CN111606309A - Composite separation membrane for extracting tellurium and preparation method thereof - Google Patents
Composite separation membrane for extracting tellurium and preparation method thereof Download PDFInfo
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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Abstract
The invention discloses a composite separation membrane for extracting tellurium and a preparation method thereof. The prepared composite membrane has stable mechanical property, good repeatability and complete form, and the carbon nano tube and the manganese dioxide nano wire which are uniformly dispersed after being activated are mutually crosslinked to form a stable structure, so that the base membrane has higher specific surface area, and the agglomeration problem of zero-valent iron is effectively solved; the high adsorption performance of zero-valent iron ensures that the membrane material has high adsorption separation efficiency on tellurium ions in a solution, the separation rate can reach 98 percent at most, the separation membrane has good repeatability and can be well recycled, and meanwhile, the preparation method of the separation membrane is simple and easy to operate, has low cost and no secondary pollution, and is suitable for industrial extraction and application of tellurium.
Description
Technical Field
The invention relates to the technical field of chemical separation, in particular to a composite separation membrane for extracting tellurium and a preparation method thereof.
Background
Tellurium is a rare element, and the total amount of tellurium is far lower than that of noble metals such as silver, gold, platinum and the like. In nature, in addition to the simple substance tellurium, tellurium is mainly compounded with gold, silver, and platinum group elements and metal elements such as lead, bismuth, copper, iron, zinc, and nickel to form tellurides, tellurium sulfides, oxides, and oxygen-containing salts of tellurium, and the like. Tellurium is mainly applied to a plurality of fields such as metallurgy, petrochemical industry, electronics, electricity, solar batteries, glass, ceramics, medicine and the like in industrial production. With the rapid development of economy and technology and the emergence of new application fields, the demand of tellurium in the industrial industry is continuously increasing, but the yield of tellurium is slowly increasing and the annual production is limited, so that the tellurium always stays in a state of short supply and short demand. Meanwhile, tellurium is an unnecessary recessive toxic trace element in human body, more than 95% of tellurium can be combined with proteins in various tissues of human body and stored in kidney, spleen, heart and liver, and once the concentration exceeds 2.5 mg/kg, the function of liver and kidney can be degraded, so that the problem of tellurium pollution in environment is very necessary to be controlled and solved.
The separation of the tellurium element from the environmental pollutants can not only effectively solve the problem of resource shortage of tellurium, but also reduce the environmental burden and create a safer and healthier living atmosphere for human beings. The prior art for extracting tellurium mostly uses tellurium-containing anode slime generated by electrolytic copper as a raw material, and tellurium is extracted by utilizing a combined treatment method of acidification and calcination, alkaline leaching, oxidation-acid leaching or dressing-metallurgy after the anode slime is subjected to pyrogenic treatment. Furthermore, the method is simple. The extraction of tellurium from the electrolytic sludge needs to consume a large amount of mineral resources, along with the continuous development and utilization of human beings, the reserves of the mineral resources are also continuously reduced, and the excessive development can make people face more severe resource shortage and environmental pollution situations. Therefore, the method has important application value for recovering rare resources from photovoltaic wastes by developing simple, convenient, efficient, environment-friendly, cheap and controllable separation materials and processes.
The zero-valent iron has high surface activity and a micro-sodium hierarchical structure, the micro-structure can provide higher mechanical strength for the material, the nano-structure can improve higher surface activity for the material, but the zero-valent iron is easy to agglomerate; the high-dispersion carbon nano tube has good thermal, mechanical and electrical properties, has good adsorption capacity on tellurium due to the characteristics of low density and high porosity, and can well solve the problem of agglomeration of zero-valent iron; MnO with three-dimensional network structure2The nano wire is a traditional one-dimensional material and also has good mechanical property and chemical resistance.
On the basis, the invention fully utilizes the respective advantages of the three substances and designs the composite separation membrane for extracting tellurium. Effectively recycling tellurium element in the environment, improving the resource utilization rate, solving the pollution problem caused by the resource utilization rate and further protecting the living space of human beings.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a composite separation membrane for extracting tellurium and a preparation method thereof.
In order to achieve the technical purpose, the invention is realized by the following technical scheme: the present invention provides
The utility model provides a compound separation membrane for extracting tellurium, its comprises base film and secondary membrane, and the reduction of secondary membrane in situ is loaded on the base film surface, the base film material is manganese dioxide nano wire and carbon nanotube, guarantees the stability of tellurium separation membrane and has improved the life of membrane, and the nanometer pipeline is crosslinked each other and is formed the laminated structure, the secondary membrane comprises the zero-valent iron nano-rod that has tellurium adsorption performance, guarantees the adsorption enrichment effect of complex film to tellurium.
