CN107999033B - Polydopamine/aminated carbon nanotube/sodium alginate microspheres for adsorbing arsenic - Google Patents
Polydopamine/aminated carbon nanotube/sodium alginate microspheres for adsorbing arsenic Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The invention discloses a polydopamine/aminated carbon nanotube/sodium alginate microsphere for adsorbing arsenic, wherein Fe in the microsphere3O4The weight ratio of PDA, aminated carbon nanotube and sodium alginate is 1:0.8-1.2: 0.8-1.2. The preparation method of the microsphere comprises Fe3O4Preparation of Fe3O4Preparation of PDA, preparation of aminated carbon nanotube, Fe3O4Preparation of/PDA/aminated carbon nanotube, Fe3O4Preparation of PDA/aminated carbon nanotube/sodium alginate microspheres. The beneficial effects are that: the poly-dopamine/aminated carbon nanotube/alginic acid microsphere has the advantages of uniform particle size, good dispersibility, regular sphericity, more functional groups capable of adsorbing arsenic, good stability of the functional groups, higher adsorption capacity, higher adsorption rate, strong arsenic adsorption capacity and strong reusability, and is expected to greatly reduce the use cost of the adsorbent.
Description
Technical Field
The invention relates to the technical field of adsorption separation, in particular to a polydopamine/aminated carbon nanotube/sodium alginate microsphere for adsorbing arsenic.
Background
Arsenic is a gray and glossy chemical element, has nonmetal and metal properties, has a content of about 3mg/kg in the earth crust, is ranked in the second ten places in abundance in nature, and widely exists in nature. Along with human activities such as mining, metallurgy, various pesticides, arsenate drugs and the like and geochemical evolution, arsenic metal enters the environment in large quantity, and has extremely strong harm effect in the environment because the toxicity and certain properties of the arsenic metal are similar to those of heavy metal elements and the arsenic metal and other harmful elements coexist under different systems. Generally, arsenic poisoning is caused by food containing arsenic, air, and particularly water, and most of the poisoning is chronic poisoning, and since symptoms of the chronic poisoning are difficult to appear in a short time, it is important to treat arsenic pollution in water environment. Due to the great harm of arsenic in water, arsenic pollution is difficult to eliminate once formed in the environment, particularly the pollution to water bodies, and finally the arsenic can enter human bodies through underground water, surface water or biological enrichment so as to harm health. In the face of the increasingly severe global arsenic pollution problem of water bodies, economic and efficient arsenic removal technologies need to be developed to solve the threat of arsenic pollution to human beings as soon as possible.
In the prior art, for example, a Chinese patent with an issued publication number of CN 105381780B discloses a magnetic adsorbent for removing arsenic and antimony by adsorption-superconducting magnetic separation and a preparation method thereof, weak-magnetic material iron-based gel with strong adsorption capacity is loaded on a ferrite material with weak adsorption capacity and strong magnetism by an in-situ reaction method, so that the material with strong adsorption capacity and excellent magnetic separation property is obtained. After the material adsorbs arsenic and antimony, solid-liquid separation is completed by using a continuous superconducting magnetic separation system. The adsorbent can be used for removing arsenic and antimony pollutants in drinking water, underground water, industrial wastewater, water bodies such as lakes, reservoirs and rivers, and can also be used for removing heavy metals such as copper, chromium, cadmium, lead and thallium and pollutants such as phosphate in water and treating water body pollution in sudden pollution events. But the adsorbent has slower adsorption capacity and adsorption rate and poor reusability, thus causing higher use cost of the adsorbent.
Disclosure of Invention
The invention aims to provide a polydopamine/aminated carbon nanotube/sodium alginate microsphere for adsorbing arsenic, which has the advantages of uniform particle size, good dispersibility, regular sphericity, more functional groups capable of adsorbing arsenic, good stability of the functional groups, higher adsorption capacity, higher adsorption rate, strong arsenic adsorption capacity, strong reusability and hopeful great reduction of the use cost of an adsorbent.
