CN111111606A - Method for selectively removing heavy metals in wastewater system simultaneously containing organic pollutants and heavy metals - Google Patents

Method for selectively removing heavy metals in wastewater system simultaneously containing organic pollutants and heavy metals Download PDF

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CN111111606A
CN111111606A CN201911359815.8A CN201911359815A CN111111606A CN 111111606 A CN111111606 A CN 111111606A CN 201911359815 A CN201911359815 A CN 201911359815A CN 111111606 A CN111111606 A CN 111111606A
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wastewater
manganese oxide
mesoporous material
ordered mesoporous
mesoporous
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王挺
施敏慧
章珊琦
吴礼光
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Zhejiang Gongshang University
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Zhejiang Gongshang University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

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  • Hydrology & Water Resources (AREA)
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Abstract

The application discloses a method for selectively removing heavy metals in a wastewater system containing both organic pollutants and heavy metals, which comprises the steps of adding a manganese oxide ordered mesoporous material into wastewater to be treated, and selectively adsorbing heavy metal ions in the wastewater to be treated; the wastewater to be treated is wastewater containing heavy metal ions and dye pollutants. The preparation method of the manganese oxide ordered mesoporous material is simple, easy to operate and low in energy consumption and cost, and the structure and the adsorption performance of the mesoporous material can be regulated and controlled simply and conveniently by changing the type of the organic solvent, the template dosage, the calcination temperature and the adsorption frequency. The treatment method keeps high-selectivity adsorption on heavy metal ions, and can overcome the interference of organic pollutants in a wastewater system.

Description

Method for selectively removing heavy metals in wastewater system simultaneously containing organic pollutants and heavy metals
Technical Field
The application relates to the technical field of complex wastewater treatment containing various pollutants, in particular to a method for removing heavy metals in a wastewater system simultaneously containing organic pollutants and heavy metals.
Background
The high-speed development of economy and industry in China also brings about a plurality of serious environmental pollution problems, wherein water pollution is one of the main problems of inhibiting the sustainable development of the economy in China and harming the life health of people. In particular, heavy metal ions (such as Cr, Cu, Pb, and the like) in rivers and other water bodies in China become an urgent problem to be solved. However, the water body has a plurality of pollution sources, and various waste waters of industry, agriculture, life and the like exist, wherein the pollutants in the water body environment are often very complicated. In most cases, water pollution remediation is faced with complex wastewater systems of multiple pollutants, such as both organic pollutants and heavy metal ion pollutants. However, treatment methods for different pollutants are different, for example, the adsorption method for treating organic pollutants requires less hydrophilic groups of the adsorbent, so that selective adsorption on organic matters is remarkable, and heavy metal ions are hydrophilic, so that the surface of the adsorbent is required to have certain hydrophilicity and binding force to the heavy metal ions. Therefore, in a complex wastewater system containing organic matters and heavy metal ions, how to enhance the selective removal capacity of certain pollutants becomes a key factor of research and application in the field of environmental management at present.
At present, the treatment methods of water bodies polluted by heavy metal ions mainly comprise a chemical precipitation method, an electrolysis method and the like, the methods have high energy consumption and complex operation management, the technologies can only treat single metal ion pollution and cannot be used for directly treating a complex wastewater system, the solvent extraction separation method has good selectivity, but the extraction agent has high cost and has the problems of secondary pollution and the like, so that the application of the extraction agent is limited.
Disclosure of Invention
The application provides a method for selectively removing heavy metals in a wastewater system containing organic pollutants and heavy metals at the same time, which is used for preparing an adsorbent with a specific structure, keeping high selective adsorption on heavy metal ions and overcoming the interference of the organic pollutants in the wastewater system.
The preparation method of the manganese oxide ordered mesoporous material for selectively removing the heavy metals in the complex wastewater system comprises the following steps:
(1) adding ordered mesoporous silicon template powder into an organic solvent for ultrasonic dispersion until a stable suspension system is formed;
(2) dropwise adding a manganese nitrate aqueous solution into the suspension system while stirring in a water bath at 0 ℃, and continuously stirring and adsorbing for 50-60 min to obtain a suspension;
(3) filtering, washing and drying the obtained suspension solution in sequence, and then calcining to generate a compound of the manganese oxide and the ordered mesoporous silicon template; re-dispersing the obtained compound in an organic solvent, and sequentially repeating the steps (2) and (3);
(4) and (4) removing the redundant ordered mesoporous silicon template agent in the compound obtained in the last repeated step (3), and washing and drying to obtain the manganese oxide ordered mesoporous material.
And (4) directly removing template molecules without re-dispersing the organic solvent in the compound of the manganese oxide and the ordered mesoporous silicon template obtained in the last operation step (3).