Further, the diameter of the base film is 10-40 nm, and the length of the manganese dioxide nanowire is not less than 8 mu m; the size of the zero-valent iron nanorod is 200-500 nm.
The preparation method of the composite separation membrane for extracting tellurium comprises the following steps:
(1) activating the carbon nano tube by using acid, then mixing the activated carbon nano tube with a surfactant, adding the mixture into water, carrying out ultrasonic treatment for 10-15 h, and centrifuging to remove undispersed carbon nano tube solids to finally obtain a highly dispersed carbon nano tube dispersion liquid;
(2) adding manganese dioxide nanowires into deionized water, mechanically stirring for 12-48 h, and performing ultrasonic treatment for 5 minutes to obtain manganese dioxide nanowire suspension with uniform dispersion and concentration of 4-6 g/L;
(3) adding the carbon nano tube dispersion liquid into the manganese dioxide nanowire suspension, mixing and stirring, performing suction filtration to form a membrane by taking a 0.45-micron cellulose filter membrane as a supporting layer, washing the membrane for 2-6 times by using deionized water and absolute ethyl alcohol, and drying the membrane for 8-12 hours at the temperature of 30-80 ℃ to obtain a carbon nano tube and manganese dioxide nanowire composite membrane;
(4) adding a ferrous chloride solution into absolute ethyl alcohol, carrying out ultrasonic dispersion for 10min, uniformly dropwise adding a dispersion liquid onto the surface of the prepared composite membrane, slowly dropwise adding a reducing agent onto the surface of the membrane, washing for 2-6 times by using deionized water and absolute ethyl alcohol after complete reaction, and carrying out vacuum drying for 4-6 h at 40-80 ℃ to obtain the composite membrane material.
Further, in the step (1), the acid used comprises one or more of concentrated sulfuric acid and concentrated nitric acid; the surfactant comprises one or more of stearic acid, sodium dodecyl benzene sulfonate, fatty glyceride, and lecithin.
Further, in the step (1), the mass ratio of the carbon nano tube to the surfactant is 1: 1-1.5.
Further, in the step (1), the ultrasonic power is 400-800 w, the rotation speed during centrifugation is 9000-12000 r, and the centrifugation time is 30-50 min.
Further, in the step (2), the volume ratio of the carbon nanotube dispersion liquid to the manganese dioxide nanowire suspension liquid is 3-8: 1.
further, in the step (2), the manganese dioxide nanowire is obtained by carrying out hydrothermal synthesis on a manganese precursor, an oxidant, a cosolvent and deionized water, wherein the molar volume ratio of the manganese precursor to the oxidant to the cosolvent to water is 1mmol:3mmol:1mmol:26.67mL, the reaction temperature is 170-260 ℃, and the reaction time is 60-80 h; the oxidant comprises one or more of potassium permanganate, potassium dichromate, ammonium persulfate, potassium persulfate, boron peroxide and sodium perchlorate, the cosolvent comprises one or more of sodium benzoate, sodium salicylate, acetamide, ammonium sulfate and potassium sulfate, and the water is deionized water.
Further, in the step (3), the concentration of the ferrous chloride solution is 0.01-0.1 mol/L; the volume ratio of the ferrous chloride solution to the absolute ethyl alcohol is 1: 1-5; the reducing agent comprises one or more of sodium borohydride, potassium borohydride, hydrazine hydrate and sodium citrate.
The invention has the beneficial effects that:
1. the composite membrane prepared by the method disclosed by the invention is composed of a base membrane and a secondary membrane, the base membrane formed by mutually crosslinking the activated carbon nano tube and the manganese dioxide nanowire has stable mechanical property and higher specific surface area, the agglomeration problem of zero-valent iron is effectively solved, the secondary membrane formed by loading the nano zero-valent iron on the surface of the base membrane can provide higher surface activity, and meanwhile, the composite membrane has higher specific surface area, strong reducing capability and higher tellurium separation efficiency;
2. the preparation of the composite membrane mainly comprises the processes of activation, hydrothermal reaction and in-situ reduction of the carbon nano tube, the whole process is simple and easy to operate, the preparation cost is low, and the problem of secondary pollution is avoided;
3. the composite membrane has the advantages of high flux, strong interception capability, convenient cleaning and good reutilization, accords with the sustainable development concept guided by national science and technology development, and is suitable for industrial application.