Aiming at the problems mentioned in the technology, the invention adopts the technical scheme that:
polydopamine/aminated carbon nanotube/sodium alginate microspheres capable of adsorbing arsenic, wherein Fe in microspheres3O4The weight ratio of PDA to aminated carbon nanotube to sodium alginate is 1:0.8-1.2:0.8-1.2, and the diameter of the composite microsphere is 0.1-0.5 mm. The composite microsphere has more functional groups capable of adsorbing arsenic, has good stability, is an ideal adsorption material, has higher adsorption capacity and faster adsorption rate, has strong arsenic adsorption capacity, occupies a leading position in the adsorption process along with chemical integration of electron transfer, can be well separated and recovered from water through precipitation filtration after arsenic adsorption, has strong reusability, and still shows strong adsorption capacity after undergoing 8 adsorption-desorption cycles.
A method for preparing polydopamine/aminated carbon nanotube/sodium alginate microspheres for adsorbing arsenic comprises Fe3O4Preparation of Fe3O4Preparation of PDA, preparation of aminated carbon nanotube, Fe3O4Preparation of/PDA/aminated carbon nanotube, Fe3O4The preparation method of the/PDA/aminated carbon nanotube/sodium alginate microspheres specifically comprises the following steps:
Fe3O4preparation: introducing nitrogen into deionized water at 70-80 deg.C for 20-40min to remove oxygen in the solution, and adding FeCl at weight ratio of 2.2-3:1 into deionized water at 4-5:100(g/mL)3·6H2O and FeCl2·4H2O, fully stirring for 10-20min, adjusting pH to 9-10 with ammonia water, fully reacting for 20-40min, cooling to room temperature, separating the resultant under the action of external magnetic field, and adding deionized water and ethanolWashing for three times alternately, and freeze-drying to obtain Fe3O4For standby, the step adopts magnetic Fe synthesized by a coprecipitation method3O4Nano particles, ferrous ions are easy to be oxidized into ferric ions, the dosage of ferrous ions in the reaction is properly larger than the theoretical dosage so as to ensure that the ferric ions can completely react to obtain enough ferroferric oxide product, Fe3O4The nano particles are an environment-friendly material, have a large surface area, can adsorb arsenic, are compounded with other materials, can realize the magnetization of the material, and are convenient for magnetic separation;
Fe3O4preparation of PDA: fe at a ratio of 1:480-520(g/mL)3O4Ultrasonically dispersing in Tris solution with pH of 8-9, and adding dopamine hydrochloride and Fe3O4The weight ratio of the Fe salt to the dopamine hydrochloride is 1:0.9-1.2, ultrasonic stirring is carried out for 5-7h under the condition of room temperature, the generated product is separated under the action of an external magnetic field, and is frozen and dried after being washed for three times by deionized water to obtain Fe3O4PDA, which is formed of magnetic Fe3O4Fe with nanoparticle as core and polydopamine as shell and in core-shell structure3O4The PDA surface has a large amount of phenolic hydroxyl groups, when the pH value of the environment is more than 3, the PDA surface carries negative charges to form mutual repulsion electrostatic action, which is beneficial to Fe3O4PDA has dispersion stability in water phase and magnetic response;
preparing an aminated carbon nanotube: ultrasonically dispersing carbon nanotubes in deionized water according to the material-liquid ratio of 1:740-760(g/mL), adding polyethyleneimine according to the weight ratio of 1:0.8-1.2, mechanically stirring for 22-25h at room temperature, centrifuging after the reaction is finished, washing the obtained product with deionized water for three times, drying to obtain the aminated carbon nanotubes, wherein the surface of the carbon nanotubes is grafted with amino groups, so that the characteristics of strong van der Waals force on the surface of the carbon nanotubes, difficult dispersion and incapability of fully utilizing the huge specific surface area of the carbon nanotubes can be changed, the dispersibility of the carbon nanotubes in the deionized water is improved, the structure of the tube body is not damaged, amino bonds appear at the end of the tube body, the amino groups have high reaction activity and can react with PDA to promote the formation of a PDA cross-linking network at the initial stage of the reaction, so that the mechanical property and the arsenic adsorption property of the PDA are improved, the application range to the adsorption pH value is wider;
