally obtaining golden yellow solid, namely a bis (4-hydroxyphenyl) selenide monomer;
Step B2: preparation of N, se co-doped phenolic resin nano adsorbent
Adding ammonia water into ethanol-water solution with a certain proportion, adding resorcinol and the bis (4-hydroxyphenyl) selenide monomer synthesized in the step B1, performing ultrasonic dispersion, then adding a certain amount of formaldehyde water solution, then inserting into a high-speed stirrer, stirring and reacting for a certain time t 3 at a certain rotating speed r 2, performing centrifugal separation on the obtained solid, washing with water and ethanol for several times to obtain the product N, se co-doped phenolic resin nano adsorbent (Se-RF-H), and placing into a vacuum oven for full drying.
6. The preparation method according to claim 5, wherein in the step B1, the selenium powder, chloroform A, sulfonyl chloride, chloroform B, phenol and anhydrous diethyl ether are used in an amount ratio of 1.98-7.90g:50-200mL:3.38-13.50g:50-200mL:4.70-18.80g:50-200mL.
7. The process according to claim 5, wherein in step B1, the reaction time t 1 is 2 to 4 hours and the mass concentration of Na 2CO3 solution is 10.50 to 42.00wt%.
8. The method of claim 5, wherein in step B2, the ratio of ammonia, ethanol, deionized water, resorcinol, aqueous formaldehyde solution, and bis (4-hydroxyphenyl) selenide is 35 to 150 μl:1-6mL:1-6mL:5-20mg:35-150 μl:12-50mg; wherein the mass percentage concentration of the formaldehyde aqueous solution is 37.0-40.0%.
9. The process according to claim 5, wherein in step B2, the rotation speed r 2 of the high-speed stirrer is 5000 to 15000rpm and the reaction time t 3 is 3 to 7 minutes.
10. Use of the heteroatom-doped phenolic resin nano-adsorbent prepared by the preparation method of claim 1 for adsorbing palladium ions.
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