Drawings
Fig. 1 is an SEM image of a tellurium-extracting composite film material prepared in example 1, wherein a is a low-magnification SEM image of a base film, B is a high-magnification SEM image of the base film, C is a low-magnification SEM image of the composite film after loading zero-valent iron, and D is a low-magnification SEM image of the composite film after loading zero-valent iron;
FIG. 2 is a statistical graph of the separation efficiency of the membrane material for tellurium under different interfering ion conditions;
FIG. 3 is a statistical plot of the separation efficiency of the composite membranes prepared in example 5 after multiple reuses.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
Example 1
(1) Taking 1.5 g of multi-walled carbon nanotubes in a 50mL beaker, adding 20mL of concentrated nitric acid into the beaker, magnetically stirring for 15-20 min, transferring the mixed solution into a 100 mL polytetrafluoroethylene autoclave, reacting for 4.5-6 h in a 150 ℃ oven, cooling to room temperature, filtering to obtain a sample, washing for 3-5 times with deionized water and ethanol respectively, and drying in a 60 ℃ oven for 8 h to obtain the activated carbon nanotubes. Taking 10 mg of activated carbon nano tube and 10 mg of sodium dodecyl benzene sulfonate into a 150mL beaker, adding 100 mL of deionized water, carrying out ultrasonic treatment for 10-15 h under 600 w of ultrasonic power, transferring the dispersion into a centrifugal tube after the ultrasonic treatment is finished, centrifuging for 30 min at 10000 r, and transferring the upper-layer dispersion into a 250 mL beaker to obtain highly dispersed carbon nano tube dispersion;
(2) according to the weight percentage of potassium sulfate: potassium persulfate: the molar ratio of the manganese sulfate monohydrate is 1:3:1, 5mmol of potassium sulfate, 15 mmol of potassium persulfate and 5mmol of manganese sulfate monohydrate are dissolved in 133.35 mL of deionized water, and then the mixture is transferred into a 250 mL reaction kettle to react for 60 hours at 250 ℃. Cooling and filtering after reaction, washing for many times by deionized water at 85 ℃, and drying for 8 h at 60 ℃ to obtain MnO2Aggregating the nanowires to obtain black blocky solids, adding 1 g of the black blocky solids into 250 mL of deionized water, stirring for 24 hours, and performing ultrasonic treatment to obtain manganese dioxide nanowire suspension; 30 mL of the carbon nanotube dispersion was added to a 100 mL beaker containing 10 mL of the manganese dioxide nanowire suspension, and stirred for 1 hour to obtain a uniform mixed solution. Placing a 0.45-micrometer cellulose filter membrane on a sand core device, performing suction filtration to form a membrane, finally washing with deionized water and absolute ethyl alcohol for 2-6 times, and drying at 60 ℃ for 8 hours to obtain a carbon nano tube and manganese dioxide nanowire composite membrane;
(3) 5 mL of 0.1M FeCl was taken2·4H2Placing the O solution in a beaker containing 20mL of absolute ethyl alcohol and 50mL, and carrying out ultrasonic treatment for 10min to obtain a uniform solution. Then slowly dripping the solution on the composite membrane prepared in the step (2) to ensure that FeCl is added2The solution is uniformly dispersed on the surface of the membrane. Then 20mL of 0.01M NaBH was taken4And dropwise adding the solution onto the surface of the membrane, controlling the dropwise adding speed to be 2 drops/S, continuously reacting for 30 min after the dropwise adding is finished, washing for 2-6 times by using deionized water and absolute ethyl alcohol after the reaction is completed, and then drying for 6h in a vacuum drying oven at 60 ℃ to obtain the composite separation membrane material for extracting tellurium.
(4) A tellurium separation test is carried out on the sodium tellurite solution by using the prepared composite membrane material, and the separation rate of the material to tellurium is found to reach 95%.
(5) The base film and the zero-valent iron-loaded composite film prepared in this example were characterized by SEM, as shown in fig. 1, from which it can be seen that the carbon nanotube and manganese dioxide nanowire composite film is composed of a large number of randomly oriented ultra-long nanowires and carbon nanotubes. Meanwhile, the manganese dioxide nanowires and the carbon nanotubes are dispersed and wound to form a three-dimensional network structure, the structure is stable, and MnO is used2The film may have excellent flexibility and mechanical stability due to the ultra-long structural characteristics and high dispersibility of the nanowires, and meanwhile, the porous structure on the surface of the film can facilitate the loading of zero-valent iron, so that the problem of zero-valent iron agglomeration is solved. After zero-valent iron is loaded on the surface of the base film in situ, a porous structure is formed on the surface of the base film. Meanwhile, the enriched zero-valent iron provides more active sites for tellurium, and is beneficial to the effective separation of tellurium.
