CN108905970B - Preparation method and application of clinoptilolite modification-based water body cadmium removal adsorbent - Google Patents
Preparation method and application of clinoptilolite modification-based water body cadmium removal adsorbent Download PDFInfo
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Abstract
A preparation method and application of zeolite modification-based water body cadmium removal adsorbent are disclosed, wherein the preparation method comprises the following steps: (1) crushing, screening and grinding natural clinoptilolite to obtain fine powder particle size zeolite; (2) carrying out high-temperature and lanthanum chloride modification on the fine powder particle size zeolite to obtain modified fine powder particle size zeolite; (3) the method comprises the steps of taking lignin as a raw material, preparing carbon nanofiber-coated modified zeolite, and obtaining the zeolite-modified water body cadmium removal adsorbent. The zeolite-modified water body cadmium removal adsorbent prepared by the method is filled in a nylon mesh bag and moves in a polluted natural water body aiming at the cadmium-polluted natural water body, or the water body cadmium removal adsorbent is filled in an adsorption packed tower or a pool, so that the aim of removing cadmium in wastewater is fulfilled. The raw materials are cheap and easy to obtain, the prepared adsorbent has wide application range, good adsorption effect and no secondary pollution, is particularly suitable for emergency treatment of low-concentration sudden cadmium pollution natural water or treatment of cadmium-containing wastewater with the concentration of 10-40mg/L, and has the treatment efficiency of more than 95%.
Description
Technical Field
The invention relates to a preparation method and application of an adsorbent for removing cadmium from a cadmium-polluted water body, belonging to the technical field of treatment of heavy metal pollution of the water body.
Background
With the development of industries such as metallurgy, mining, plastics and the like, cadmium is used as a raw material for producing batteries, plastics, alloys and the like, and the wide application of cadmium increases the discharge amount of wastewater containing insulation. Cadmium is not an essential element of the human body, has carcinogenicity, can accumulate in the human body through food chains, and damages the liver, the cardiovascular system, the immune system and the reproductive system. Therefore, the cadmium pollution treatment technology of the water body is always a hot point of research of environmental protection workers.
Conventional cadmium-containing wastewater and water treatment technologies can be broadly divided into physical, chemical and biological methods. The physical and chemical methods are usually membrane separation, bleaching oxidation and ion exchange. The membrane separation method requires stable components of the wastewater, high requirements on the performance of the finished membrane and large investment; cadmium-containing waste residues generated by a bleaching powder oxidation method do not have a good treatment method at present; the ion exchange method has high treatment efficiency, but has the defects of high treatment cost, easy oxidation failure of ion exchange resin and the like; although the biological method has low cost, the treatment efficiency is low, the biological facility is greatly influenced by natural environmental factors, and the cadmium-containing bottom mud has the problem of secondary pollution.
Some current literature for treating cadmium-containing wastewater has some disadvantages, such as: chinese patent document CN107126931A discloses a method for preparing an adsorbent for removing cadmium by using oyster shells, which is characterized in that when oyster shells are used as raw materials to remove cadmium in water, a certain amount of Sodium Dodecyl Sulfate (SDS) is required to be added to modify the oyster shells, and when the SDS is applied, the risk of secondary pollution caused by the release of the SDS into water is generated; the method for removing low-concentration cadmium ions in water by using the compound flocculant disclosed in CN104276689A is characterized in that a biological flocculant is required to be used when the compound flocculant is prepared, the preparation period is long, the steps are complex, the arsenic removal efficiency is to be improved, and the popularization and application are limited to a certain extent; the method for treating the cadmium-containing wastewater disclosed in CN103482738A includes the steps of adding trisodium trithiocyanate and polyaluminum chloride in sequence when treating the cadmium-containing wastewater, introducing pollutants with secondary release risk, and only adapting to the low-concentration cadmium-containing wastewater, wherein the medicine cost is high.