Fe3O4preparation of PDA/aminated carbon nanotubes: fe at the ratio of 1:120-130(g/mL)3O4Dispersing PDA and aminated carbon nanotube in deionized water, ultrasonic treating for 20-40min, mixing and stirring for 5-7 hr, magnetically separating, washing with deionized water for three times, and freeze drying to obtain Fe3O4PDA/aminated carbon nanotube, dopamine has both reducing and crosslinking effects, and can be crosslinked with aminated carbon nanotube to form Fe3O4The PDA/aminated carbon nanotube has more functional groups capable of adsorbing arsenic, has good stability, is an ideal adsorbing material, has good adsorption effect, can be well separated and recovered from water through precipitation and filtration after adsorbing arsenic, has high cyclic utilization degree, and still shows strong adsorption capacity after undergoing 8 adsorption-desorption cycles;
Fe3O4preparation of PDA/aminated carbon nanotube/sodium alginate microspheres: mixing sodium alginate and Fe at a ratio of 1:40-60(g/mL)3O4Dissolving PDA/aminated carbon nanotube in deionized water, mixing, dripping the mixture into 1.8-2.2wt% calcium chloride solution with transverse flow pump, solidifying for 110-3O4The method comprises the following steps of controlling the dynamic process of the sodium alginate, and preparing the polydopamine/aminated carbon nanotube/sodium alginate microspheres by wrapping, wherein the microspheres have uniform particle size, good dispersibility and regular sphericity, can realize industrial production, have higher adsorption capacity and higher adsorption rate, have stronger arsenic adsorption capacity, have the removal rate of trivalent arsenic as high as 92.38 percent, have good regeneration cycle service performance, and are expected to greatly reduce the use cost of the adsorbent.
Compared with the prior art, the invention has the advantages that: 1) the composite microsphere has more functional groups capable of adsorbing arsenic, and the functional groups have good stability and are ideal adsorption materials; 2) the composite microsphere has higher adsorption capacity, faster adsorption rate and strong arsenic adsorption capacity, the removal rate of trivalent arsenic reaches 92.38%, and chemical integration accompanied with electron transfer occupies a dominant position in the adsorption process; 3) the composite microsphere can be well separated and recovered from water through precipitation and filtration after being used for adsorbing arsenic, has strong reusability, and still shows strong adsorption capacity after undergoing 8 adsorption-desorption cycles; 4) the preparation method comprises the steps of crosslinking dopamine and the aminated carbon nanotube, and preparing the microspheres by wrapping the dopamine and the aminated carbon nanotube with sodium alginate, wherein the microspheres have uniform particle size, good dispersibility and regular sphericity, and can realize industrial production.
Detailed Description
The scheme of the invention is further illustrated by the following examples:
example 1:
polydopamine/aminated carbon nanotube/sodium alginate microspheres capable of adsorbing arsenic, wherein Fe in microspheres3O4The weight ratio of PDA to aminated carbon nanotube to sodium alginate is 1:0.8-1.2:0.8-1.2, and the diameter of the composite microsphere is 0.1-0.5 mm.
A method for preparing polydopamine/aminated carbon nanotube/sodium alginate microspheres for adsorbing arsenic comprises Fe3O4Preparation of Fe3O4Preparation of PDA, preparation of aminated carbon nanotube, Fe3O4Preparation of/PDA/aminated carbon nanotube, Fe3O4The preparation method of the/PDA/aminated carbon nanotube/sodium alginate microspheres specifically comprises the following steps:
1）Fe3O4preparation: introducing nitrogen into deionized water at 70-80 deg.C for 20-40min to remove oxygen in the solution, and adding FeCl at weight ratio of 2.2-3:1 into deionized water at 4-5:100(g/mL)3·6H2O and FeCl2·4H2O, fully stirring for 10-20min, adjusting the pH value to 9-10 by using ammonia water, fully reacting for 20-40min, and cooling to room temperature to obtain the productSeparating the materials under the action of an external magnetic field, alternately washing the materials with deionized water and ethanol for three times, and freeze-drying the materials to obtain Fe3O4And is ready for use;
2）Fe3O4preparation of PDA: fe at a ratio of 1:480-520(g/mL)3O4Ultrasonically dispersing in Tris solution with pH of 8-9, and adding dopamine hydrochloride and Fe3O4The weight ratio of the Fe salt to the dopamine hydrochloride is 1:0.9-1.2, ultrasonic stirring is carried out for 5-7h under the condition of room temperature, the generated product is separated under the action of an external magnetic field, and is frozen and dried after being washed for three times by deionized water to obtain Fe3O4/PDA；