Example 2
(1) Taking 1.5 g of single-walled carbon nanotube in a 50mL beaker, adding 10 mL of concentrated nitric acid and 10 mL of concentrated sulfuric acid into the beaker, magnetically stirring for 15-20 min, transferring the mixed solution into a 100 mL polytetrafluoroethylene autoclave, reacting for 4.5-6 h in a 150 ℃ oven, cooling to room temperature, filtering to obtain a sample, washing for 3-5 times with deionized water and ethanol respectively, and drying in a 60 ℃ oven for 8 h to obtain the activated carbon nanotube. And (2) putting 10 mg of activated carbon nano tube and 15 mg of stearic acid in a 150mL beaker, adding 100 mL of deionized water, carrying out ultrasonic treatment for 10-15 h under the ultrasonic power of 700 w, transferring the dispersion liquid into a centrifugal tube after the ultrasonic treatment is finished, centrifuging at 10000 r for 30 min, and transferring the upper-layer dispersion liquid into a 250 mL beaker to obtain the highly dispersed carbon nano tube dispersion liquid.
(2) According to the ammonium sulfate: ammonium persulfate: the molar ratio of sodium perchlorate to manganese sulfate monohydrate is 1:2:1:1, 8 mmol of ammonium sulfate, 16 mmol of ammonium persulfate, 8 mmol of sodium perchlorate and 8 mmol of manganese sulfate monohydrate are dissolved in 213.36 mL of deionized water, and then transferred to a 250 mL reaction kettle to react for 60 hours at 250 ℃. Cooling and filtering after reaction, washing for many times by deionized water at 85 ℃, and drying for 8 h at 60 ℃ to obtain MnO2Aggregating the nanowires to obtain black blocky solids, adding 1 g of the black blocky solids into 250 mL of deionized water, and stirring for 24 hours to obtain manganese dioxide nanowire suspension; 60 mL of the carbon nanotube dispersion was added to a 100 mL beaker containing 20mL of the manganese dioxide nanowire suspension, and stirred for 1 hour to obtain a uniform mixture. And (3) placing the cellulose filter membrane with the diameter of 0.45 mu m on a sand core device, carrying out suction filtration to form a film, finally washing the film for 2-6 times by using deionized water and absolute ethyl alcohol, and placing the film at the temperature of 60 ℃ for drying for 8 hours to obtain the carbon nano tube and manganese dioxide nanowire composite film.
(3) 5 mL of 0.05M FeCl was taken2·4H2The O solution is placed in a 50mL beaker containing 20mL of absolute ethanol and sonicated for 10min to obtain a homogeneous solution. Then slowly dripping the solution on the composite membrane prepared in the step (2) to ensure that FeCl is added2The solution is uniformly dispersed on the surface of the membrane. Then 20mL of 0.05M NaBH was taken4And dropwise adding the solution onto the surface of the membrane, controlling the dropwise adding speed to be 2 drops/S, continuously reacting for 30 min after the dropwise adding is finished, washing for 2-6 times by using deionized water and absolute ethyl alcohol after the reaction is completed, and then drying for 6h in a vacuum drying oven at 60 ℃ to obtain the composite separation membrane material for extracting tellurium.
(4) The prepared composite membrane material is used for carrying out a tellurium separation test on a sodium tellurite solution, and the separation rate of the material to tellurium is found to be 92%.
Example 3
(1) Putting 1 g of multi-walled carbon nanotube and 0.5 g of single-walled carbon nanotube into a 50mL beaker, adding 20mL of concentrated nitric acid into the beaker, magnetically stirring for 15-20 min, transferring the mixed solution into a 100 mL polytetrafluoroethylene autoclave, reacting for 4.5-6 h in a 150 ℃ oven, cooling to room temperature, filtering to obtain a sample, washing for 3-5 times by deionized water and ethanol respectively, and drying in a 60 ℃ oven for 8 h to obtain the activated carbon nanotube. And (2) putting 10 mg of activated carbon nano tube and 10 mg of sodium dodecyl benzene sulfonate into a 150mL beaker, adding 100 mL of deionized water into the beaker, carrying out ultrasonic treatment for 10-15 h under the ultrasonic power of 800 w, transferring the dispersion liquid into a centrifugal tube after the ultrasonic treatment is finished, centrifuging for 30 min at 10000 r, and transferring the upper-layer dispersion liquid into a 250 mL beaker to obtain the highly dispersed carbon nano tube dispersion liquid.
