CN111068615B - Multi-element composite adsorption material for removing vanadium and preparation method and application thereof - Google Patents
Multi-element composite adsorption material for removing vanadium and preparation method and application thereof Download PDFInfo
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- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides a multi-element composite adsorption material for removing vanadium, which is prepared by mixing CuO-SnO2‑La2O3The composite oxide is loaded on the active carbon, develops an adsorbent material capable of effectively removing vanadium, and has the advantages of large adsorption capacity, low regeneration energy consumption and the like.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a multi-element composite adsorption material for removing vanadium, and a preparation method and application thereof.
Background
In modern industrial production, the fossil fuels used contain vanadium, for example, hard coal contains vanadium in about 19ppm (ash content 126ppm), lignite contains vanadium in about 10ppm (ash content 63ppm) and petroleum contains vanadium in an amount as high as 36-114ppm all over the world. Vanadium discharged to the atmosphere when fossil fuel is combusted is up to 20000 tons only if half of vanadium in petroleum enters the atmosphere, and thus vanadium in the atmosphere mainly comes from petroleum combustion, if calculated as 20 hundred million tons of oil consumed all over the world every year. And vanadium in the atmosphere has strong catalytic SO2To SO3The conversion capability is one of the key substances for the formation of acid rain. The environmental vanadium pollution mainly comes from vanadium ore mining and smelting, production of vanadium-containing alloy steel, organic and inorganic chemistry, glass and ceramic manufacturing, textile, electronic, pigment, printing and dyeing, paint, leather, national defense and other industries, and generally, waste gas is discharged to pollute the atmosphere and can be settled after diffusion, thereby further polluting water sources, crops, pasture and the like.
With the continuous expansion of the production quantity of vanadium, the use amount of coal and petroleum is continuously increased, the problem of environmental vanadium pollution is gradually increased, and the problem of vanadium pollution is necessary to develop environmental monitoring, strengthen medical research, reform the process, recycle vanadium-containing smoke dust in waste gas and reduce the emission of vanadium-containing three wastes. The 'design and sanitation standard of industrial enterprises' in China stipulates that: the maximum allowable concentration of the vanadium in the surface water is 0.1 mg/L.
In the environmental control of industrial domestic sewage, waste water and waste gas, the vanadium removal and control technology is always a thermoelectric and difficult problem studied at home and abroad. The vanadium removal technology commonly adopted at present mainly comprises active material adsorption filtration, electrodialysis, a coagulating sedimentation method, membrane filtration and the like. The adsorption filtration method uses an insoluble solid material with high specific surface area and excellent mechanical strength as an adsorbent, and achieves the purpose of removing pollutants such as vanadium in water vapor through the actions of physical adsorption, chemical adsorption or ion exchange and the like. The whole process does not need a complex medicine adding process, is simple and easy to implement and is most widely applied.
In the adsorption filtration method, the most widely used is porous adsorption material represented by activated carbon, and the porous structure not only provides an adsorption carrier for trace pollutants, but also can introduce active sites through loading metal oxides to further enhance the adsorption effect. However, the adsorption effect of the material on ionic pollutants such as vanadium is limited, and the urgent advanced treatment and standard improvement requirements are difficult to meet. Therefore, the development of an activated carbon adsorption material with high vanadium removal efficiency is more urgent and important.
Further, a commonly used method for synthesizing activated carbon is to heat organic raw materials such as coal, wood and the like under the condition of isolating air. Organic raw materials such as coal and wood are used as non-renewable resources, and long-term use of the organic raw materials inevitably aggravates the pressure of resource exhaustion. At present, the chemical composition of municipal solid waste contains high organic matter content, which accounts for about 60-80%. After the domestic garbage is subjected to microwave pyrolysis treatment, products in three forms of solid, gas and liquid can be usually decomposed, and pyrolysis gas and pyrolysis oil (obtained after separation of liquid products) can be combusted to generate power. Considering that the existing solid residue is basically decarbonized, the carbon-containing component is abandoned, and only the residual silicon-calcium residue is used as the building filler, but certain procedures such as electric separation, flotation and the like are still needed for decarbonization to reach certain purity. The processes consume energy and time, and simultaneously abandon carbon-containing components, thereby causing certain waste and pollution. Along with the rapid soaring of Chinese economy and the rapid development of the house and land industry, the discharge amount of construction waste is increased year by year, and the construction waste accounts for 30-40% of the total solid waste amount of a city at present. Landfill is far from meeting the current development situation as the main treatment means of building waste. Therefore, research and development of novel activated carbon adsorption materials using construction and household garbage as raw materials are hot spots and difficulties of research at home and abroad at present.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides a multi-element composite adsorbing material for removing vanadium, which is prepared by mixing CuO-SnO2-La2O3The composite oxide is loaded on the active carbon, develops an adsorbent material capable of effectively removing vanadium, and has the advantages of large adsorption capacity, low regeneration energy consumption and the like.
