CN114405484A - Magnetically separable modified red mud adsorbent and application thereof - Google Patents
Magnetically separable modified red mud adsorbent and application thereof Download PDFInfo
- Publication number
- CN114405484A CN114405484A CN202210017450.6A CN202210017450A CN114405484A CN 114405484 A CN114405484 A CN 114405484A CN 202210017450 A CN202210017450 A CN 202210017450A CN 114405484 A CN114405484 A CN 114405484A
- Authority
- CN
- China
- Prior art keywords
- red mud
- adsorbent
- cyclodextrin
- magnetic separation
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 71
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 64
- 238000007885 magnetic separation Methods 0.000 claims abstract description 47
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000010306 acid treatment Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000010865 sewage Substances 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
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- 239000000243 solution Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000001116 FEMA 4028 Substances 0.000 claims description 16
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 16
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
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- 230000008929 regeneration Effects 0.000 claims description 8
- PCRSJGWFEMHHEW-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-dicarbonitrile Chemical compound FC1=C(F)C(C#N)=C(F)C(F)=C1C#N PCRSJGWFEMHHEW-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
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- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 4
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
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Images
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to the technical field of environmental remediation and protection, and particularly discloses a magnetically separable modified red mud adsorbent and application thereof. The magnetically separable modified red mud adsorbent takes red mud generated in alumina production as a raw material, the red mud is subjected to acid treatment, then the red mud subjected to acid treatment is impregnated with a carbon-containing organic solution, and then the red mud is dried and calcined to obtain the red mud with magnetic separation performance; and (3) carrying out cyclodextrin modification on the red mud with the magnetic separation performance to obtain the magnetically separable modified red mud adsorbent. According to the invention, waste red mud industrial waste is selected as a raw material, magnetic performance of the red mud material is regulated and controlled through a simple acid treatment and high-temperature atmosphere calcination mode, and on the basis of endowing a new magnetic separation function to the red mud powder, a cyclodextrin polymer with a cavity structure is loaded on the surface to provide a more ideal reaction interface for interface adsorption, so that a new method is provided for safe and green removal of pollutants in water while resource utilization of the red mud is realized.
Description
Technical Field
The invention relates to the technical field of environmental remediation and protection, in particular to a magnetically separable modified red mud adsorbent and application thereof.
Background
China is the largest alumina production country in the world, and about 1.0-1.8 t of red mud solid waste residue is discharged when 1t of alumina is produced in the alumina production process. The red mud not only contains a large amount of strong alkaline substances and directly influences the water quality safety of surface water and underground water, but also causes great waste of land resources due to large-amount piling.
At present, the treatment of the red mud is mainly focused on the harmless treatment of the red mud so as to reduce the influence of the accumulation on the environment. The comprehensive utilization of red mud is limited, and reports mainly include that the red mud is used for manufacturing building materials such as cement, wallboards and the like, or is used as a flue gas desulfurizer, or valuable metals are extracted and recovered from the red mud.
The effective utilization and treatment of a large amount of red mud still are difficult problems which plague the alumina industry. Therefore, it is necessary to search for a better method for comprehensive utilization of red mud.
Disclosure of Invention
The invention mainly solves the technical problem of providing a magnetically separable modified red mud adsorbent, which is prepared from red mud, can be used for sewage purification treatment, has good sewage treatment effect and is easy to separate from sewage.
Meanwhile, the invention also provides an application method of the adsorbent.
In order to solve the technical problems, the invention adopts the technical scheme that: a magnetically separable modified red mud adsorbent is prepared by taking red mud generated in alumina production as a raw material, carrying out acid treatment on the red mud, then impregnating the acid-treated red mud with a carbon-containing organic solution, and then drying and calcining to obtain the red mud with magnetic separation performance; and performing cyclodextrin modification on the red mud with the magnetic separation performance to obtain the magnetically separable modified red mud adsorbent.
Red mud is called red mud because it contains iron oxide and is similar to red mud in appearance. The invention takes industrial solid waste red mud discharged in the production of alumina as a raw material, and preferably the red mud with the iron oxide content of more than 5 percent by mass. The red mud contains a large amount of alkaline substances, so the red mud is firstly subjected to acid treatment to remove alkali metals and alkaline earth metals in the red mud, and the acid adopted in the acid treatment is inorganic acid, such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and the like; after the red mud is treated by acid, the red mud is impregnated by a carbon-containing organic solution, so that carbon-containing organic molecules are loaded on the surface of the red mud, then the red mud is dried and calcined at high temperature under an inert environment, the magnetic property of iron substances contained in the red mud is regulated and controlled by utilizing the thermal reduction effect of reducing substances generated by decomposing the carbon-containing organic molecules, specifically, in the heating reaction process, the carbon-containing organic molecules such as glucose and the like can be decomposed to generate gases with reducibility, such as carbon monoxide and the like, and the gases with reducibility can react with iron oxide in the red mud at high temperature to convert the iron oxides into ferroferric oxide with magnetism, so that the red mud with magnetic separation performance is obtained; and then the red mud with the magnetic separation performance is taken as a carrier, a cyclodextrin polymer is polymerized on the surface of the red mud to form an ideal site for the efficient adsorption of pollutant molecules by forming a rich cavity structure, so that the cyclodextrin modified red mud adsorbent with the magnetic separation performance is prepared. The realization shows that the adsorbent prepared by the invention can be used for adsorbing and removing organic pollutants in wastewater or waste gas, can realize effective separation by means of the magnetism of iron-containing oxides in red mud after use, does not generate secondary pollution, and has good application prospect in environmental remediation.