(2) According to the weight percentage of potassium sulfate: potassium permanganate: the molar ratio of the manganese sulfate monohydrate is 1:3:1, 2.5 mmol of potassium sulfate, 7.5mmol of potassium permanganate and 2.5 mmol of manganese sulfate monohydrate are dissolved in 66.68 mL of deionized water, and then the solution is transferred to a 250 mL reaction kettle and reacted for 60 hours at 250 ℃. Cooling and filtering after reaction, washing for many times by deionized water at 85 ℃, and drying for 8 h at 60 ℃ to obtain MnO2Aggregating the nanowires to obtain black blocky solids, adding 1 g of the black blocky solids into 250 mL of deionized water, and stirring for 24 hours to obtain manganese dioxide nanowire suspension; 60 mL of the carbon nanotube dispersion was added to a 100 mL beaker containing 10 mL of the manganese dioxide nanowire suspension, and stirred for 1 hour to obtain a uniform mixture. And (3) placing the cellulose filter membrane with the diameter of 0.45 mu m on a sand core device, carrying out suction filtration to form a film, finally washing the film for 2-6 times by using deionized water and absolute ethyl alcohol, and drying the film for 8 hours at the temperature of 60 ℃ to obtain the carbon nano tube and manganese dioxide nanowire composite film.
(3) 5 mL of 0.01M FeCl was taken2·4H2The O solution is placed in a 50mL beaker containing 20mL of absolute ethanol and sonicated for 10min to obtain a homogeneous solution. Then slowly dripping the solution on the composite membrane prepared in the step (2) to ensure that FeCl is added2The solution is uniformly dispersed on the surface of the membrane. Then 20mL of hydrazine hydrate solution is dripped on the surface of the membrane, the dripping speed is controlled to be 2 drops/S, the reaction is continued for 30 min after the dripping is finished, and deionized water are used for no reaction after the reaction is finishedWashing with water and ethanol for 2-6 times, and then drying in a vacuum drying oven at 60 ℃ for 6h to prepare the composite separation membrane material for extracting tellurium.
(4) The prepared composite membrane material is used for carrying out a tellurium separation test on a sodium tellurite solution, and the separation rate of the material to tellurium is found to be 94%.
(5) In order to study the influence of the existence of interfering ions on the tellurium separation efficiency, other variables were controlled to be unchanged, and 10 ml of 100 ppm each containing F was measured-、CH3COO-、Cl-、NO3 -、CO3 -The solution is added into a sodium tellurite solution for membrane separation experiment, the experimental result is shown in figure 2, and the result shows that: comparison with blank group, CH3COO-Has the smallest influence of F-And Cl-The impact on separation efficiency is close, secondly CO3 -The most significant inhibitory effect is NO3 -Is due to NO3 -The strong oxidizing property of (2) causes zero-valent iron on the surface of the membrane material to be oxidized, thereby inhibiting the separation of tellurium. From the above results, it can be seen that zero-valent iron plays a crucial role in the separation reaction, and thus it can be used for complicated water treatment.
Example 4
(1) Taking 1 g of single-walled carbon nanotube and 0.5 g of multi-walled carbon nanotube in a 50mL beaker, adding 20mL of concentrated nitric acid into the beaker, magnetically stirring for 15-20 min, transferring the mixed solution into a 100 mL polytetrafluoroethylene autoclave, reacting for 4.5-6 h in a 150 ℃ oven, naturally cooling to room temperature, filtering to obtain a sample, washing for 3-5 times by deionized water and ethanol respectively, and drying in a 60 ℃ oven for 8 h to obtain the activated carbon nanotube. And (2) taking 20 mg of activated carbon nano tube and 20 mg of sodium dodecyl benzene sulfonate into a 150mL beaker, adding 100 mL of deionized water into the beaker, carrying out ultrasonic treatment for 10-15 h under the ultrasonic power of 700 w, transferring the dispersion liquid into a centrifugal tube after the ultrasonic treatment is finished, centrifuging for 30 min at 10000 r, and transferring the upper-layer dispersion liquid into a 250 mL beaker to obtain the highly dispersed carbon nano tube dispersion liquid.