Zeolite is an aqueous alkali or alkaline earth aluminosilicate mineral. The crystal structure of zeolite is a three-dimensional lattice formed by connecting silicon (aluminum) oxygen tetrahedrons, the lattice has cavities and channels with different sizes, and has great openness, and cations can freely exchange through pore channels. The nano-scale zeolite has the characteristics of large specific surface area, rich and uniform micropores and the like, and has stronger ion exchange and adsorption performances on heavy metals; however, the nano zeolite is generally prepared by artificial synthesis, has high production cost and is mostly applied to the field of industrial catalysis. The fine powder zeolite and the coarse powder zeolite can be obtained by crushing and grinding natural zeolite, and the production cost is low. The coarse powder zeolite is often used as an adsorbing material for pollutants in wastewater, compared with the coarse powder, the fine powder has small particle size (10-74 microns) and large specific surface area, and has higher decontamination effect when being used as an adsorbent in water treatment, but has the defects of easy agglomeration, easy loss along with effluent and the like.
The common cadmium-containing wastewater adsorbent at present has the defects of easy generation of secondary pollution, easy oxidation failure, high cost, low adsorption efficiency and the like in the application process.
Disclosure of Invention
Aiming at the defects of the existing cadmium-containing wastewater adsorbent, the invention provides a preparation method of zeolite-modification-based water body cadmium removal adsorbent which takes natural clinoptilolite as a base material and has low cost, no secondary pollution and high adsorption efficiency, and also provides an application method of the adsorbent.
The invention discloses a preparation method of a clinoptilolite modification-based water body cadmium removal adsorbent, which comprises the following steps:
(1) cleaning, crushing, screening and grinding natural clinoptilolite, and sieving with 1600-200 mesh sieve to obtain fine powder zeolite with particle size of 10-74 μm;
(2) carrying out high-temperature and lanthanum chloride modification on the fine powder particle size zeolite to obtain modified fine powder particle size zeolite;
(3) the method comprises the steps of taking lignin as a raw material, and preparing the nano carbon fiber coated modified zeolite through electrostatic spinning to obtain the zeolite modification-based water body cadmium removal adsorbent.
The process for obtaining the modified fine powder particle size zeolite in the step (2) comprises the following steps:
firstly, treating the obtained zeolite with the fine powder particle size in a muffle furnace at 400-600 ℃ for 3-4 hours, removing water and impurities in holes and channels of the zeolite with the fine powder particle size, increasing the internal surface area, and activating natural zeolite to improve the adsorption capacity of the zeolite with the fine powder particle size; then putting the mixture into a dryer to cool to room temperature;
secondly, placing the fine powder particle size zeolite processed in the step I into NaOH solution with the concentration of 1.5-2.5mol/L, wherein the mass ratio of the fine powder particle size zeolite to the NaOH solution is 1:10-20, placing the fine powder particle size zeolite into an ultrasonic cleaning machine, ultrasonically cleaning the fine powder particle size zeolite for 2-4 hours at the stirring speed of 1500-2000 r/min at the temperature of 15-30 ℃, then cleaning the fine powder particle size zeolite with deionized water, and drying the fine powder particle size zeolite for 2-4 hours in an oven at the temperature of 100-110 ℃;
thirdly, placing the fine powder particle size zeolite treated in the second step into a lanthanum chloride solution with the concentration of 0.15-0.25mol/L (for secondary modification), wherein the mass ratio of the fine powder particle size zeolite to the lanthanum chloride solution is 1:10-15, and stirring by using a magnetic stirrer with the rotation speed of 1000 plus materials and 1500 revolutions/minute to enable the fine powder particle size zeolite to be in a suspension state; taking out, and adjusting the pH of the mixed solution to 9.5-10.5 by using NaOH solution (the concentration is 2 mol/L);
fourthly, performing solid-liquid separation on the mixed liquid obtained in the third step, cleaning the solid by using deionized water until the pH value of the supernatant is 6.5 to 7.5, and finally drying the solid in a drying oven at the temperature of 100 ℃ and 110 ℃ to obtain the modified fine powder particle size zeolite.
The lignin in the step (3) takes reed stems as raw materials.