As a preferred embodiment of the present invention, the carbon-containing organic solution is a solution including any one or more of urea, melamine, glucose, chitosan, starch, oxalic acid, and citric acid.
Preferably, the mass ratio of the effective components in the carbon-containing organic solution to the red mud after acid treatment is as follows: red mud after acid treatment: the effective component in the carbon-containing organic solution is 1 (0.3 to 3), and more preferably 1 (0.5 to 1.8).
In a preferred embodiment of the invention, the calcination is carried out under the protection of inert gas, and the calcination temperature is 400-900 ℃; preferably, the heating rate of calcination is 4-8 ℃/min. The inert gas may be nitrogen, argon, or the like.
As a preferred embodiment of the present invention, the cyclodextrin monomer used for cyclodextrin modification is any one of α -cyclodextrin, β -cyclodextrin, and γ -cyclodextrin, or a mixture of several thereof.
Preferably, the weight ratio of the cyclodextrin monomer to the red mud with magnetic separation performance is 1 (1-5).
In a preferred embodiment of the present invention, a cross-linking agent and/or an initiator is further added during the cyclodextrin modification.
Preferably, the crosslinking agent is any one of epichlorohydrin, tetrafluoroterephthalonitrile and citric acid or a mixture of the epichlorohydrin, the tetrafluoroterephthalonitrile and the citric acid. The initiator is one or a mixture of potassium dihydrogen phosphate, potassium carbonate, calcium carbonate and sodium chloride.
As a preferred embodiment of the present invention, the cyclodextrin modification comprises the steps of: and (2) putting the red mud with the magnetic separation performance, the cyclodextrin monomer and the cross-linking agent and/or the initiator into a polar solvent for mixing, and performing a concurrent thermal cross-linking reaction to obtain the magnetically separable modified red mud adsorbent.
Further preferably, in the modification treatment, the reaction temperature of the co-thermal crosslinking reaction is controlled to be 30-140 ℃, and the reaction time is 12-60 hours.
In a preferred embodiment of the present invention, the polar solvent is any one or a mixture of water, tetrahydrofuran, N-dimethylformamide and dimethylsulfoxide. Preferably, the polar solvent is water or a mixed solvent of dimethyl sulfoxide or tetrahydrofuran and N, N-dimethylformamide.
The invention also provides application of the magnetically separable modified red mud adsorbent, preferably application in water purification or gas purification treatment, and further preferably application in sewage purification treatment.
Preferably, the wastewater is wastewater containing organic pollutants including dye molecules, antibiotics, fluorine-containing compounds, and endocrine disruptors. The invention respectively uses the sewage containing methylene blue dye, tetracycline hydrochloride, bisphenol A, rhodamine b and the like to carry out tests, and obtains good sewage treatment effect.
Further preferably, during sewage purification treatment, the dosage of the adsorbent is 0.2-5 g/L, namely 0.2-5 g of the adsorbent prepared by the invention is added to each liter of sewage.
As a preferred embodiment of the present invention, the sewage purification treatment comprises the steps of:
putting the adsorbent into sewage to be purified;
stirring for reaction to make the adsorbent fully enrich the organic pollutants in the sewage;
when the content of the organic pollutants in the sewage is stable, for example, the content of the organic pollutants is kept stable and does not decrease, or the content of the organic pollutants is decreased to reach the standard level, the adsorbent enriched with the organic pollutants is subjected to magnetic separation and recovery through an external magnetic field, and then the purified water is obtained.
Further preferably, the sewage purification treatment further comprises the following steps:
and (3) regenerating and utilizing the adsorbent recovered by magnetic separation, wherein the regeneration method comprises the steps of carrying out centrifugal washing on the adsorbent by adopting a regeneration solvent, and drying to obtain the regenerated adsorbent capable of being recycled.
Wherein the regeneration solvent is any one of methanol, ethanol, tetrahydrofuran, sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
And during drying, the drying temperature is controlled to be 30-100 ℃, and the regenerated adsorbent obtained after drying can be reused for sewage purification treatment and recycling.