(2) According to the weight percentage of sodium benzoate: height ofPotassium manganate: the molar ratio of the manganese sulfate monohydrate is 1:3:1, 1.5 mmol of potassium persulfate, 4.5 mmol of potassium permanganate and 1.5 mmol of manganese sulfate monohydrate are dissolved in 40 mL of deionized water, and then the solution is transferred to a 250 mL reaction kettle to react for 60 hours at 250 ℃. Cooling and filtering after reaction, washing for many times by deionized water at 85 ℃, and drying for 8 h at 60 ℃ to obtain MnO2Aggregating the nanowires to obtain black blocky solids, adding 1 g of the black blocky solids into 250 mL of deionized water, and stirring for 24 hours to obtain manganese dioxide nanowire suspension; 40 mL of the carbon nanotube dispersion was added to a 100 mL beaker containing 10 mL of the manganese dioxide nanowire suspension, and stirred for 1 hour to obtain a uniform mixture. And (3) placing the cellulose filter membrane with the diameter of 0.45 mu m on a sand core device, carrying out suction filtration to form a film, finally washing the film for 2-6 times by using deionized water and absolute ethyl alcohol, and drying the film for 8 hours at the temperature of 60 ℃ to obtain the carbon nano tube and manganese dioxide nanowire composite film.
(3) 5 mL of 0.01M FeCl was taken2·4H2The O solution is placed in a 50mL beaker containing 20mL of absolute ethanol and sonicated for 10min to obtain a homogeneous solution. Then slowly dripping the solution on the composite membrane prepared in the step (2) to ensure that FeCl is added2The solution is uniformly dispersed on the surface of the membrane. And then, dropwise adding 20mL of 0.01M potassium borohydride solution onto the surface of the membrane, controlling the dropwise adding speed to be 2 drops/S, continuously reacting for 30 min after the dropwise adding is finished, washing for 2-6 times by using deionized water and absolute ethyl alcohol after the reaction is completed, and then drying for 6h in a vacuum drying oven at 60 ℃ to obtain the composite separation membrane material for extracting tellurium.
(4) The prepared composite membrane material is used for carrying out a tellurium separation test on a sodium tellurite solution, and the separation rate of the material to tellurium is found to be 90%.
Example 5
(1) Taking 1.5 g of multi-walled carbon nanotube in a 50mL beaker, adding 20mL of concentrated nitric acid into the beaker, magnetically stirring for 15-20 min, transferring the mixed solution into a 100 mL polytetrafluoroethylene autoclave, reacting for 4.5-6 h in a 150 ℃ oven, naturally cooling to room temperature, filtering to obtain a sample, washing for 3-5 times with deionized water and ethanol respectively, and drying in a 60 ℃ oven for 8 h to obtain the activated carbon nanotube. And (2) taking 20 mg of activated carbon nano tube and 20 mg of sodium dodecyl benzene sulfonate into a 150mL beaker, adding 100 mL of deionized water into the beaker, carrying out ultrasonic treatment for 10-15 h under 600 w of ultrasonic power, transferring the dispersion liquid into a centrifugal tube after the ultrasonic treatment is finished, centrifuging for 30 min at 10000 r, and transferring the upper-layer dispersion liquid into a 250 mL beaker to obtain the highly dispersed carbon nano tube dispersion liquid.
(2) According to the weight percentage of ammonium chloride: ammonium persulfate: the molar ratio of the manganese sulfate monohydrate is 1:3:1, 2.75 mmol of ammonium chloride, 8.25mmol of ammonium persulfate and 2.75 mmol of manganese sulfate monohydrate are dissolved in 73.34 mL of deionized water, and then the solution is transferred into a 250 mL reaction kettle to react for 60 hours at 250 ℃. Cooling and filtering after reaction, washing for many times by deionized water at 85 ℃, and drying for 8 h at 60 ℃ to obtain MnO2Aggregating the nanowires to obtain black blocky solids, adding 1 g of the black blocky solids into 250 mL of deionized water, and stirring for 24 hours to obtain manganese dioxide nanowire suspension; 80 mL of the carbon nanotube dispersion was added to a 100 mL beaker containing 10 mL of the manganese dioxide nanowire suspension, and stirred for 1 hour to obtain a uniform mixed solution. And (3) placing the cellulose filter membrane with the diameter of 0.45 mu m on a sand core device, carrying out suction filtration to form a film, finally washing the film for 2-6 times by using deionized water and absolute ethyl alcohol, and drying the film for 8 hours at the temperature of 60 ℃ to obtain the carbon nano tube and manganese dioxide nanowire composite film.