The process for preparing the nano carbon fiber coated modified zeolite in the step (3) comprises the following steps:
transversely cutting lignin into sections at the rotating speed of 4000 plus 50000 revolutions per minute and the fiber length of 1.5-1.0 mm;
secondly, preparing a lignin spinning solution with the mass fraction of 10% by taking the lignin fiber obtained in the step I and Dimethylacetamide (DMAC) as a solvent, and adding Polyacrylonitrile (PAN) to prepare a mixed spinning solution, wherein the mass ratio of the lignin to the polyacrylonitrile is 2:1-4:1, and the lignin and the polyacrylonitrile are heated in a water bath at 70 ℃ and stirred until dissolved; preparing lignin-based nanofiber precursor filaments by electrostatic spinning, pre-oxidizing at 500 ℃ in 300-;
adding the carbon nanofibers obtained in the step two into a mixed solution with the same volume of deionized water and ethanol (wherein the mass fraction of the carbon nanofibers is 20-40%), and performing ultrasonic treatment for 10-20 minutes by using an ultrasonic probe with the power of 200-400W, so that the carbon nanofibers are fully dispersed in the mixed solution;
adding the modified fine powder particle size zeolite obtained in the step (2) into the mixed solution obtained in the step (II), wherein the mass ratio of the modified fine powder particle size zeolite to the nano carbon fiber is 1:1-3:1, and performing ultrasonic treatment for 10-20 minutes by using an ultrasonic probe with the power of 200-400W, so that the modified fine powder particle size zeolite and the nano carbon fiber are uniformly mixed;
fifthly, performing vacuum filtration on the mixed solution obtained in the step (IV) at room temperature (through a glass fiber filter), adjusting the pH value to 6.5-7.5 by using deionized water, drying for 20-24 hours at room temperature, then drying for 20-24 hours in a vacuum furnace at 80 ℃ to obtain modified zeolite coated with carbon nanofibers, and grinding and sieving to obtain the zeolite-modified-based water cadmium removal adsorbent with the particle size of 0.5-3 cm.
When the prepared zeolite-modified water body cadmium removal adsorbent is applied, the water body cadmium removal adsorbent with the diameter of 0.5-3cm is selected for a natural water body polluted by cadmium and is filled in a nylon mesh bag with 10 meshes-100 meshes, and the nylon mesh bag is moved in the polluted natural water body to achieve the purpose of removing metal cadmium in the water body by adsorption; aiming at industrial wastewater containing cadmium, a water body cadmium removal adsorbent is filled in an adsorption packed tower or a tank, and single-stage or multi-stage series connection is adopted according to the concentration of cadmium in the wastewater, so that the aim of removing cadmium in the wastewater is fulfilled.
The nylon mesh bag can be fixed at the stern and driven by a ship to move.
The invention has the following characteristics:
1. the zeolite adsorbent with the modified carbon nanofiber-coated fine powder particle size is prepared by taking the fine powder clinoptilolite as a raw material, and the material is low in price and easy to obtain and has a regeneration function.
2. The carbon nanofiber is prepared by taking the reed stem lignin as a raw material, the reed is wide in planting, strong in growing capacity and easy to obtain. After the carbon nanofibers are used as a composite framework and coated with the modified fine powder particle size zeolite, the specific surface area and the adsorption sites are both greatly increased, and the adsorption performance is enhanced.
3. The adsorbent has wide application range, low cost, good adsorption effect and no secondary pollution, is particularly suitable for emergency treatment of low-concentration sudden cadmium pollution natural water or treatment of cadmium-containing wastewater with the concentration of 10-40mg/L, and has the treatment efficiency of more than 95 percent.
Drawings
FIG. 1 is an electron micrograph of the modified fine powder particle size zeolite of example 1.
FIG. 2 is a sectional electron microscope image of the modified zeolite adsorbent coated with carbon nanofibers in example 1.
Detailed Description
Example 1
(1) Crushing, screening and grinding natural clinoptilolite, and sieving with 1600 mesh sieve to obtain fine powder zeolite with particle size of 10-15 μm.