The invention provides a multi-element composite adsorption material for removing vanadium, which comprises an active component and a porous loading matrix, wherein the active component is CuO-SnO2-La2O3The porous load matrix is active carbon, CuO or SnO2、La2O3The weight ratio of the composite oxide to the active carbon is 20-40: 60-80.
Preferably, CuO-SnO2-La2O3In the composite oxide of (2), CuO-SnO2-La2O3In a molar ratio of 2:1: 1.
Preferably, the activated carbon is prepared by adopting carbon-containing building and/or household garbage as a carbon source; preferably, the activated carbon is prepared by the following method: crushing, sieving, deoiling and acid dissolving the carbon-containing building and/or household garbage, adding alkali to adjust the pH value to be neutral, drying, transferring to a high-temperature furnace, heating to 800 ℃ under the protection of inert gas for calcination reaction, floating to obtain carbon materials, washing and drying to obtain the activated carbon.
Preferably, CuO-SnO2-La2O3The composite oxide is loaded on the surface of the active carbon by an in-situ loading method.
Preferably, the adsorbent material has spherical and rod-shaped particles with a particle size of 500-3000 nm.
The invention also provides a preparation method of the multi-element composite adsorption material for removing vanadium, which comprises the following steps: dissolving activated carbon, tin salt, lanthanum salt and copper salt in a dilute acid solution, adding an alkali solution to adjust the pH value to 7-12, reacting under the condition of microwave or ultrasonic microwave combination, filtering and drying to obtain the multi-element composite adsorbing material.
Preferably, the tin salt is selected from one or more of tin sulfate, tin nitrate and tin chloride; the lanthanum salt is selected from one or more of lanthanum chloride and lanthanum nitrate; the copper salt is selected from one or more of copper sulfate, copper nitrate and copper chloride.
Preferably, when the reaction is carried out under the condition of the combination of the ultrasonic waves and the microwaves, the power of the ultrasonic waves is 800-.
Furthermore, the invention provides an application of the multi-element composite adsorption material for removing vanadium in treating vanadium-containing sewage.
Preferably, under the illumination condition, the sewage containing any one or more of 3-valent vanadium, 4-valent vanadium and 5-valent vanadium is in sufficient contact with the multi-element composite adsorbing material, so that the vanadium in the sewage is adsorbed and removed.
Compared with the prior art, the invention has the following advantages:
1. the multi-element composite adsorption material adopts a porous adsorption material as a carrier, and the composite oxide of copper oxide, tin oxide and lanthanum oxide is loaded on the surface of the carrier, so that the porous adsorption activity of the activated carbon is maintained, and the surface polarity of the activated carbon can be changed by the composite oxide of copper oxide, tin oxide and lanthanum oxide, so that the composite material can effectively adsorb vanadium.
2. The multi-element composite adsorbing material adopts active carbon in-situ loaded CuO-SnO2-La2O3The composite oxide is prepared by the method, and can effectively retain CuO-SnO2-La2O3The surface activity of the composite oxide, and simultaneously avoids the phenomena of particle aggregation, even specific surface area reduction and the like caused by sintering and other processes.
3. In the multi-element composite adsorption material, the activated carbon is prepared from carbon-containing construction and household garbage, so that the construction and household carbon-containing garbage is treated, the pollution is reduced, the activated carbon can be prepared, the resources are reasonably and fully reused, and the prepared activated carbon has better adsorption and catalysis performances than porous carbon materials from other sources due to the unique composition and structure.