(3) 5 mL of 0.03M FeCl was taken2·4H2The O solution is placed in a 50mL beaker containing 20mL of absolute ethanol and sonicated for 10min to obtain a homogeneous solution. Then slowly dripping the solution on the composite membrane prepared in the step (2) to ensure that FeCl is added2The solution is uniformly dispersed on the surface of the membrane. And then, dropwise adding 20mL of 0.01M sodium citrate solution onto the surface of the membrane, controlling the dropwise adding speed to be 2 drops/S, continuously reacting for 30 min after the dropwise adding is finished, washing for 2-6 times by using deionized water and absolute ethyl alcohol after the reaction is completed, and then drying for 6h in a vacuum drying oven at 60 ℃ to obtain the composite separation membrane material for extracting tellurium.
(4) The prepared composite membrane material is used for carrying out a tellurium separation test on a sodium tellurite solution, and the separation rate of the material to tellurium is found to be 98%.
(5) In order to research the recycling effect of the composite membrane material, the composite membrane prepared in the example is subjected to a recycling experiment, and the result is shown in fig. 3, and it can be seen from the figure that after 10 times of repeated use, the tellurium separation efficiency of the membrane material can still reach 95%, and is reduced by about 3% compared with the first time, which indicates that the separation membrane has excellent recycling performance.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.
Claims (10)
1. The composite separation membrane for extracting tellurium is characterized by comprising a base membrane and a secondary membrane, wherein the secondary membrane is in-situ reduced and loaded on the surface of the base membrane, the base membrane is made of manganese dioxide nanowires and carbon nanotubes, the nanotube wires are mutually crosslinked to form a laminated structure, and the secondary membrane is made of zero-valent iron nanorods with tellurium adsorption performance.
2. The composite separation membrane for extracting tellurium as claimed in claim 1, wherein the diameter of the base membrane is 10 to 40 nm, the length of the manganese dioxide nanowire is not less than 8 μm; the size of the zero-valent iron nanorod is 200-500 nm.
3. The method for preparing a composite separation membrane for extracting tellurium, according to any one of claims 1 to 2, comprising the specific steps of:
(1) activating the carbon nano tube by using acid, then mixing the activated carbon nano tube with a surfactant, adding the mixture into water, carrying out ultrasonic treatment for 10-15 h, and centrifuging to remove undispersed carbon nano tube solids to obtain a highly dispersed carbon nano tube dispersion liquid;
(2) adding manganese dioxide nanowires into deionized water, mechanically stirring for 12-48 h, and performing ultrasonic treatment for 5 minutes to obtain manganese dioxide nanowire suspension with uniform dispersion and concentration of 4-6 g/L;
(3) adding the carbon nano tube dispersion liquid into the manganese dioxide nanowire suspension, mixing and stirring, performing suction filtration to form a membrane by taking a 0.45-micron cellulose filter membrane as a supporting layer, washing the membrane for 2-6 times by using deionized water and absolute ethyl alcohol, and drying the membrane for 8-12 hours at the temperature of 30-80 ℃ to obtain a carbon nano tube and manganese dioxide nanowire composite membrane;
(4) adding a ferrous chloride solution into absolute ethyl alcohol, carrying out ultrasonic dispersion for 10min, uniformly dropwise adding a dispersion liquid onto the surface of the prepared composite membrane, slowly dropwise adding a reducing agent onto the surface of the membrane, washing for 2-6 times by using deionized water and absolute ethyl alcohol after complete reaction, and carrying out vacuum drying for 4-6 h at 40-80 ℃ to obtain the composite membrane material.
4. The method according to claim 3, wherein in the step (1), the acid includes one or more of concentrated sulfuric acid and concentrated nitric acid; the surfactant comprises one or more of stearic acid, sodium dodecyl benzene sulfonate, fatty glyceride, and lecithin.
5. The method for preparing a composite separation membrane for extracting tellurium, according to claim 3, wherein in the step (1), the mass ratio of the carbon nanotubes to the surfactant is 1:1 to 1.5.
6. The method for preparing a composite separation membrane for extracting tellurium according to claim 3, wherein in the step (1), the ultrasonic power is 400-800 w, the rotation speed during centrifugation is 9000-12000 r, and the centrifugation time is 30-50 min.
7. The method for preparing a composite separation membrane for extracting tellurium according to claim 3, wherein in the step (2), the volume ratio of the carbon nanotube dispersion liquid to the manganese dioxide nanowire suspension liquid is 3-8: 1.