3) Preparing an aminated carbon nanotube: ultrasonically dispersing a carbon nano tube in deionized water according to the material-liquid ratio of 1:740-760(g/mL), adding polyethyleneimine according to the weight ratio of 1:0.8-1.2 of the carbon nano tube to the polyethyleneimine, mechanically stirring for 22-25h at room temperature, centrifuging after the reaction is finished, washing the obtained product with the deionized water for three times, and drying to obtain an aminated carbon nano tube for later use;
4）Fe3O4preparation of PDA/aminated carbon nanotubes: fe at the ratio of 1:120-130(g/mL)3O4Dispersing PDA and aminated carbon nanotube in deionized water, ultrasonic treating for 20-40min, mixing and stirring for 5-7 hr, magnetically separating, washing with deionized water for three times, and freeze drying to obtain Fe3O4PDA/aminated carbon nanotubes;
5）Fe3O4preparation of PDA/aminated carbon nanotube/sodium alginate microspheres: mixing sodium alginate and Fe at a ratio of 1:40-60(g/mL)3O4Dissolving PDA/aminated carbon nanotube in deionized water, mixing, dripping the mixture into 1.8-2.2wt% calcium chloride solution with transverse flow pump, solidifying for 110-3O4the/PDA/aminated carbon nano tube/sodium alginate microspheres are polydopamine/aminated carbon nano tube/sodium alginate microspheres.
Example 2:
polydopamine/aminated carbon nanotube/seaweed for adsorbing arsenicSodium salt microsphere, Fe in microsphere3O4The weight ratio of PDA to aminated carbon nanotube to sodium alginate is 1:1.2:0.8, and the diameter of the composite microsphere is 0.1-0.5 mm.
A method for preparing polydopamine/aminated carbon nanotube/sodium alginate microspheres for adsorbing arsenic comprises Fe3O4Preparation of Fe3O4Preparation of PDA, preparation of aminated carbon nanotube, Fe3O4Preparation of/PDA/aminated carbon nanotube, Fe3O4The preparation method of the/PDA/aminated carbon nanotube/sodium alginate microspheres specifically comprises the following steps:
1）Fe3O4preparation: introducing nitrogen into deionized water at 80 ℃ for 25min to remove oxygen in the solution, and adding FeCl into the deionized water according to the material-to-liquid ratio of 5:100(g/mL) in the weight ratio of 2.2:13·6H2O and FeCl2·4H2O, fully stirring for 20min, adjusting the pH value to 9 by using ammonia water, fully reacting for 40min, cooling to room temperature, separating the generated product under the action of an external magnetic field, alternately washing with deionized water and ethanol for three times, and freeze-drying to obtain Fe3O4And is ready for use;
2）Fe3O4preparation of PDA: fe at a ratio of 1:520 (g/mL)3O4Ultrasonically dispersing in Tris solution with pH of 8, and adding dopamine hydrochloride and Fe3O4The weight ratio of the Fe salt to the dopamine hydrochloride is 1:1.2, ultrasonic stirring is carried out for 5 hours at room temperature, the generated product is separated under the action of an external magnetic field, and is frozen and dried after being washed for three times by deionized water to obtain Fe3O4/PDA；
3) Preparing an aminated carbon nanotube: ultrasonically dispersing a carbon nano tube in deionized water according to the material-liquid ratio of 1:760 (g/mL), adding polyethyleneimine according to the weight ratio of 1:0.8 of the carbon nano tube to the polyethyleneimine, mechanically stirring for 22-25h at room temperature, centrifuging after the reaction is finished, washing the obtained product with the deionized water for three times, and drying to obtain an aminated carbon nano tube for later use;
4）Fe3O4PDA/amino carbon nanoPreparing a rice tube: fe at a ratio of 1:130 (g/mL)3O4Dispersing PDA and aminated carbon nanotube in deionized water, ultrasonic treating for 20min, mixing and stirring for 5 hr, magnetically separating, washing with deionized water for three times, and freeze drying to obtain Fe3O4PDA/aminated carbon nanotubes;
5）Fe3O4preparation of PDA/aminated carbon nanotube/sodium alginate microspheres: mixing sodium alginate and Fe at a ratio of 1:60 (g/mL)3O4Dissolving PDA/aminated carbon nanotube in deionized water, mixing, dripping the mixture into 1.8wt% calcium chloride solution with transverse flow pump, solidifying for 130min, filtering, washing, and oven drying to obtain Fe3O4the/PDA/aminated carbon nano tube/sodium alginate microspheres are polydopamine/aminated carbon nano tube/sodium alginate microspheres.