Novel materials such as mesoporous materials, nano materials, carbon materials and the like are used as adsorbents, and the adsorbents show superior performances such as low cost, strong adsorption performance and the like, and are increasingly applied to treatment of heavy metal ions in water. The manganese oxide is a transition metal oxide, has strong stability and large specific surface area, and a large number of hydroxyl active groups exist on the surface. And is also susceptible to protonation and deprotonation, and can provide binding sites for metal ions.
Besides increasing the surface hydrophilicity of the adsorbent to improve the adsorption performance of the adsorbent on heavy metal ions, how to effectively improve the surface area of the adsorbent is also the key for enhancing the selective adsorption performance of the adsorbent on the heavy metal ions. The novel mesoporous material has the advantages of uniform size, uniform pore channel structure, higher specific surface area and pore volume, and greatly improved adsorption performance of manganese oxide.
The preparation principle of the adsorbent is as follows:
introducing a manganese precursor into an organic solvent, effectively adsorbing manganese ions for multiple times through the ordered mesoporous silicon template, and carrying out in-situ reduction in the ordered pore structure of the template in multiple calcination processes to generate manganese oxide and forming. Firstly, a large amount of hydrophilic surface groups contained on the surface of the ordered mesoporous pore canal of the manganese oxide are beneficial to selectively adsorbing inorganic heavy metal ions. In addition, the special manganese oxide valence state formed by the ordered mesoporous channel structure can effectively improve the adsorption capacity of the material in a complex wastewater system on inorganic heavy metal ions.
Several alternatives are provided below, but not as an additional limitation to the above general solution, but merely as a further addition or preference, each alternative being combinable individually for the above general solution or among several alternatives without technical or logical contradictions.
Optionally, the repetition times of the step (2) and the step (3) are 2-6 times. Further, the number of repetitions is 2 to 4, and further, the number of repetitions is 3. The times of the impregnation adsorption and calcination processes are increased, the ordered mesoporous pore channel is easier to form, so that the ordered mesoporous pore channel with large pore diameter is formed, the specific surface area of the material is improved, and the surface hydrophilicity is improved, so that the adsorption capacity of the ordered mesoporous manganese oxide material on heavy metal ions is improved.
The mesoporous silicon template has an ordered mesoporous pore structure, and the specific surface area of ordered mesoporous silicon template powder is 550-600 m2·g-1The pore volume is 1-2 cm3·g-1The pore diameter is 6-11 nm. Furthermore, the mesoporous silicon template is SBA-15 mesoporous silicon template agent, so that a stable suspension system can be formed in an organic solvent, and the stabilization time is more than 5 h. Can be commercially obtained or self-made.
Optionally, the ratio of the ordered mesoporous silicon template powder to the organic solvent in the step (1) is 1-5.0 g:50 mL. Further, it was 2.0g:50 mL.
Optionally, the organic solvent is ethanol, cyclohexane, or n-hexane.
Optionally, the mass concentration of the manganese nitrate aqueous solution added in the step (2) is 10-50%, and the volume ratio of the manganese nitrate aqueous solution to the organic solvent added in each step (2) is 1-3: 50.
Further, the mass concentration of the manganese nitrate aqueous solution added in the step (2) is 20%, and the volume ratio of the manganese nitrate aqueous solution to the organic solvent added each time the operation of the step (2) is performed is 2: 50.
Optionally, the calcining temperature is 400-700 ℃, and the calcining time is 1-5 hours. Further, the calcination temperature was 500 ℃ and the calcination time was 1 hour.
The method for removing the redundant ordered mesoporous silicon template comprises the following steps:
mixing the obtained compound with 6mol/L NaOH aqueous solution according to the weight ratio of 1-5.0 g: 200mL of the mixture was mixed well and stirred at 80 ℃ for 2 hours. And (3) cooling the ordered mesoporous silicon template to room temperature, centrifuging and washing with deionized water for multiple times until the pH value of supernatant liquor after centrifugation is 7.0. And then, drying the powder in a vacuum oven at 100 ℃ for 24 hours to obtain the ordered mesoporous material of the manganese oxide.
The preparation method can change the pore channel structure of the manganese oxide ordered mesoporous material simply and conveniently by changing the type of the organic solvent, the dosage of the template, the calcination temperature, particularly the times of the steps of dipping, adsorbing and calcining and the like.
The application also provides the manganese oxide ordered mesoporous material prepared by the preparation method.
The application also provides a method for selectively removing heavy metals in a wastewater system containing both organic pollutants and heavy metals, which comprises the following steps:
adding the manganese oxide ordered mesoporous material into wastewater to be treated, and selectively adsorbing heavy metal ions in the wastewater to be treated; the wastewater to be treated is wastewater containing heavy metal ions and dye pollutants.
Optionally, the mass-volume ratio of the added amount of the manganese oxide ordered mesoporous material to the wastewater to be treated is 10-15 mg:100 mL.