(2) Carrying out high-temperature and lanthanum chloride modification on the fine powder zeolite to obtain modified fine powder particle size zeolite, wherein the specific process is as follows:
the obtained zeolite with fine powder particle size is treated in a muffle furnace at 400 ℃ for 4 hours, water molecules in holes and channels of the zeolite with fine powder particle size are removed, the internal surface area of the zeolite is increased, and the adsorption capacity of the zeolite is improved. And taking out the modified fine powder particle size zeolite, and putting the modified fine powder particle size zeolite into a dryer to cool the modified fine powder particle size zeolite to room temperature.
Placing the modified fine powder particle size zeolite obtained in the step I into 1.5mol/L NaOH solution (the mass ratio of the modified fine powder particle size zeolite to the NaOH solution is 1:20), placing the modified fine powder particle size zeolite into an ultrasonic cleaning machine under the action of 1500 revolutions per minute, ultrasonically cleaning the modified fine powder particle size zeolite for 4 hours at 15 ℃, cleaning the modified fine powder particle size zeolite with deionized water, and drying the modified fine powder particle size zeolite in an oven at 110 ℃ for 2 hours.
And thirdly, placing the modified fine powder particle size zeolite obtained in the second step into 0.15mol/L lanthanum chloride solution (the mass ratio of the modified fine powder particle size zeolite to the lanthanum chloride solution is 1:15) for secondary modification, stirring by using a magnetic stirrer with the rotating speed of 1000 revolutions/minute to enable the modified fine powder particle size zeolite to be in a suspended state, taking out, and adjusting the pH value of the mixed solution to be 9.5 by using 2mol/L NaOH solution.
Fourthly, carrying out solid-liquid separation on the solution obtained in the third step, cleaning the solid by using deionized water until the pH value of the supernatant is 6.5, and finally drying the solid in a drying oven at 100 ℃ to obtain the modified fine powder particle size zeolite. FIG. 1 shows an electron microscope image of the modified fine powder zeolite of this example.
(3) The method comprises the steps of taking reed stem lignin as a raw material, and preparing the zeolite with the nano carbon fiber coated and modified fine powder particle size through electrostatic spinning to obtain the zeolite modification-based water body cadmium removal adsorbent. The specific process is as follows:
firstly, a Valley type beater is utilized to transversely cut the lignin into sections, the rotating speed is 4000 revolutions per minute, and the fiber length is 1.5 mm.
Secondly, preparing the lignin fiber obtained in the step one, taking Dimethylacetamide (DMAC) as a solvent, preparing a lignin spinning solution with the mass fraction of 10%, adding Polyacrylonitrile (PAN) to prepare a mixed spinning solution (the mass ratio of the lignin to the polyacrylonitrile is 2:1), heating in a water bath at 70 ℃, and stirring until the lignin fiber is dissolved. After preparing the lignin-based nanofiber precursor filaments by an electrostatic spinning process, placing the precursor filaments into a high-temperature furnace for pre-oxidation at 300 ℃, and performing carbonization treatment at 1000 ℃ to prepare the lignin-based carbon nanofibers.
And thirdly, adding the carbon nanofibers obtained in the second step into a mixed solution with the same volume of deionized water and ethanol (wherein the mass fraction of the carbon nanofibers is 20%), and performing ultrasonic treatment for 20 minutes by using an ultrasonic probe with the power of 200W to fully disperse the carbon nanofibers in the mixed solution.
And fourthly, adding the modified fine powder particle size zeolite obtained in the step 2 into the mixed solution obtained in the step II (the mass ratio of the modified fine powder particle size zeolite to the carbon nanofibers is 1:1), and performing ultrasonic treatment for 20 minutes by using an ultrasonic probe with the power of 200W to uniformly mix the modified zeolite and the carbon nanofibers.