According to the invention, the red mud is subjected to component analysis, and is treated by utilizing the composition characteristics and the granularity characteristics of the red mud, so that the adsorbing material with the magnetic separation performance is obtained, and a new idea for developing and utilizing the red mud is provided.
During research, it was found that the original red mud and the conventional acid-treated red mud, although having a fine particle size and a large specific surface area, have a very limited ability to adsorb and remove pollutants from water and are difficult to separate from water effectively. Through the treatment of the invention, the magnetic property of the red mud is regulated and controlled, and the red mud with magnetic separation performance is obtained; and then, a cyclodextrin polymer is polymerized on the surface of the red mud with the magnetic separation performance to form a rich cavity structure, so that an ideal site is provided for efficient adsorption of pollutant molecules, an ideal interface is provided for aggregation and adsorption of pollutants on the surface of the red mud adsorbent, and the red mud-based adsorbing material with efficient adsorption property is obtained. Because the adsorbent material has magnetic separation performance, after sewage treatment is finished, solid-liquid separation can be conveniently realized from water under the assistance of a magnetic field, and the use is very convenient. In addition, the adsorbent material can be regenerated and recycled, and no waste is generated.
The performance of removing pollutants in water by adsorbing the red mud solid waste is improved through surface modification, the iron-containing composition of the red mud solid waste is regulated and controlled to realize magnetic separation performance, and the obtained multifunctional adsorbing material with both adsorption performance and magnetic property is expected to be developed into an efficient water purifying material for removing toxic and harmful pollutants in water. The method not only has profound significance for resource utilization of the red mud, but also provides a low-cost material for sewage treatment.
The method for preparing the adsorbent is simple and easy to control, the applicability is strong, the obtained adsorbent can quickly capture organic pollutants in water, separation and regeneration are realized after magnetic separation and simple soaking and cleaning, and an effective way is provided for resource utilization of red mud solid waste.
According to the preparation method of the cyclodextrin modified red mud adsorbent with the magnetic separation performance, waste red mud industrial waste is selected as a raw material, the magnetic performance of the red mud material is regulated and controlled through a simple acid treatment and high-temperature atmosphere calcination mode, on the basis of endowing a new magnetic separation function to red mud powder, a cyclodextrin polymer with a cavity structure is loaded on the surface of the red mud powder, a more ideal reaction interface is provided for interface adsorption, and a new method is provided for safe and green removal of pollutants in water while resource utilization of the red mud is realized. The preparation method of the adsorbent provided by the invention is simple to operate, rich in material source, low in production cost and good in method universality.
Drawings
FIG. 1 is a TEM image of a cyclodextrin-modified red mud adsorbent having magnetic separation properties prepared in example 1 of the present invention;
FIG. 2 is a graph showing the effect of removing bisphenol A in water obtained in effect test example 1 of the present invention;
FIG. 3 is a graph showing the effect of removing rhodamine b from water obtained in effect test example 2 of the present invention;
FIG. 4 is a graph showing the effect of removing methylene blue from water obtained in effect test example 2 of the present invention;
FIG. 5 is a graph showing the effect of the present invention on the adsorption performance of rhodamine b in water;
fig. 6 is an XRD pattern of the red mud raw material used in the examples of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer and clearer, embodiments and experimental examples of the present invention will be described below to further explain the present invention in detail. It should be noted that the following described embodiments are only some typical examples of the present invention, and not all embodiments of the present invention. Those skilled in the art should appreciate that they can make various changes, substitutions and alterations herein without departing from the scope of the invention as defined by the appended claims.
The reagents and instruments used in the following examples are commercially available and are all commercially available.
The XRD analysis composition of the red mud used in the following examples is shown in fig. 6, and it can be used without grinding.
Example 1
The embodiment provides a cyclodextrin modified red mud adsorbent with magnetic separation performance, and the preparation process comprises the following steps:
taking the red mud as a reaction raw material, carrying out acid treatment on the reaction raw material red mud, adding the red mud into a 1M hydrochloric acid solution, wherein the solid-to-liquid ratio of the red mud to the hydrochloric acid is 1:10g/mL, stirring and reacting at room temperature for 12 hours, and fully removing alkali metals and alkaline earth metals in the red mud;
then carrying out solid-liquid separation, and fully washing the red mud subjected to acid treatment;
dispersing the washed red mud in deionized water to obtain a suspension, adding urea into the suspension, wherein the mass ratio of the red mud to the urea is 1:1, and stirring and uniformly mixing the red mud and the urea at room temperature; then, separating the red mud with the urea impregnated on the surface by solid-liquid separation, and then drying;
heating the red mud with urea loaded on the surface to 550 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, and calcining at high temperature for 4 hours to generate red mud particles with magnetic separation performance;
alpha-cyclodextrin monomer (1025mg), tetrafluoroterephthalonitrile (500mg), potassium carbonate (1600mg) and red mud particles (2050mg) with magnetic separation performance are mixed and dispersed in a mixed solvent of tetrahydrofuran and N, N-dimethylformamide (the volume ratio of tetrahydrofuran to N, N-dimethylformamide is 9: 1), the mass ratio of the alpha-cyclodextrin monomer to the red mud particles is 1:2, the mixture is stirred for 48 hours at the reaction temperature of 65 ℃, and the cyclodextrin modified red mud adsorbent with magnetic separation performance is formed through the co-thermal crosslinking.