Optionally, the heavy metal ion is Cr6+The content is 2-10 mg.L-1(ii) a The dye pollutant is azo dye with the content of 20-100 mg.L-1. Optionally, the azo dye is methyl orange. The content of the manganese oxide ordered mesoporous material in azo dyes, particularly methyl orange, is 20-100 mg.L-1And Cr6+The content is 2-10 mg.L-1In a complex wastewater system of (2), to Cr6+The heavy metal ions have good adsorption removal rate.
Further, the dye pollutant in the wastewater to be treated is methyl orange with the content of 50 mg.L-1The heavy metal ion is Cr6+The content is preferably 5 mg.L-1。
Compared with the prior art, the application has at least the following beneficial effects:
1) the mesoporous material is prepared by a mature preparation method or by purchasing a stable silicon template with an ordered mesoporous structure as a template agent, so that the stability of the mesoporous material in the preparation process can be maintained to the greatest extent.
2) The nano etching preparation method is that in an organic solvent, the manganese source precursor is driven to enter a pore channel of a template by utilizing the hydrophobicity of the organic solvent; reducing the manganese source precursor entering the pore channel into manganese oxide in situ by using a high-temperature calcination method; the manganese oxide can be promoted to be formed through multiple adsorption and calcination processes to form the ordered mesoporous material. The structure of the generated mesoporous material can be regulated according to reaction conditions, and the prepared manganese oxide mesoporous material has an ordered mesoporous structure and higher specific surface area and adsorption capacity.
3) The preparation method is simple, easy to operate and low in energy consumption and cost. The preparation method can be used for simply and conveniently regulating and controlling the structure and the adsorption performance of the mesoporous material by changing the type of the organic solvent, the template dosage, the calcination temperature and the adsorption frequency.
(4) The adsorbent prepared by the method can keep high-selectivity adsorption on heavy metal ions, and can overcome the interference of organic pollutants in a wastewater system.
Drawings
FIG. 1 is a photograph showing the appearance of powders of mesoporous manganese oxide materials prepared in comparative examples and examples 1 to 3 of the present application.
FIG. 2 is an infrared spectrum (FT-IR) chart of the mesoporous manganese oxide material prepared in the comparative example and examples 1 to 3.
FIG. 3 is a Transmission Electron Microscope (TEM) photograph of mesoporous manganese oxide materials prepared in comparative examples and examples 1 to 3 of the present application.
FIG. 4 shows N of mesoporous manganese oxide materials prepared in comparative examples and examples 1 to 3 of the present application2Adsorption-desorption curve.
FIG. 5 is a graph showing the distribution of the pore diameters of mesoporous manganese oxide materials prepared in comparative examples and examples 1 to 3.
FIG. 6 is an X-ray photoelectron (XPS) spectrum of the mesoporous manganese oxide material prepared in the comparative example and examples 1 to 3.
FIG. 7 is an adsorption curve of the mesoporous manganese oxide material prepared in the comparative example and examples 1 to 3 of the present application in heavy metal wastewater.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
The following description is of the preferred embodiment of the present invention and is not intended to limit the invention thereto. In the embodiment, the commercial mesoporous silicon material SBA-15 is selected as a mesoporous silicon template with an ordered pore structure, and the specific surface area is 550-600 m2·g-1The pore volume is 1-2 cm3·g-1The pore diameter is 6-11 nm.
Comparative example
The mesoporous manganese oxide material obtained by using the mesoporous silicon material SBA-15 as a mesoporous silicon template and only performing the processes of primary dispersion, impregnation adsorption, drying and calcination is used as a control group.
(1) Preparation of manganese oxide mesoporous material
2.0g of SBA-15 silicon template was added to 50ml of cyclohexane and dispersed by sonication (over 5 h) until a stable suspension system was formed. Then, under the condition of water bath at 0 ℃, 4.0mL of manganese nitrate solution (10%) is added into the suspension system dropwise while stirring, and the mixture is stirred and adsorbed for 1 hour. And filtering, washing and drying the suspension system, completely transferring the suspension system into a crucible, covering the crucible, and stably putting the crucible into a muffle furnace for calcining for 1 hour at 500 ℃. After the reaction is finished, taking out the crucible and placing the crucible at room temperature to naturally cool the crucible. After the temperature is reduced to the room temperature, 200mL of 6.0mol/L NaOH is added, the mixture is stirred at the temperature of 80 ℃ until the SBA-15 template is completely removed, and the mixture is cooled to the room temperature, centrifuged and washed by deionized water for a plurality of times until the pH value of supernatant after centrifugation is 7.0. Then, the powder is placed in a vacuum oven to be dried for 24 hours at the temperature of 100 ℃, and the manganese oxide mesoporous material is obtained and is marked as U-MnOx。
U-MnO prepared in this comparative examplexThe appearance of the mesoporous material powder is shown in the comparative example sheet in FIG. 1; U-MnO prepared in this comparative examplexThe infrared spectrum (FT-IR) of the mesoporous material is shown as a control graph sheet in figure 2; U-MnO prepared in this comparative examplexThe Transmission Electron Microscope (TEM) photograph of the mesoporous material is shown as the comparative picture in FIG. 3; U-MnO prepared in this comparative examplexN of mesoporous material2The adsorption-desorption curve is shown in the comparative example in fig. 4, and the pore size distribution is shown in the comparative example in fig. 5; U-MnO prepared in this comparative examplexAn X-ray photoelectron (XPS) spectrum of the mesoporous material is shown in a control graph in FIG. 6; U-MnO prepared in this comparative examplexThe numerical table of the specific surface area, the pore volume and the pore diameter of the mesoporous material is shown in table 1; U-MnO prepared in this comparative examplexXPS parameters of the mesoporous material are shown in table 2.