4. When the multi-element composite adsorption material is used for industrial and domestic sewage waste water and waste gas containing vanadium (3-valent vanadium, 4-valent vanadium and 5-valent vanadium), the adsorption capacity of the composite adsorption material with different compositions to the vanadium-containing sewage solution is greatly different. Wherein the composition is 30 wt% of CuO-SnO2-La2O3(2:1:1) the active component and 70 wt% of carbon-containing building and/or domestic garbage have the best adsorption effect, and the adsorption capacity reaches 236mg/g, so that the method can be widely applied to industrial vanadium-containing wastewater treatment.
Drawings
FIG. 1 is an XRD diffractogram of the multi-component composite adsorbent material of example 1;
FIG. 2 is an SEM image of the multi-element composite adsorbing material in example 1 at different magnifications;
FIG. 3 is a graph showing adsorption performance of the corresponding adsorbent materials of examples 1 to 6 and comparative examples 1 to 3;
FIG. 4 is a graph showing the adsorption amounts of the adsorbent materials according to examples 1 to 6 and comparative examples 1 to 3.
Detailed Description
Example 1
A multi-element composite adsorption material for removing vanadium, which is prepared from CuO-SnO2-La2O3The composite oxide of (A) as an active component and activated carbon as a porous supporting matrix, wherein CuO-SnO2-La2O3The weight ratio of the composite oxide to the active carbon is 30:70, CuO and SnO2、La2O3In a molar ratio of 2:1: 1.
The preparation method of the multi-element composite adsorption material specifically comprises the following steps: 14.8309g of activated carbon, 1.8960g of stannous chloride (0.01mol), 8.6600g of lanthanum nitrate (0.02mol) and 3.7512g of copper nitrate (0.02mol) are respectively added into 40mL of 0.20mol/L dilute nitric acid and stirred to be dissolved, then ammonia water solution is added under magnetic stirring to adjust the pH value to 10, the mixture is transferred to an ultrasonic microwave combined reactor after being fully stirred by magnetic force, a microwave and ultrasonic dual-function device is started, and the mixture reacts for 0.5h under the conditions of 1000W ultrasonic waves and 1000W microwaves at the same time, so that fine black powder is obtained by filtration, and the black powder is put into a 120 ℃ oven to be dried for 2h, and the multi-element composite adsorbing material is obtained; the activated carbon is prepared by taking carbon-containing building or household garbage as a carbon source, and specifically, the carbon-containing building or household garbage is crushed, sieved, deoiled, dissolved in acid, added with alkali to adjust the pH value to be neutral, dried at 110 ℃, transferred to a high-temperature furnace, heated to 750 ℃ under the protection of nitrogen for calcination reaction, floated to obtain a carbon material, washed and dried to obtain the activated carbon.
And (3) carrying out XRD and SEM microstructure test analysis on the obtained multi-element composite adsorption material, and testing the adsorption performance (taking vanadium-containing heavy metal ion solution as a sewage treatment object).
The XRD pattern of the multi-component composite adsorption material is analyzed, so that the diffraction intensity peak of the material basically corresponds to the corresponding composition, and the diffraction pattern of the multi-component composite adsorption material has obvious difference compared with the peak position of a single active carbon diffraction peak: the XRD diffraction pattern has obvious CuO and SnO2、La2O3Diffraction peaks, and all are comparedThe result is sharp, which indicates that the synthesized multi-element composite adsorbing material is matched with the designed target product in phase.
Analysis on an SEM image of the multi-element composite adsorbing material shows that the adsorbing material has a spherical and rod-like mixed structure, the pore channel structure is obvious, the microstructure of the adsorbing material is in a multi-level and multi-scale mode, and the size range of the adsorbing material is 500nm-3 um.
In this example, and in the following examples and comparative examples, the types and manufacturers of the reaction apparatuses used in the preparation methods are as follows:
also, in this example, and in the following examples and comparative examples, the chemical raw material reagents used in the preparation methods thereof are as follows:
example 2
A multi-element composite adsorption material for removing vanadium, which is prepared from CuO-SnO2-La2O3The composite oxide of (A) as an active component and activated carbon as a porous supporting matrix, wherein CuO-SnO2-La2O3The weight ratio of the composite oxide to the active carbon is 30:70, CuO and SnO2、La2O3In a molar ratio of 1:1: 1.