Example 3:
polydopamine/aminated carbon nanotube/sodium alginate microspheres capable of adsorbing arsenic, wherein Fe in microspheres3O4The weight ratio of PDA to aminated carbon nanotube to sodium alginate is 1:1:1, and the diameter of the composite microsphere is 0.1-0.5 mm.
A method for preparing polydopamine/aminated carbon nanotube/sodium alginate microspheres for adsorbing arsenic comprises Fe3O4Preparation of Fe3O4Preparation of PDA, preparation of aminated carbon nanotube, Fe3O4Preparation of/PDA/aminated carbon nanotube, Fe3O4The preparation method of the/PDA/aminated carbon nanotube/sodium alginate microspheres specifically comprises the following steps:
1）Fe3O4preparation: introducing nitrogen into deionized water at 75 ℃ for 30min to remove oxygen in the solution, and adding FeCl into the deionized water according to the material-liquid ratio of 4.5:100 (g/mL) in the weight ratio of 2.6:13·6H2O and FeCl2·4H2O, fully stirring for 15min, adjusting the pH value to 9.5 by using ammonia water, fully reacting for 30min, cooling to room temperature, separating the generated product under the action of an external magnetic field, alternately washing with deionized water and ethanol for three times, and freeze-drying to obtain Fe3O4And is ready for use;
2）Fe3O4preparation of PDA: fe at a ratio of 1:500 (g/mL)3O4Ultrasonically dispersing in Tris solution with pH of 8.5, and adding dopamine hydrochloride and Fe3O4The weight ratio of the Fe-B-C-D-3O4/PDA；
3) Preparing an aminated carbon nanotube: ultrasonically dispersing a carbon nano tube in deionized water according to the material-liquid ratio of 1:750 (g/mL), adding polyethyleneimine according to the weight ratio of 1:1 of the carbon nano tube to the polyethyleneimine, mechanically stirring for 24 hours at room temperature, centrifuging after the reaction is finished, washing the obtained product with the deionized water for three times, and drying to obtain an aminated carbon nano tube for later use;
4）Fe3O4preparation of PDA/aminated carbon nanotubes: fe at a ratio of 1:125 (g/mL)3O4Dispersing PDA and aminated carbon nanotube in deionized water, ultrasonic treating for 30min, mixing and stirring for 6 hr, magnetically separating, washing with deionized water for three times, and freeze drying to obtain Fe3O4PDA/aminated carbon nanotubes;
5）Fe3O4preparation of PDA/aminated carbon nanotube/sodium alginate microspheres: sodium alginate and Fe according to the material-liquid ratio of 1:50 (g/mL)3O4Dissolving PDA/aminated carbon nanotube in deionized water, mixing, dripping the mixture into 2.0wt% calcium chloride solution with transverse flow pump, solidifying for 120min, filtering, washing, and oven drying to obtain Fe3O4the/PDA/aminated carbon nano tube/sodium alginate microspheres are polydopamine/aminated carbon nano tube/sodium alginate microspheres.
Example 4:
polydopamine/aminated carbon nanotube/sodium alginate microspheres capable of adsorbing arsenic, wherein Fe in microspheres3O4The weight ratio of PDA to aminated carbon nanotube to sodium alginate is 1:1:1, and the diameter of the composite microsphere is 0.1-0.5 mm.