From the IR spectrum of FIG. 2574nm has an obvious characteristic peak which is a Mn-O characteristic peak, and the substance is manganese oxide. It can be seen from the TEM image (fig. 3) that the manganese oxide can not be mesoporous-molded and can only form the structural feature of "flocculent" disordered mesoporous channel due to only one impregnation, adsorption and calcination process, and N is the ratio of the number of the pores in the manganese oxide to the number of the pores in the manganese oxide2The adsorption-desorption curve and the specific surface area, pore volume and aperture numerical values in table 1 can also prove that the mesoporous material belongs to a mesoporous structure and has a large specific surface area. However, the data in Table 2 show that the pore structure is not shaped, so that the content of high valence manganese in the manganese oxide is not high, and the hydrophilic groups such as hydroxyl groups on the surface are not abundant.
(2) Contains methyl orange and Cr6+Cr in complex wastewater system6+Adsorption removal process of
0.05g of U-MnO obtained in the comparative example was weighedxMesoporous material, uniformly mixed in 250mL of a mixture containing methyl orange and Cr6+The concentration of methyl orange is 50mg/L, Cr is in the complex wastewater6+Has a concentration of 5 mg.L-1) Placing in a reactor with magnetic stirring, controlling water bath temperature at 30 deg.C, sampling every 10 minutes for the first 30 minutes, sampling every 30 minutes (till 2 hr), centrifuging, collecting supernatant, and measuring Cr in the supernatant by diphenylcarbonyldihydrazine method6+The adsorption removal rate was calculated from the change in concentration of (2).
U-MnO prepared in this comparative examplexMesoporous material for Cr in wastewater system6+The adsorption curve (2 hours) of (A) is shown in FIG. 7 for the comparative example. The curve shows that the adsorption removal rate of the mesoporous material to the heavy metal wastewater is only about 10%. This shows that although the specific surface area of the mesoporous material with the disordered mesoporous structure is relatively large, the manganese content of the manganese oxide mesoporous material at the high price in China is not large, and the hydrophilic groups on the surface of the mesoporous material are not abundant enough. Therefore, in a composite wastewater system containing organic pollutants and heavy metal ions, the interference of the organic pollutants is difficult to overcome to adsorb the hexavalent chromium ions.
Example 1
(1) Preparation of ordered mesoporous manganese oxide material
2.0g of SBA-15 silicon template was added to 50ml of cyclohexane and dispersed by sonication (over 5 h) until a stable suspension system was formed. Then, under the condition of water bath at 0 ℃, 2.0mL of manganese nitrate solution (10%) is added into the suspension system dropwise while stirring, and the mixture is stirred and adsorbed for 1 hour. And filtering, washing and drying the suspension system, completely transferring the suspension system into a crucible, covering the crucible, and stably putting the crucible into a muffle furnace for calcining for 1 hour at 500 ℃. After the reaction is finished, taking out the crucible and placing the crucible at room temperature to naturally cool the crucible.
After cooling to room temperature, the composite powder was again added to 50ml of cyclohexane and dispersed by sonication (over 5 h) until a stable suspension system was formed. Then, under the condition of water bath at 0 ℃, 2.0mL of manganese nitrate solution (10%) is added into the suspension system dropwise while stirring, and the mixture is stirred and adsorbed for 1 hour. And filtering, washing and drying the suspension system, completely transferring the suspension system into a crucible, covering the crucible, and stably putting the crucible into a muffle furnace for calcining for 1 hour at 500 ℃. After the reaction is finished, taking out the crucible and placing the crucible at room temperature to naturally cool the crucible. After the temperature is reduced to the room temperature, 200mL of 6.0mol/L NaOH is added, the mixture is stirred at the temperature of 80 ℃ until the SBA-15 template is completely removed, and the mixture is cooled to the room temperature, centrifuged and washed by deionized water for a plurality of times until the pH value of supernatant after centrifugation is 7.0. Then, the powder is placed in a vacuum oven to be dried for 24 hours at the temperature of 100 ℃, and the manganese oxide mesoporous material is obtained and is marked as M-MnOx-1。
M-MnO prepared in example 1x-1 powder appearance of mesoporous material is shown in figure 1 as example 1 picture; M-MnO prepared in example 1x-1 infrared spectrum (FT-IR) of mesoporous material as shown in figure 2, example 1; M-MnO prepared in this examplex-1 Transmission Electron Microscopy (TEM) picture of mesoporous material as shown in figure 3, example 1 picture; M-MnO prepared in this examplex-1N of mesoporous material2The adsorption-desorption curve is shown in example 1 in fig. 4, and the pore size distribution is shown in example in fig. 5; M-MnO prepared in this examplex-1X-ray photoelectron (XPS) spectrum of mesoporous material as shown in the control panel of fig. 6; M-MnO prepared in this examplex-1 the specific surface area, pore volume and pore diameter numerical table of the mesoporous material is shown in table 1; the control wasExample prepared U-MnOxXPS parameters of the mesoporous material are shown in table 2.