Fifthly, the mixed solution obtained in the step IV is filtered in vacuum through a glass fiber filter at room temperature, the pH value is adjusted to 6.5 by deionized water, the mixed solution is dried for 20 hours at room temperature and then dried for 20 hours in a vacuum furnace at 80 ℃ to obtain the nano carbon fiber coated modified zeolite, and the nano carbon fiber coated modified zeolite is ground and sieved to obtain the zeolite modification-based water cadmium removal adsorbent 1 with the particle size of 0.5-3cm#。
FIG. 2 shows a sectional electron microscope image of the modified zeolite adsorbent coated with carbon nanofibers obtained in this example.
Example 2
(1) Crushing, screening and grinding natural clinoptilolite, and sieving with 540 mesh sieve to obtain fine powder zeolite with particle size of 10-30 μm.
(2) And (3) carrying out high-temperature and lanthanum chloride modification on the fine powder particle size zeolite to obtain the modified fine powder particle size zeolite. The specific process is as follows:
the obtained zeolite with fine powder particle size is treated in a muffle furnace at 500 ℃ for 3.5 hours, water molecules in holes and channels of the zeolite with fine powder particle size are removed, the internal surface area of the zeolite with fine powder particle size is increased, and the adsorption capacity of the zeolite with fine powder particle size is improved. And taking out the modified fine powder particle size zeolite, and putting the modified fine powder particle size zeolite into a dryer to cool the modified fine powder particle size zeolite to room temperature.
Placing the modified fine powder particle size zeolite obtained in the step (i) into a 2.0mol/L NaOH solution (the mass ratio of the modified fine powder particle size zeolite to the lanthanum chloride solution is 1:15), placing the modified fine powder particle size zeolite into an ultrasonic cleaning machine under the action of a mechanical stirrer with the rotating speed of 1750 revolutions per minute, ultrasonically cleaning the modified fine powder particle size zeolite for 3 hours at the temperature of 22 ℃, cleaning the modified fine powder particle size zeolite with deionized water, and drying the modified fine powder particle size zeolite for 3 hours in an oven at the temperature of 105 ℃.
And thirdly, placing the modified fine powder particle size zeolite obtained in the second step into 0.20mol/L lanthanum chloride solution (the mass ratio of the modified fine powder particle size zeolite to the NaOH solution is 1:12.5) for secondary modification, stirring by using a magnetic stirrer with the rotating speed of 1250 revolutions/minute to enable the zeolite to be in a suspended state, taking out, and adjusting the pH value of the mixed solution to 10.0 by using 2mol/L NaOH solution.
Fourthly, carrying out solid-liquid separation on the solution obtained in the third step, cleaning the solid by using deionized water until the pH value of the supernatant is 7.0, and finally drying the solid in a drying oven at 105 ℃ to obtain the modified fine powder particle size zeolite.
(3) The method comprises the steps of taking reed stem lignin as a raw material, and preparing the zeolite with the nano carbon fiber coated and modified fine powder particle size through electrostatic spinning to obtain the zeolite modification-based water body cadmium removal adsorbent. The specific process is as follows:
firstly, a Valley type beater is used for transversely cutting lignin into sections, the rotating speed is 22000 r/min, and the fiber length is 1.25 mm.
And secondly, preparing the lignin fiber obtained in the step one, taking Dimethylacetamide (DMAC) as a solvent, preparing a lignin spinning solution with the mass fraction of 10%, adding Polyacrylonitrile (PAN) to prepare a mixed spinning solution (the mass ratio of the lignin to the polyacrylonitrile is 3:1), heating in a water bath at 70 ℃, and stirring until the lignin fiber is dissolved. After preparing the lignin-based nanofiber precursor filaments by an electrostatic spinning process, placing the precursor filaments into a high-temperature furnace for pre-oxidation at 400 ℃, and performing carbonization treatment at 1200 ℃ to prepare the lignin-based carbon nanofibers.
And thirdly, adding the carbon nanofibers obtained in the second step into a mixed solution with the same volume of deionized water and ethanol (wherein the mass fraction of the carbon nanofibers is 30%), and performing ultrasonic treatment for 15 minutes by using an ultrasonic probe with the power of 300W to fully disperse the carbon nanofibers in the mixed solution.