The preparation method of the multi-element composite adsorption material specifically comprises the following steps: 12.9748g of activated carbon, 1.8960g of stannous chloride (0.01mol), 8.6600g of lanthanum nitrate (0.02mol) and 1.8756g of copper nitrate (0.01mol) are added into 40mL of 0.20mol/L dilute nitric acid and stirred to be dissolved, then ammonia water solution is added under magnetic stirring to adjust the pH value to 7, the mixture is transferred to an ultrasonic microwave combined reactor after being fully stirred by magnetic force, a microwave and ultrasonic dual-function device is started, and the mixture is reacted for 1 hour under the conditions of 800W ultrasonic waves and 1200W microwaves at the same time, fine black powder is obtained by filtration, and the black powder is put into a 120 ℃ oven to be dried for 2 hours, so that the multi-element composite adsorbing material is obtained; the activated carbon is prepared by taking carbon-containing building or household garbage as a carbon source, and specifically, the carbon-containing building or household garbage is crushed, sieved, deoiled, dissolved in acid, added with alkali to adjust the pH value to be neutral, dried at 110 ℃, transferred to a high-temperature furnace, heated to 700 ℃ under the protection of nitrogen for calcination reaction, floated to obtain a carbon material, washed and dried to obtain the activated carbon.
Example 3
A multi-element composite adsorption material for removing vanadium, which is prepared from CuO-SnO2-La2O3The composite oxide of (A) as an active component and activated carbon as a porous supporting matrix, wherein CuO-SnO2-La2O3The weight ratio of the composite oxide to the active carbon is 30:70, CuO and SnO2、La2O3In a molar ratio of 1:1: 2.
The preparation method of the multi-element composite adsorption material specifically comprises the following steps: 20.5770g of activated carbon, 1.8960g of stannous chloride (0.01mol), 17.3200g of lanthanum nitrate (0.04mol) and 1.8756g of copper nitrate (0.01mol) are respectively added into 40mL of 0.20mol/L dilute nitric acid and stirred to be dissolved, ammonia water solution is added under magnetic stirring to adjust the pH value to 12, the mixture is transferred to an ultrasonic microwave combined reactor after being fully stirred by magnetic force, a microwave and ultrasonic dual-function device is started, the mixture is reacted for 1 hour under the conditions of 1200W ultrasonic waves and 800W microwaves at the same time, fine black powder is obtained by filtration, and the black powder is put into a 120 ℃ oven to be dried for 2 hours, so that the multi-element composite adsorbing material is obtained; the activated carbon is prepared by taking carbon-containing building or household garbage as a carbon source, and specifically, the carbon-containing building or household garbage is crushed, sieved, deoiled, dissolved in acid, added with alkali to adjust the pH value to be neutral, dried at 110 ℃, transferred to a high-temperature furnace, heated to 800 ℃ under the protection of nitrogen for calcination reaction, floated to obtain a carbon material, washed and dried to obtain the activated carbon.
Example 4
A multi-element composite adsorption material for removing vanadium, which is prepared from CuO-SnO2-La2O3The composite oxide of (A) as an active component and activated carbon as a porous supporting matrix, wherein CuO-SnO2-La2O3The weight ratio of the composite oxide to the active carbon is 30:70, CuO and SnO2、La2O3In a molar ratio of 1:2: 1.
The preparation method of the multi-element composite adsorption material specifically comprises the following steps: 16.4914g of activated carbon, 3.7920g of stannous chloride (0.02mol), 8.6600g of lanthanum nitrate (0.02mol) and 1.8756g of copper nitrate (0.01mol) are respectively added into 40mL of 0.20mol/L dilute nitric acid and stirred to be dissolved, then ammonia water solution is added under magnetic stirring to adjust the pH value to 10, the mixture is transferred to an ultrasonic microwave combined reactor after being fully stirred by magnetic force, a microwave and ultrasonic dual-function device is started, and the mixture reacts for 0.5h under the conditions of 1000W ultrasonic waves and 1000W microwaves at the same time, so that fine black powder is obtained by filtration, and the black powder is put into a 120 ℃ oven to be dried for 2h, and the multi-element composite adsorbing material is obtained; the activated carbon is prepared by taking carbon-containing building or household garbage as a carbon source, and specifically, the carbon-containing building or household garbage is crushed, sieved, deoiled, dissolved in acid, added with alkali to adjust the pH value to be neutral, dried at 110 ℃, transferred to a high-temperature furnace, heated to 750 ℃ under the protection of nitrogen for calcination reaction, floated to obtain a carbon material, washed and dried to obtain the activated carbon.