8. the preparation method of the composite separation membrane for extracting tellurium according to claim 3, wherein in the step (2), the manganese dioxide nanowire is synthesized from a manganese precursor, an oxidant, a cosolvent and deionized water by a hydrothermal method, the molar volume ratio of the manganese precursor, the oxidant, the cosolvent and water is 1mmol:3mmol:1mmol:26.67mL, the reaction temperature is 170-260 ℃, and the reaction time is 60-80 hours; the oxidant comprises one or more of potassium permanganate, potassium dichromate, ammonium persulfate, potassium persulfate, boron peroxide and sodium perchlorate, the cosolvent comprises one or more of sodium benzoate, sodium salicylate, acetamide, ammonium sulfate and potassium sulfate, and the water is deionized water.
9. The method for preparing a composite separation membrane for extracting tellurium as claimed in claim 3, wherein in the step (3), the concentration of the ferrous chloride solution is 0.01-0.1 mol/L; the volume ratio of the ferrous chloride solution to the absolute ethyl alcohol is 1: 1-5.
10. The method of claim 3, wherein in the step (3), the reducing agent comprises one or more of sodium borohydride, potassium borohydride, hydrazine hydrate and sodium citrate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114792866A (en) * | 2022-04-11 | 2022-07-26 | 深圳市欣恒坤科技有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN116808843A (en) * | 2023-08-30 | 2023-09-29 | 新乡学院 | Loaded MnO 2-X Carbon nano tube-polyvinyl chloride mixed matrix ultrafiltration membrane and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004305948A (en) * | 2003-04-09 | 2004-11-04 | Ebara Corp | Washing method for separation membrane, and detergent |
| CN1935355A (en) * | 2006-09-07 | 2007-03-28 | 山东大学 | Manganese bioxide/carbon nano tube composite adsorbent and its preparing method |
| CN107285387A (en) * | 2017-07-27 | 2017-10-24 | 江苏大学 | It is a kind of to be used to extract the preparation method of tellurium element material and its application in photovoltaic discarded object |
| CN108339514A (en) * | 2018-01-29 | 2018-07-31 | 江苏大学 | A kind of preparation method and application of LDH load nano zero-valence iron composite material is in extraction selenium/tellurium |
| CN108854583A (en) * | 2018-06-05 | 2018-11-23 | 江苏大学 | A kind of preparation method of the hydrophily water-oil separationg film of imitative spider web frame |
| US20190218119A1 (en) * | 2018-01-18 | 2019-07-18 | Montgomery Chemicals Llc | Process for producing zero-valent iron nanoparticles and treating acid mine drainage |
-
2020
- 2020-06-30 CN CN202010609733.0A patent/CN111606309A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004305948A (en) * | 2003-04-09 | 2004-11-04 | Ebara Corp | Washing method for separation membrane, and detergent |
| CN1935355A (en) * | 2006-09-07 | 2007-03-28 | 山东大学 | Manganese bioxide/carbon nano tube composite adsorbent and its preparing method |
| CN107285387A (en) * | 2017-07-27 | 2017-10-24 | 江苏大学 | It is a kind of to be used to extract the preparation method of tellurium element material and its application in photovoltaic discarded object |
| US20190218119A1 (en) * | 2018-01-18 | 2019-07-18 | Montgomery Chemicals Llc | Process for producing zero-valent iron nanoparticles and treating acid mine drainage |
| CN108339514A (en) * | 2018-01-29 | 2018-07-31 | 江苏大学 | A kind of preparation method and application of LDH load nano zero-valence iron composite material is in extraction selenium/tellurium |
| CN108854583A (en) * | 2018-06-05 | 2018-11-23 | 江苏大学 | A kind of preparation method of the hydrophily water-oil separationg film of imitative spider web frame |
Non-Patent Citations (1)
| Title |
|---|
| HANQIANGYU等: ""In situ fabrication of dynamic nano zero-valent iron/activated carbon nanotubes membranes for tellurium separation"", 《CHEMICAL ENGINEERING SCIENCE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114792866A (en) * | 2022-04-11 | 2022-07-26 | 深圳市欣恒坤科技有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN116808843A (en) * | 2023-08-30 | 2023-09-29 | 新乡学院 | Loaded MnO 2-X Carbon nano tube-polyvinyl chloride mixed matrix ultrafiltration membrane and preparation method thereof |
| CN116808843B (en) * | 2023-08-30 | 2023-11-21 | 新乡学院 | Loaded MnO 2-X Carbon nano tube-polyvinyl chloride mixed matrix ultrafiltration membrane and preparation method thereof |
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