An obvious characteristic peak is shown at 574nm in the infrared spectrum of FIG. 2, and is a Mn-O characteristic peak, which indicates that the substance is manganese oxide; in contrast to the IR spectrum of SBA-15 in FIG. 2, there is no Si-O characteristic peak, indicating that the silicon template SBA-15 in this example has been removed. The TEM photograph (FIG. 3) shows the M-MnO after two times of impregnation-adsorption-calcinationx-1 mesoporous material with ordered channel structure, from N2The adsorption-desorption curve, and the specific surface area, pore volume and aperture value in table 1 can also prove that the mesoporous material belongs to a mesoporous structure, and the surface area is smaller than that of the disordered mesoporous material manganese oxide of the comparative example. However, as can be seen from table 2, in the ordered mesoporous manganese oxide in this embodiment, the content of high-valence manganese is increased, the proportion of surface hydroxyl oxygen is also higher, and the ordered mesoporous manganese oxide has better hydrophilicity.
(2) Contains methyl orange and Cr6+Cr in complex wastewater system6+Adsorption removal process of
0.05g of M-MnO obtained in the comparative example was weighedx-1 ordered mesoporous material uniformly mixed in 250mL containing methyl orange and Cr6+The concentration of methyl orange is 50mg/L, Cr is in the complex wastewater6+Has a concentration of 5 mg.L-1) Placing in a reactor with magnetic stirring, controlling water bath temperature at 30 deg.C, sampling every 10 minutes for the first 30 minutes, sampling every 30 minutes for the second (till 2h), centrifuging, collecting supernatant, and measuring Cr in the supernatant by using diphenylcarbonyldihydrazine method6+The adsorption removal rate was calculated from the change in concentration of (2).
M-MnO prepared in this examplex-1 the adsorption curve (reaction time 2 hours) of the mesoporous material to heavy metal ions is shown in example 1 in fig. 7. The curve shows that the adsorption removal rate of the mesoporous material to the heavy metal wastewater can reach about 30%. This shows that although the specific surface area of the manganese oxide with the ordered mesoporous channel structure is significantly reduced compared with that of the disordered mesoporous manganese oxide in the comparative example, the manganese oxide ordered mesoporous material has a more detailed content of high-valence manganese and has more hydrophilic groups on the surface. Thus is contained inIn a composite wastewater system with organic pollutants and heavy metal ions, the interference of the organic pollutants can be overcome, and hexavalent chromium ions can be obviously adsorbed.
Example 2
(1) Preparation of ordered mesoporous manganese oxide material
2.0g of SBA-15 silicon template was added to 50ml of cyclohexane and dispersed by sonication (over 5 h) until a stable suspension system was formed. Then, under the condition of water bath at 0 ℃, 2.0mL of manganese nitrate solution (10%) is added into the suspension system dropwise while stirring, and the mixture is stirred and adsorbed for 1 hour. And filtering, washing and drying the suspension system, completely transferring the suspension system into a crucible, covering the crucible, and stably putting the crucible into a muffle furnace for calcining for 1 hour at 500 ℃. After the reaction is finished, taking out the crucible and placing the crucible at room temperature to naturally cool the crucible.
After cooling to room temperature, the composite powder was again added to 50ml of cyclohexane and dispersed by sonication (over 5 h) until a stable suspension system was formed. Then, under the condition of water bath at 0 ℃, 2.0mL of manganese nitrate solution (10%) is added into the suspension system dropwise while stirring, and the mixture is stirred and adsorbed for 1 hour. And filtering, washing and drying the suspension system, completely transferring the suspension system into a crucible, covering the crucible, and stably putting the crucible into a muffle furnace for calcining for 1 hour at 500 ℃. After the reaction is finished, taking out the crucible and placing the crucible at room temperature to naturally cool the crucible.