A method for preparing polydopamine/aminated carbon nanotube/sodium alginate microspheres for adsorbing arsenic comprises Fe3O4Preparation of Fe3O4Preparation of PDA, preparation of aminated carbon nanotube, Fe3O4Preparation of/PDA/aminated carbon nanotube, Fe3O4The preparation method of the/PDA/aminated carbon nanotube/sodium alginate microspheres specifically comprises the following steps:
1）Fe3O4preparation: introducing nitrogen into deionized water at 75 ℃ for 30min to remove oxygen in the solution, and adding FeCl into the deionized water according to the material-liquid ratio of 4.5:100 (g/mL) in the weight ratio of 2.6:13·6H2O and FeCl2·4H2O, fully stirring for 15min, adjusting the pH value to 9-10 by using ammonia water, fully reacting for 30min, cooling to room temperature, separating the generated product under the action of an external magnetic field, alternately washing with deionized water and ethanol for three times, and freeze-drying to obtain Fe3O4And is ready for use;
2）Fe3O4preparation of PDA: fe at a ratio of 1:500 (g/mL)3O4Ultrasonically dispersing in Tris solution with pH of 8.5, and adding dopamine hydrochloride and Fe3O4The weight ratio of the Fe-B-C-D-3O4/PDA；
3) Preparing an aminated carbon nanotube: ultrasonically dispersing a carbon nano tube in deionized water according to the material-liquid ratio of 1:750 (g/mL), adding polyethyleneimine according to the weight ratio of 1:1 of the carbon nano tube to the polyethyleneimine of 1:1, then adding a condensing agent, mechanically stirring for 24 hours at room temperature, centrifuging after the reaction is finished, washing the obtained product with the deionized water for three times, and drying to obtain the aminated carbon nano tube, wherein the addition amount of the condensing agent is 2.2-2.8 times of the weight of the carbon nano tube, the condensing agent is a mixture of 1-hydroxy-7-azobenzotriazol, 1-hydroxybenzotriazole and 4-phenylazophenol with the weight ratio of 1:0.75-0.82:0.02-0.03, and the components in the condensing agent can exert the mutual synergistic action, so that the reaction of the carbon nano tube and the polyethyleneimine has the advantages of high reaction speed, small product derotation, high yield and the like, carboxyl negative ions in the carbon nano tube attack a condensing agent to generate active intermediate acyloxyurea positive ions, and then the active intermediate acyloxyurea positive ions react with amino components to generate corresponding muscle derivatives, so that side reactions are reduced, the racemization degree of products is effectively reduced, the condensation yield is improved, the amination degree of the carbon nano tube is improved, the number of groups adsorbing arsenic in the microspheres is finally increased, and the trouble of separation is reduced;
4）Fe3O4preparation of PDA/aminated carbon nanotubes: fe at a ratio of 1:125 (g/mL)3O4Dispersing PDA and aminated carbon nanotube in deionized water, ultrasonic treating for 30min, mixing and stirring for 6 hr, magnetically separating, washing with deionized water for three times, and freeze drying to obtain Fe3O4PDA/aminated carbon nanotubes;
5）Fe3O4preparation of PDA/aminated carbon nanotube/sodium alginate microspheres: sodium alginate and Fe according to the material-liquid ratio of 1:50 (g/mL)3O4Dissolving PDA/aminated carbon nanotube in deionized water, mixing, dripping the mixture into 2.0wt% calcium chloride solution with transverse flow pump, solidifying for 120min, filtering, washing, and oven drying to obtain Fe3O4the/PDA/aminated carbon nano tube/sodium alginate microspheres are polydopamine/aminated carbon nano tube/sodium alginate microspheres.
Example 5:
arsenic adsorption Performance test
The test group was the product of example 3 and the control group was a commercially available arsenic adsorbing product.
Preparation of standard arsenic adsorption solution for adsorption experiment: drying arsenic trioxide powder at 105 ℃ for 2 hours for later use, weighing 0.6600g of arsenic trioxide powder, dissolving in 10mL of 1mmol/L sodium hydroxide solution, transferring into a volumetric flask, and metering to 500mL to obtain 1mg/mL arsenic standard stock solution. Then transferring 20mL of 1mg/mL arsenic standard stock solution into a volumetric flask to reach the constant volume of 1000mL, and obtaining the arsenic standard adsorption solution with the concentration of 20 mg/L.