And fourthly, adding the modified fine powder particle size zeolite obtained in the step 2 into the mixed solution obtained in the step II (the mass ratio of the modified fine powder particle size zeolite to the carbon nanofibers is 2:1), and performing ultrasonic treatment for 15 minutes by using an ultrasonic probe with the power of 300W to uniformly mix the modified zeolite and the carbon nanofibers.
Fifthly, the mixed solution obtained in the step IV is filtered in vacuum through a glass fiber filter at room temperature, the pH value is adjusted to 7.0 by deionized water, the mixed solution is dried for 22 hours at room temperature and then dried for 22 hours in a vacuum furnace at 80 ℃ to obtain the modified zeolite coated with the nano carbon fibers, and the modified zeolite coated with the nano carbon fibers is ground and sieved to obtain the zeolite-modified-based water cadmium removal adsorbent 2 with the particle size of 0.5-3cm#。
Example 3
(1) Crushing, screening and grinding natural clinoptilolite, and sieving with a 200-mesh sieve to obtain fine powder zeolite with a particle size of 10-74 μm.
(2) Carrying out high-temperature and lanthanum chloride modification on the fine powder particle size zeolite to obtain the modified fine powder particle size zeolite, wherein the specific process is as follows:
the obtained zeolite with the fine powder particle size is treated in a muffle furnace at 600 ℃ for 3 hours, water molecules in holes and channels of the zeolite with the fine powder particle size are removed, the internal surface area of the zeolite with the fine powder particle size is increased, and the adsorption capacity of the zeolite with the fine powder particle size is improved. And taking out the modified fine powder particle size zeolite, and putting the modified fine powder particle size zeolite into a dryer to cool the modified fine powder particle size zeolite to room temperature.
Placing the modified fine powder particle size zeolite obtained in the step I into 2.5mol/L NaOH solution (the mass ratio of the modified fine powder particle size zeolite to the NaOH solution is 1:10), placing the modified fine powder particle size zeolite into an ultrasonic cleaning machine under the action of 2000 revolutions per minute of a mechanical stirrer, ultrasonically cleaning the modified fine powder particle size zeolite for 2 hours at 30 ℃, cleaning the modified fine powder particle size zeolite with deionized water, and drying the modified fine powder particle size zeolite in an oven at 100 ℃ for 4 hours.
And thirdly, placing the modified fine powder particle size zeolite obtained in the second step into 0.25mol/L lanthanum chloride solution (the mass ratio of the modified fine powder particle size zeolite to the lanthanum chloride solution is 1:10) for secondary modification, stirring by using a magnetic stirrer with the rotating speed of 1500 rpm to enable the fine powder particle size zeolite to be in a suspended state, taking out, and adjusting the pH value of the mixed solution to 10.5 by using 2mol/L NaOH solution.
Fourthly, carrying out solid-liquid separation on the solution obtained in the third step, cleaning the solid by using deionized water until the pH value of the supernatant is 7.5, and finally drying the solid in a drying oven at the temperature of 110 ℃ to obtain the modified fine powder particle size zeolite.
(3) The method comprises the steps of taking reed stem lignin as a raw material, and preparing the zeolite with the nano carbon fiber coated and modified fine powder particle size through electrostatic spinning to obtain the zeolite modification-based water body cadmium removal adsorbent. The specific process is as follows:
firstly, a Valley type beater is utilized to transversely cut the lignin into sections, the rotating speed is 4000-.
And secondly, preparing the lignin fiber obtained in the step one, taking Dimethylacetamide (DMAC) as a solvent, preparing a lignin spinning solution with the mass fraction of 10%, adding Polyacrylonitrile (PAN) to prepare a mixed spinning solution (the mass ratio of the lignin to the polyacrylonitrile is 4:1), heating in a water bath at 70 ℃, and stirring until the lignin fiber is dissolved. After preparing the lignin-based nanofiber precursor filament by an electrostatic spinning process, placing the precursor filament into a high-temperature furnace for pre-oxidation at 500 ℃, and performing carbonization treatment at 1400 ℃ to prepare the lignin-based nanofiber.