After cooling to room temperature, the composite powder was again added to 50ml of cyclohexane and dispersed by sonication (over 5 h) until a stable suspension system was formed. Then, under the condition of water bath at 0 ℃, 2.0mL of manganese nitrate solution (10%) is added into the suspension system dropwise while stirring, and the mixture is stirred and adsorbed for 1 hour. And filtering, washing and drying the suspension system, completely transferring the suspension system into a crucible, covering the crucible, and stably putting the crucible into a muffle furnace for calcining for 1 hour at 500 ℃. After the reaction is finished, taking out the crucible and placing the crucible at room temperature to naturally cool the crucible. After the temperature is reduced to the room temperature, 200mL of 6.0mol/L NaOH is added, the mixture is stirred at the temperature of 80 ℃ until the SBA-15 template is completely removed, and the mixture is cooled to the room temperature, centrifuged and washed by deionized water for a plurality of times until the pH value of supernatant after centrifugation is 7.0. Then, mixing the powderDrying in a vacuum oven at 100 deg.C for 24 hr to obtain mesoporous Mn oxide material, which is marked as M-MnOx-2。
M-MnO prepared in this examplex-2 powder appearance of mesoporous material is shown in figure 1 as example 2 picture; M-MnO prepared in this examplex-2 infrared spectrum (FT-IR) of mesoporous material as shown in figure 2, example 2; M-MnO prepared in this examplex-2 Transmission Electron Microscopy (TEM) picture of mesoporous material as shown in figure 3, example 2 picture; M-MnO prepared in this examplex-2 mesoporous material N2The adsorption-desorption curve is shown in example 2 in fig. 4, and the pore size distribution is shown in example 2 in fig. 5; M-MnO prepared in this examplex-2X-ray photoelectron (XPS) spectroscopy of mesoporous material as shown in figure 6, example 2 picture; M-MnO prepared in this examplex-2 the numerical table of the specific surface area, the pore volume and the pore diameter of the mesoporous material is shown in table 1; M-MnO prepared in this examplex-2 XPS parameter table of mesoporous material as shown in Table 2.
An obvious characteristic peak is shown at 574nm in the infrared spectrum of FIG. 2, and is a Mn-O characteristic peak, which indicates that the substance is manganese oxide; in contrast to the IR spectrum of SBA-15 in FIG. 2, there is no Si-O characteristic peak, indicating that the silicon template SBA-15 in this example has been removed. In the TEM photograph (FIG. 3), it can be seen that as the number of impregnation-adsorption-calcination increases, M-MnOx-2 mesoporous material with more ordered pore structure, from N2The adsorption-desorption curve, and the specific surface area, pore volume and aperture value in the table 1 can also prove that the mesoporous material belongs to a mesoporous structure, the surface area is smaller than the disordered mesoporous material manganese oxide of the comparative example, but the specific surface area is obviously larger than the M-MnO obtained in the example 1x-1 mesoporous material. As can be seen from table 2, as the times of impregnation-adsorption-calcination increase, the content of high-valence manganese in the ordered mesoporous manganese oxide in the examples increases, and the proportion of surface hydroxyl oxygen increases, so that the ordered mesoporous manganese oxide has better hydrophilicity.
(2) Contains methyl orange and Cr6+Cr in complex wastewater system6+Adsorption removal process of
Weigh 0.05g of controlM-MnO obtained in examplex-2 ordered mesoporous material uniformly mixed in 250mL containing methyl orange and Cr6+The concentration of methyl orange is 50mg/L, Cr is in the complex wastewater6+Has a concentration of 5 mg.L-1) Placing in a reactor with magnetic stirring, controlling water bath temperature at 30 deg.C, sampling every 10 minutes for the first 30 minutes, sampling every 30 minutes for the second (till 2h), centrifuging, collecting supernatant, and measuring Cr in the supernatant by using diphenylcarbonyldihydrazine method6+The adsorption removal rate was calculated from the change in concentration of (2).
M-MnO prepared in this examplex-2 adsorption curve (reaction time 2 hours) of the mesoporous material to heavy metal ions is shown in example 2 in fig. 7, and the curve shows that the adsorption removal rate of the mesoporous material to heavy metal wastewater can reach about 50%. This shows that although the specific surface area of the manganese oxide with the ordered mesoporous channel structure is obviously reduced compared with that of the disordered mesoporous manganese oxide in the comparative example, the content of high-valence manganese in the ordered mesoporous manganese oxide material is obviously increased, and the surface hydrophilic groups are also richer. Therefore, in a composite wastewater system containing organic pollutants and heavy metal ions, the interference of the organic pollutants can be overcome, and hexavalent chromium ions can be obviously adsorbed. With the increase of the times of dipping, adsorption and calcination, mesoporous channels in the material become more ordered, and the content of high-valence manganese and surface hydrophilic groups are increased, so that the selective adsorption capacity of hexavalent chromium ions is enhanced.