Example 5
A multi-element composite adsorption material for removing vanadium, which is prepared from CuO-SnO2-La2O3The composite oxide of (A) as an active component and activated carbon as a porous supporting matrix, wherein CuO-SnO2-La2O3The weight ratio of the composite oxide to the active carbon is 30:70, CuO and SnO2、La2O3In a molar ratio of 2:1: 2.
The preparation method of the multi-element composite adsorption material specifically comprises the following steps: 22.4331g of activated carbon, 1.8960g of stannous chloride (0.01mol), 17.3200g of lanthanum nitrate (0.04mol) and 3.7512g of copper nitrate (0.02mol) are added into 40mL of 0.20mol/L dilute nitric acid and stirred to be dissolved, then ammonia water solution is added under magnetic stirring to adjust the pH value to 10, the mixture is transferred to an ultrasonic microwave combined reactor after being fully stirred by magnetic force, a microwave and ultrasonic dual-function device is started, and the mixture reacts for 0.5h under the conditions of 1000W ultrasonic and 1000W microwave, and fine black powder is obtained by filtration and is put into a 120 ℃ oven to be dried for 2h, so that the multi-element composite adsorbing material is obtained; the activated carbon is prepared by taking carbon-containing building or household garbage as a carbon source, and specifically, the carbon-containing building or household garbage is crushed, sieved, deoiled, dissolved in acid, added with alkali to adjust the pH value to be neutral, dried at 110 ℃, transferred to a high-temperature furnace, heated to 750 ℃ under the protection of nitrogen for calcination reaction, floated to obtain a carbon material, washed and dried to obtain the activated carbon.
Example 6
A multi-element composite adsorption material for removing vanadium, which is prepared from CuO-SnO2-La2O3The composite oxide of (A) as an active component and activated carbon as a porous supporting matrix, wherein CuO-SnO2-La2O3The weight ratio of the composite oxide to the active carbon is 30:70, CuO and SnO2、La2O3In a molar ratio of 2:2: 1.
The preparation method of the multi-element composite adsorption material specifically comprises the following steps: 18.3474g of activated carbon, 3.7920g of stannous chloride (0.02mol), 8.6600g of lanthanum nitrate (0.02mol) and 3.7512g of copper nitrate (0.02mol) are respectively added into 40mL of 0.20mol/L dilute nitric acid and stirred to be dissolved, then ammonia water solution is added under magnetic stirring to adjust the pH value to 10, the mixture is transferred to an ultrasonic microwave combined reactor after being fully stirred by magnetic force, a microwave and ultrasonic dual-function device is started, and the mixture reacts for 0.5h under the conditions of 1000W ultrasonic waves and 1000W microwaves at the same time, so that fine black powder is obtained by filtration, and the black powder is put into a 120 ℃ oven to be dried for 2h, and the multi-element composite adsorbing material is obtained; the activated carbon is prepared by taking carbon-containing building or household garbage as a carbon source, and specifically, the carbon-containing building or household garbage is crushed, sieved, deoiled, dissolved in acid, added with alkali to adjust the pH value to be neutral, dried at 110 ℃, transferred to a high-temperature furnace, heated to 750 ℃ under the protection of nitrogen for calcination reaction, floated to obtain a carbon material, washed and dried to obtain the activated carbon.
Comparative example 1
The adsorption material for removing vanadium comprises CuO as an active component and activated carbon as a porous loading matrix, wherein the weight ratio of the CuO to the activated carbon is 30: 70.
The preparation method of the adsorbing material specifically comprises the following steps: adding 5.5682g of activated carbon and 5.6268g of copper nitrate (0.03mol) into 40mL of dilute nitric acid with the concentration of 0.20mol/L, stirring and dissolving, adding an ammonia water solution under magnetic stirring to adjust the pH value to 10, transferring the mixture to an ultrasonic and microwave combined reactor after full magnetic stirring, starting a microwave and ultrasonic dual-function device, reacting for 0.5h under the conditions of 1000W ultrasonic waves and 1000W microwaves, filtering to obtain powder, and drying the powder in a 120 ℃ oven for 2h to obtain the adsorbing material; the activated carbon is prepared by taking carbon-containing building or household garbage as a carbon source, and specifically, the carbon-containing building or household garbage is crushed, sieved, deoiled, dissolved in acid, added with alkali to adjust the pH value to be neutral, dried at 110 ℃, transferred to a high-temperature furnace, heated to 750 ℃ under the protection of nitrogen for calcination reaction, floated to obtain a carbon material, washed and dried to obtain the activated carbon.