And thirdly, adding the carbon nanofibers obtained in the second step into a mixed solution with the same volume of deionized water and ethanol (wherein the mass fraction of the carbon nanofibers is 40%), and performing ultrasonic treatment for 10 minutes by using an ultrasonic probe with the power of 400W to fully disperse the carbon nanofibers in the mixed solution.
And fourthly, adding the modified fine powder particle size zeolite obtained in the step 2 into the mixed solution obtained in the step II (the mass ratio of the modified fine powder particle size zeolite to the carbon nanofibers is 3:1), and performing ultrasonic treatment for 10 minutes by using an ultrasonic probe with the power of 400W to uniformly mix the modified zeolite and the carbon nanofibers.
Fifthly, the mixed solution obtained in the step IV is filtered in vacuum through a glass fiber filter at room temperature, the pH value is adjusted to 7.5 by deionized water, the mixed solution is dried for 24 hours at room temperature and then dried for 24 hours in a vacuum furnace at 80 ℃ to obtain the modified zeolite coated with the carbon nanofibers, and the modified zeolite coated with the carbon nanofibers is ground and sieved to obtain the zeolite-modified-based water cadmium removal adsorbent 3 with the particle size of 0.5-3cm#。
When the prepared zeolite-modified water body cadmium removal adsorbent is applied, adsorption treatment is carried out on different polluted water bodies in different ways:
1. aiming at the cadmium-polluted natural water body, selecting a water body cadmium removal adsorbent with the diameter of 0.5-3cm, putting the water body cadmium removal adsorbent into a nylon mesh bag with 10 meshes-100 meshes, and moving the nylon mesh bag in the polluted natural water body to achieve the purpose of removing metal cadmium in the water body by adsorption;
2. aiming at industrial wastewater containing cadmium, a water body cadmium removal adsorbent is filled in an adsorption packed tower or a tank, and the aim of removing cadmium in the wastewater is fulfilled by single-stage or multi-stage series connection according to the concentration of cadmium in the wastewater.
The three modified fine powder particle size zeolite adsorbents prepared in example 1, example 2 and example 3 were used for treating cadmium-containing wastewater with a cadmium ion concentration of 10-40mg/L, respectively, and the adsorption capacity and the adsorption efficiency of the adsorbent are shown in the following table.
Adsorption effect of modified fine powder particle size zeolite-carbon nanofiber composite adsorbent on cadmium-containing wastewater
From the treatment results, the modified fine powder particle size zeolite-carbon nanofiber composite adsorbent prepared by the invention has large adsorption capacity and high adsorption efficiency.
Claims (4)
1. A preparation method of a zeolite modification-based water body cadmium removal adsorbent is characterized by comprising the following steps:
(1) crushing, screening and grinding natural clinoptilolite, and sieving with 1600-200 mesh sieve to obtain fine powder zeolite with particle size of 10-74 μm;
(2) carrying out high-temperature and lanthanum chloride modification on the fine powder particle size zeolite to obtain modified fine powder particle size zeolite;
(3) preparing carbon nanofiber-coated modified fine powder particle size zeolite by taking lignin as a raw material through electrostatic spinning to obtain a zeolite-modified water body cadmium removal adsorbent;
the process for preparing the nano carbon fiber coated modified fine powder particle size zeolite in the step (3) comprises the following steps:
transversely cutting lignin into sections at the rotating speed of 4000 plus 50000 revolutions per minute and the fiber length of 1.5-1.0 mm;
secondly, preparing a lignin spinning solution with the mass fraction of 10% by taking the lignin fiber obtained in the step one and dimethylacetamide as a solvent, and adding polyacrylonitrile to prepare a mixed spinning solution, wherein the mass ratio of the lignin to the polyacrylonitrile is 2:1-4:1, heating in a water bath at 70 ℃, and stirring until the lignin and the polyacrylonitrile are dissolved; preparing lignin-based nanofiber precursor filaments by electrostatic spinning, pre-oxidizing at 500 ℃ in 300-;