Example 3
(1) Preparation of ordered mesoporous manganese oxide material
2.0g of SBA-15 silicon template was added to 50ml of cyclohexane and dispersed by sonication (over 5 h) until a stable suspension system was formed. Then, under the condition of water bath at 0 ℃, 2.0mL of manganese nitrate solution (10%) is added into the suspension system dropwise while stirring, and the mixture is stirred and adsorbed for 1 hour. And filtering, washing and drying the suspension system, completely transferring the suspension system into a crucible, covering the crucible, and stably putting the crucible into a muffle furnace for calcining for 1 hour at 500 ℃. After the reaction is finished, taking out the crucible and placing the crucible at room temperature to naturally cool the crucible.
After cooling to room temperature, the composite powder was again added to 50ml of cyclohexane and dispersed by sonication (over 5 h) until a stable suspension system was formed. Then, under the condition of water bath at 0 ℃, 2.0mL of manganese nitrate solution (10%) is added into the suspension system dropwise while stirring, and the mixture is stirred and adsorbed for 1 hour. And filtering, washing and drying the suspension system, completely transferring the suspension system into a crucible, covering the crucible, and stably putting the crucible into a muffle furnace for calcining for 1 hour at 500 ℃. After the reaction is finished, taking out the crucible and placing the crucible at room temperature to naturally cool the crucible.
After cooling to room temperature, the composite powder was again added to 50ml of cyclohexane and dispersed by sonication (over 5 h) until a stable suspension system was formed. Then, under the condition of water bath at 0 ℃, 2.0mL of manganese nitrate solution (10%) is added into the suspension system dropwise while stirring, and the mixture is stirred and adsorbed for 1 hour. And filtering, washing and drying the suspension system, completely transferring the suspension system into a crucible, covering the crucible, and stably putting the crucible into a muffle furnace for calcining for 1 hour at 500 ℃. After the reaction is finished, taking out the crucible and placing the crucible at room temperature to naturally cool the crucible.
After cooling to room temperature, the composite powder was again added to 50ml of cyclohexane and dispersed by sonication (over 5 h) until a stable suspension system was formed. Then, under the condition of water bath at 0 ℃, 2.0mL of manganese nitrate solution (10%) is added into the suspension system dropwise while stirring, and the mixture is stirred and adsorbed for 1 hour. And filtering, washing and drying the suspension system, completely transferring the suspension system into a crucible, covering the crucible, and stably putting the crucible into a muffle furnace for calcining for 1 hour at 500 ℃. After the reaction is finished, taking out the crucible and placing the crucible at room temperature to naturally cool the crucible. After the temperature is reduced to the room temperature, 200mL of 6.0mol/L NaOH is added, the mixture is stirred at the temperature of 80 ℃ until the SBA-15 template is completely removed, and the mixture is cooled to the room temperature, centrifuged and washed by deionized water for a plurality of times until the pH value of supernatant after centrifugation is 7.0. Then, the powder is placed in a vacuum oven to be dried for 24 hours at the temperature of 100 ℃, and the manganese oxide mesoporous material is obtained and is marked as M-MnOx-3。
M-MnO prepared in this examplex-3 powder appearance of mesoporous material as shown in figure 1, example 3 picture; M-MnO prepared in this examplex-3 infrared spectrum (FT-IR) of mesoporous material as shown in figure 2, example 3; M-MnO prepared in this examplex-3 Transmission Electron Microscopy (TEM) picture of mesoporous material as shown in figure 3, example 3 picture; M-MnO prepared in this examplex-3N of mesoporous material2The adsorption-desorption curve is shown in example 3 in fig. 4, and the pore size distribution is shown in example 3 in fig. 5; M-MnO prepared in this examplex-3X-ray photoelectron (XPS) spectroscopy of mesoporous material as shown in figure 6, example 3 picture; M-MnO prepared in this examplex-3 the specific surface area, pore volume and pore diameter numerical table of the mesoporous material is shown in table 1; M-MnO prepared in this examplex-3 XPS parameter table of mesoporous material as shown in Table 2.
An obvious characteristic peak is shown at 574nm in the infrared spectrum of FIG. 2, and is a Mn-O characteristic peak, which indicates that the substance is manganese oxide; in contrast to the IR spectrum of SBA-15 in FIG. 2, there is no Si-O characteristic peak, indicating that the silicon template SBA-15 in this example has been removed. TEM photograph (FIG. 3) shows M-MnO after four times of impregnation-adsorption-calcinationx-3 the mesoporous material has a more ordered pore structure, but the order degree is weaker than that of the mesoporous material in example 2. From N2The adsorption-desorption curve, and the specific surface area, pore volume and aperture value in the table 1 can also prove that the mesoporous material belongs to a mesoporous structure, the surface area is smaller than the disordered mesoporous material manganese oxide of the comparative example, but the specific surface area is smaller than the M-MnO obtained in the example 2xAnd 2, the mesoporous material shows that excessive times of impregnation, adsorption and calcination can cause the wall thickness of mesoporous channels to be too thick, so that the order degree of the mesoporous channels is weakened, and the surface area is reduced. As can be seen from table 2, after four times of impregnation-adsorption-calcination, the content of higher-valent manganese in the ordered mesoporous manganese oxide of example 3 was rather less than that of the mesoporous material of example 2, and the proportion of surface hydroxyl oxygen was also reduced.