Comparative example 2
An adsorbing material for removing vanadium from the surface of a substrate made of SnO2As an active component, activated carbon as a porous supporting matrix, wherein SnO2The weight ratio of the active carbon to the active carbon is 30: 70.
The preparation method of the adsorbing material specifically comprises the following steps: adding 10.5497g of activated carbon and 5.6880g of stannous chloride (0.03mol) into 40mL of dilute nitric acid with the concentration of 0.20mol/L, stirring and dissolving, adding an ammonia water solution under magnetic stirring to adjust the pH value to 10, transferring the mixture to an ultrasonic and microwave combined reactor after full magnetic stirring, starting a microwave and ultrasonic dual-function device, reacting for 0.5h under the conditions of 1000W ultrasonic waves and 1000W microwaves, filtering to obtain powder, and drying the powder in a 120 ℃ oven for 2h to obtain the adsorbing material; the activated carbon is prepared by taking carbon-containing building or household garbage as a carbon source, and specifically, the carbon-containing building or household garbage is crushed, sieved, deoiled, dissolved in acid, added with alkali to adjust the pH value to be neutral, dried at 110 ℃, transferred to a high-temperature furnace, heated to 750 ℃ under the protection of nitrogen for calcination reaction, floated to obtain a carbon material, washed and dried to obtain the activated carbon.
Comparative example 3
An adsorbing material for removing vanadium, in the form of La2O3As an active component, activated carbon as a porous supporting matrix, wherein La2O3The weight ratio of the active carbon to the active carbon is 30: 70.
The preparation method of the adsorbing material specifically comprises the following steps: 22.8066g of activated carbon and 25.9800g of lanthanum nitrate (0.06mol) are added into 40mL of dilute nitric acid with the concentration of 0.20mol/L to be stirred and dissolved, ammonia water solution is added under magnetic stirring to adjust the pH value to 10, the mixture is transferred into an ultrasonic-microwave combined reactor after full magnetic stirring, a microwave-ultrasonic dual-function device is started, the mixture reacts for 0.5h under the conditions of 1000W ultrasonic waves and 1000W microwaves at the same time, powder is obtained through filtering, and the powder is put into a 120 ℃ oven to be dried for 2h, so that the adsorbing material is obtained; the activated carbon is prepared by taking carbon-containing building or household garbage as a carbon source, and specifically, the carbon-containing building or household garbage is crushed, sieved, deoiled, dissolved in acid, added with alkali to adjust the pH value to be neutral, dried at 110 ℃, transferred to a high-temperature furnace, heated to 750 ℃ under the protection of nitrogen for calcination reaction, floated to obtain a carbon material, washed and dried to obtain the activated carbon.
Adsorption test 1
The adsorption materials corresponding to the above examples 1 to 6 and comparative examples 1 to 3 were subjected to adsorption performance tests (using a vanadium-containing heavy metal ion solution as a sewage treatment object).
Preparing a sewage treatment object to be detected: taking 100ml of vanadium-containing (3-valent vanadium, 4-valent vanadium and 5-valent vanadium) sewage as a sewage treatment object to be detected, and determining that the concentration of vanadium element is 100 mg/L.
Treating the sewage to be detected:
40mg of the adsorbing materials corresponding to the above examples 1 to 6 and comparative examples 1 to 3 were added to the 9 parts of wastewater to be tested, respectively, and stirred under the irradiation of sunlight, and the vanadium removal rate after the treatment reaction for 0 to 80min was measured, respectively, with the results shown in FIG. 3 below:
as can be seen from fig. 3, the adsorbent according to example 1 had the best adsorption effect, and the removal rate reached 99.2%, and the adsorption removal effect was the better with the lapse of time for all the adsorbents.
Adsorption test 2
The adsorption capacity test was performed on the adsorption materials corresponding to examples 1 to 6 and comparative examples 1 to 3 described above (using the vanadium-containing heavy metal ion solution as the object of sewage treatment).