The adsorption experiment method comprises the following steps: preparing two 20mg/L arsenic adsorption standard solutions, respectively adding the solutions into a test group product and a control group product according to the dosage of 0.5g/L, then putting the products into a magnetic stirrer, continuously stirring at the rotating speed of 150r/min, taking the products out for 3 hours, filtering, taking a proper amount of adsorbed arsenic solution, and measuring the residual arsenic content according to a silver diethyldithiocarbamate spectrophotometry (GB/T5750.6-2006).
The removal rate of the test group arsenic is 92.38%, and the removal rate of the control group arsenic is 53.69%, which shows that the product of example 3 has far better arsenic adsorption effect than the control group.
Conventional operations in the operation steps of the present invention are well known to those skilled in the art and will not be described herein.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A polydopamine/aminated carbon nanotube/sodium alginate microsphere for adsorbing arsenic is characterized in that: fe in said microspheres3O4The weight ratio of PDA, aminated carbon nanotube and sodium alginate is 1:0.8-1.2: 0.8-1.2; the preparation method of the microsphere comprises Fe3O4Preparation of Fe3O4Preparation of PDA, preparation of aminated carbon nanotube, Fe3O4Preparation of/PDA/aminated carbon nanotube, Fe3O4Preparing PDA/aminated carbon nanotube/sodium alginate microspheres; the method specifically comprises the following steps:
said Fe3O4The preparation steps of the PDA are as follows: fe at a ratio of 1:480-520(g/mL)3O4Ultrasonically dispersing in Tris solution with pH of 8-9, and adding dopamine hydrochloride and Fe3O4The weight ratio of the Fe salt to the dopamine hydrochloride is 1:0.9-1.2, ultrasonic stirring is carried out for 5-7h under the condition of room temperature, the generated product is separated under the action of an external magnetic field, and is frozen and dried after being washed for three times by deionized water to obtain Fe3O4/PDA；
The preparation steps of the aminated carbon nanotube are as follows: ultrasonically dispersing a carbon nano tube in deionized water according to the material-liquid ratio of 1:740-760(g/mL), adding polyethyleneimine according to the weight ratio of 1:0.8-1.2 of the carbon nano tube to the polyethyleneimine, mechanically stirring for 22-25h at room temperature, centrifuging after the reaction is finished, washing the obtained product with the deionized water for three times, and drying to obtain an aminated carbon nano tube for later use; said Fe3O4The preparation steps of the/PDA/aminated carbon nano tube are as follows: fe at the ratio of 1:120-130(g/mL)3O4Dispersing PDA and aminated carbon nanotube in deionized water, ultrasonic treating for 20-40min, mixing and stirring for 5-7 hr, magnetically separating, washing with deionized water for three times, and freeze drying to obtain Fe3O4PDA/aminated carbon nanotubes;
said Fe3O4The preparation method of the/PDA/aminated carbon nanotube/sodium alginate microspheres comprises the following steps: mixing sodium alginate and Fe at a ratio of 1:40-60(g/mL)3O4Dissolving PDA/aminated carbon nanotube in deionized water, mixing, dripping the mixture into 1.8-2.2wt% calcium chloride solution with transverse flow pump, solidifying for 110-3O4the/PDA/aminated carbon nano tube/sodium alginate microspheres are polydopamine/aminated carbon nano tube/sodium alginate microspheres.
2. The poly-dopamine/aminated carbon nanotube/sodium alginate microsphere for adsorbing arsenic as claimed in claim 1, wherein: the diameter of the composite microsphere is 0.1-0.5 mm.
3. The preparation method of the polydopamine/aminated carbon nanotube/sodium alginate microsphere capable of adsorbing arsenic according to claim 1, which is characterized by comprising the following steps: said Fe3O4The preparation steps are as follows: introducing nitrogen into deionized water at 70-80 deg.C for 20-40min, and adding FeCl at weight ratio of 2.2-3:1 into deionized water at 4-5:100(g/mL)3·6H2O and FeCl2·4H2O, fully stirring for 10-20min,adjusting pH to 9-10 with ammonia water, reacting for 20-40min, cooling to room temperature, separating the resultant under the action of external magnetic field, washing with deionized water and ethanol for three times, and lyophilizing to obtain Fe3O4And then standby.
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