(2) Contains methyl orange and Cr6+Cr in complex wastewater system6+Adsorption removal process of
0.05g of M-MnO obtained in the comparative example was weighedx-3 ordered mesoporous material, uniformly mixed in 250mL containing methyl orange and Cr6+The concentration of methyl orange is 50mg/L, Cr is in the complex wastewater6+Has a concentration of 5 mg.L-1) Placing in a reactor with magnetic stirring, controlling water bath temperature at 30 deg.C, sampling every 10 minutes for the first 30 minutes, sampling every 30 minutes for the second (till 2h), centrifuging, collecting supernatant, and measuring Cr in the supernatant by using diphenylcarbonyldihydrazine method6+The adsorption removal rate was calculated from the change in concentration of (2).
M-MnO prepared in this examplex-3 mesoporous material to heavy metal ion (Cr)6+) The adsorption curve (reaction time 2 hours) of (A) is shown in FIG. 7. The curve shows that the adsorption removal rate of the mesoporous material to the heavy metal wastewater can reach about 45%. This shows that although the specific surface area of the manganese oxide with the ordered mesoporous channel structure is obviously reduced compared with that of the disordered mesoporous manganese oxide in the comparative example, the content of high-valence manganese in the ordered mesoporous manganese oxide material is obviously increased, and the surface hydrophilic groups are also richer. Therefore, in a composite wastewater system containing organic pollutants and heavy metal ions, the interference of the organic pollutants can be overcome, and hexavalent chromium ions can be obviously adsorbed. The excessive times of dipping, adsorption and calcination cause the reduction of the order degree of mesoporous channels in the material, the reduction of the specific surface area, the reduction of the content of high-valence manganese and the reduction of surface hydrophilic groups, so the selective adsorption and adsorption capacity of hexavalent chromium ions is slightly reduced.
The specific surface area, the pore volume and the aperture numerical value of the manganese oxide mesoporous material prepared in the comparative example and the examples 1 to 4 are shown in table 1; XPS parameters of the mesoporous manganese oxide materials prepared in the comparative examples and examples 1 to 4 are shown in Table 2.
TABLE 1
Figure RE-GDA0002430667160000161
TABLE 2
Figure RE-GDA0002430667160000162
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The preparation method of the manganese oxide ordered mesoporous material for selectively removing the heavy metals in the complex wastewater system is characterized by comprising the following steps:
(1) adding ordered mesoporous silicon template powder into an organic solvent for ultrasonic dispersion until a stable suspension system is formed;
(2) dropwise adding a manganese nitrate aqueous solution into the suspension system while stirring in a water bath at 0 ℃, and continuously stirring and adsorbing for 50-60 min to obtain a suspension;
(3) filtering, washing and drying the obtained suspension solution in sequence, and then calcining to generate a compound of the manganese oxide and the ordered mesoporous silicon template;
re-dispersing the obtained compound in an organic solvent, and sequentially repeating the steps (2) and (3);
(4) and (4) removing the redundant ordered mesoporous silicon template agent in the compound obtained in the last repeated step (3), and washing and drying to obtain the manganese oxide ordered mesoporous material.
2. The method according to claim 1, wherein the steps (2) and (3) are repeated 2 to 6 times.
3. The preparation method according to claim 1, wherein the ordered mesoporous silicon template powder has a specific surface area of 550 to 600m2·g-1The pore volume is 1-2 cm3·g-1The pore diameter is 6-11 nm.
4. The preparation method according to claim 1, wherein the ratio of the ordered mesoporous silicon template powder to the organic solvent in the step (1) is 1-5.0 g:50 mL.
5. The preparation method according to claim 1, wherein the mass concentration of the manganese nitrate aqueous solution added in the step (2) is 10-50%, and the volume ratio of the manganese nitrate aqueous solution to the organic solvent added each time the operation of the step (2) is performed is 1-3: 50.
6. The preparation method according to claim 1, wherein the calcination temperature is 400 ℃ to 700 ℃ and the calcination time is 1 to 5 hours.
7. The manganese oxide ordered mesoporous material prepared by the preparation method according to any one of claims 1 to 6.
8. The method for selectively removing heavy metals in a wastewater system containing organic pollutants and heavy metals is characterized by comprising the following steps:
adding the manganese oxide ordered mesoporous material of claim 7 into wastewater to be treated, and selectively adsorbing heavy metal ions in the wastewater to be treated; the wastewater to be treated is wastewater containing heavy metal ions and dye pollutants.
9. The method according to claim 8, wherein the mass-to-volume ratio of the added amount of the manganese oxide ordered mesoporous material to the wastewater to be treated is 10-15 mg:100 mL.
10. The method of claim 8, wherein the heavy metal ion is Cr6+And the dye pollutant is azo dye.
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