Preparing a sewage treatment object to be detected: 500ml of vanadium-containing (3-valent vanadium, 4-valent vanadium and 5-valent vanadium) sewage is taken as a sewage treatment object to be detected, and the concentration of vanadium element is determined to be 100 mg/L.
Treating the sewage to be detected:
50mg of the adsorbing materials corresponding to the above examples 1 to 6 and comparative examples 1 to 3 were added to 9 parts of the above sewage to be measured, respectively, and stirred under the irradiation of sunlight, and the adsorption amount of vanadium after the reaction of treatment for 0 to 90min was measured, respectively, and the results are shown in fig. 4 below:
as can be seen from fig. 4, the adsorbing material according to example 1 had the best adsorbing effect, the adsorbing amount reached 236mg/g, and all the adsorbing materials reached substantially stable adsorbing amount with the increase of time after the adsorbing time reached 50 minutes, indicating that the adsorbing process was mainly completed within 50 minutes, and the adsorbing effect was good.
From the above, the adsorption material prepared by the invention can be used for the environmental treatment of industrial sewage and wastewater containing heavy metal solution containing vanadium (3-valent vanadium, 4-valent vanadium and 5-valent vanadium), and can be used for enriching vanadium in alloy steel and catalysts, so that the adsorption material is widely applied to the field of steel and iron, and is applied to various fields such as aerospace, chemistry, batteries, pigments, glass, optics, medicine and the like.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical scope of the present invention, and equivalents and modifications thereof should be included in the technical scope of the present invention.
Claims (9)
1. The multielement composite adsorption material for removing vanadium is characterized by comprising an active component and a porous loading matrix, wherein the active component is CuO-SnO2-La2O3The porous load matrix is active carbon, CuO-SnO2-La2O3The weight ratio of the composite oxide to the active carbon is 30: 70; CuO-SnO2-La2O3In the composite oxide of (2), CuO and SnO2、La2O3In a molar ratio of 2:1: 1.
2. The multi-element composite adsorption material for removing vanadium according to claim 1, wherein the activated carbon is prepared by using carbon-containing construction and/or household garbage as a carbon source; the active carbon is prepared by adopting the following method: crushing, sieving, deoiling and acid dissolving the carbon-containing building and/or household garbage, adding alkali to adjust the pH value to be neutral, drying, transferring to a high-temperature furnace, heating to 800 ℃ under the protection of inert gas for calcination reaction, floating to obtain carbon materials, washing and drying to obtain the activated carbon.
3. The multi-element composite adsorption material for removing vanadium of claim 1, wherein CuO-SnO2-La2O3The composite oxide is loaded on the surface of the active carbon by an in-situ loading method.
4. The multi-element composite adsorbing material for removing vanadium, as claimed in claim 1, wherein the adsorbing material has spherical and rod-shaped particles with a particle size of 500-3000 nm.
5. A method for preparing the multi-element composite adsorption material for removing vanadium according to any one of claims 1 to 4, which is characterized by comprising the following steps: dissolving activated carbon, tin salt, lanthanum salt and copper salt in a dilute acid solution, adding an alkali solution to adjust the pH value to 7-12, reacting under the condition of microwave or ultrasonic microwave combination, filtering and drying to obtain the multi-element composite adsorbing material.
6. The preparation method of the multi-element composite adsorption material for removing vanadium according to claim 5, characterized in that the tin salt is selected from one or more of tin sulfate, tin nitrate and tin chloride; the lanthanum salt is selected from one or more of lanthanum chloride and lanthanum nitrate; the copper salt is selected from one or more of copper sulfate, copper nitrate and copper chloride.
7. The method for preparing the multi-element composite adsorption material for removing vanadium according to claim 5, characterized in that when the reaction is carried out under the condition of the combination of the ultrasonic waves and the microwaves, the power of the ultrasonic waves is 800-.
8. The use of the multi-element composite adsorption material for removing vanadium according to any one of claims 1 to 4 in treating vanadium-containing sewage.
9. The use according to claim 8, comprising: and under the illumination condition, the sewage containing any one or more of 3-valent vanadium, 4-valent vanadium and 5-valent vanadium is fully contacted with the multi-element composite adsorbing material, so that the vanadium in the sewage is adsorbed and removed.
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