adding the carbon nanofibers obtained in the step two into a mixed solution with the same volume of deionized water and ethanol, wherein the mass fraction of the carbon nanofibers is 20-40%, and performing ultrasonic treatment for 10-20 minutes by using an ultrasonic probe with the power of 200 plus 400W, so that the carbon nanofibers are fully dispersed in the mixed solution;
adding the modified fine powder particle size zeolite obtained in the step (2) into the mixed solution obtained in the step (II), wherein the mass ratio of the modified fine powder particle size zeolite to the nano carbon fiber is 1:1-3:1, and performing ultrasonic treatment for 10-20 minutes by using an ultrasonic probe with the power of 200-400W, so that the modified fine powder particle size zeolite and the nano carbon fiber are uniformly mixed;
fifthly, vacuum filtering the mixed solution obtained in the step IV at room temperature, adjusting the pH value to 6.5-7.5 by using deionized water, drying at room temperature for 20-24 hours, drying in a vacuum furnace at 80 ℃ for 20-24 hours to obtain the nano carbon fiber coated modified fine powder zeolite, and grinding and sieving to obtain the zeolite-modified water body cadmium removal adsorbent with the particle size of 0.5-3 cm.
2. The preparation method of zeolite-modified water body cadmium removal adsorbent as claimed in claim 1, wherein the process of obtaining the modified fine powder particle size zeolite in the step (2) comprises the following steps:
firstly, treating the obtained zeolite with the fine powder particle size in a muffle furnace at 400-600 ℃ for 3-4 hours, removing holes and water molecules in a channel of the zeolite with the fine powder particle size, and increasing the internal surface area of the zeolite to improve the adsorption capacity of the zeolite with the fine powder particle size; then putting the mixture into a dryer to cool to room temperature;
secondly, placing the fine powder particle size zeolite processed in the step I into NaOH solution with the concentration of 1.5-2.5mol/L, wherein the mass ratio of the fine powder particle size zeolite to the NaOH solution is 1:10-20, placing the fine powder particle size zeolite into an ultrasonic cleaning machine, ultrasonically cleaning the fine powder particle size zeolite for 2-4 hours at the stirring speed of 1500-2000 r/min at the temperature of 15-30 ℃, then cleaning the fine powder particle size zeolite with deionized water, and drying the fine powder particle size zeolite for 2-4 hours in an oven at the temperature of 100-110 ℃;
thirdly, placing the fine powder particle size zeolite treated in the second step into a lanthanum chloride solution with the concentration of 0.15-0.25mol/L for secondary modification, wherein the mass ratio of the fine powder particle size zeolite to the lanthanum chloride solution is 1:10-15, and stirring by using a magnetic stirrer with the rotation speed of 1000-1500 revolutions/minute to enable the fine powder particle size zeolite to be in a suspension state; taking out, and adjusting the pH of the mixed solution to 9.5-10.5 by using NaOH solution;
fourthly, performing solid-liquid separation on the mixed liquid obtained in the third step, cleaning the solid by using deionized water until the pH value of the supernatant is 6.5 to 7.5, and finally drying the solid in a drying oven at the temperature of 100 ℃ and 110 ℃ to obtain the modified fine powder particle size zeolite.
3. The preparation method of the zeolite-modified water body cadmium removal adsorbent as claimed in claim 1, wherein the lignin in step (3) is prepared from reed stems.
4. The zeolite-modified water body cadmium removal adsorbent prepared by the method of any one of claims 1 to 3 is prepared by selecting a water body cadmium removal adsorbent with the diameter of 0.5-3cm for a cadmium-polluted natural water body, putting the water body cadmium removal adsorbent into a nylon mesh bag with 10 meshes-100 meshes, and moving the nylon mesh bag in the polluted natural water body to achieve the purpose of adsorbing and removing metal cadmium in the water body; aiming at the industrial wastewater containing cadmium, a water body cadmium removal adsorbent is filled in an adsorption packed tower or a tank to achieve the aim of removing cadmium in the wastewater.
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