A TEM image of the cyclodextrin modified red mud absorbent with magnetic separation performance prepared in this example is shown in fig. 1.
The alpha-cyclodextrin monomer is respectively replaced by the beta-cyclodextrin monomer and the gamma-cyclodextrin monomer, so that the cyclodextrin modified red mud adsorbent with the magnetic separation performance can be respectively prepared.
Example 2
In this example, compared with example 1, the cyclodextrin-modified red mud adsorbent with magnetic separation performance was prepared by replacing urea with glucose and replacing α -cyclodextrin monomer with β -cyclodextrin monomer.
Example 3
In the embodiment, compared with embodiment 1, the urea is replaced by oxalic acid; replacing an alpha-cyclodextrin monomer with a beta-cyclodextrin monomer; the cross-linking agent is the mixture of epichlorohydrin and tetrafluoroterephthalonitrile.
The preparation process comprises the following steps: beta-cyclodextrin monomer (1025mg), tetrafluoroterephthalonitrile (500mg), epichlorohydrin (7.5ml), potassium carbonate (1600mg) and red mud particles (2050mg) with magnetic separation performance are mixed and dispersed in a mixed solvent of tetrahydrofuran and N, N-dimethylformamide (the volume ratio of tetrahydrofuran to N, N-dimethylformamide is 9: 1), the mass ratio of the beta-cyclodextrin monomer to the red mud particles is 1:2, the mixture is stirred for 48 hours at a reaction temperature of 65 ℃, and the cyclodextrin modified red mud adsorbent with magnetic separation performance is formed through the co-thermal crosslinking.
Example 4
Compared with example 1, the alpha-cyclodextrin monomer is replaced by the beta-cyclodextrin monomer; citric acid is used as a crosslinking agent, and potassium dihydrogen phosphate is used as an initiator; the solvent is water.
The preparation process comprises the following steps: beta-cyclodextrin monomer (1025mg), citric acid (1000mg), potassium dihydrogen phosphate (550mg) and red mud particles (2050mg) with magnetic separation performance are mixed and dispersed in water, the mass ratio of the beta-cyclodextrin monomer to the red mud particles is 1:2, the mixture is stirred in a reaction kettle at 135 ℃ for 12 hours, and the cyclodextrin modified red mud adsorbent with magnetic separation performance is formed by means of co-thermal crosslinking.
Example 5
Compared with example 1, the alpha-cyclodextrin monomer is replaced by the beta-cyclodextrin monomer; the co-thermal crosslinking reaction is carried out in dimethyl sulfoxide as a solvent.
The preparation process comprises the following steps: beta-cyclodextrin monomer (1025mg), tetrafluoroterephthalonitrile (528mg), potassium carbonate (1218mg) and red mud particles (2050mg) with magnetic separation performance are mixed and dispersed in dimethyl sulfoxide, the mass ratio of the beta-cyclodextrin monomer to the red mud particles is 1:2, the mixture is stirred for 18 hours at the reaction temperature of 80 ℃, and the cyclodextrin modified red mud adsorbent with magnetic separation performance is formed by thermal crosslinking.
Example 6
Compared with example 1, the alpha-cyclodextrin monomer is replaced by the beta-cyclodextrin monomer; the concurrent thermal crosslinking reaction is carried out in dimethyl sulfoxide as a solvent; the thermal crosslinking reaction is carried out without adding an initiator; the cross-linking agent adopts epichlorohydrin.
The preparation process comprises the following steps: beta-cyclodextrin monomer (1025mg), epichlorohydrin (7.5ml) and red mud particles (2050mg) with magnetic separation performance are mixed and dispersed in dimethyl sulfoxide, the mass ratio of the beta-cyclodextrin monomer to the red mud particles is 1:2, the mixture is stirred for 18 hours at the reaction temperature of 80 ℃, and the cyclodextrin modified red mud adsorbent with magnetic separation performance is formed by means of co-thermal crosslinking.
Effect test example 1
The water purification treatment test was carried out by using the cyclodextrin modified red mud adsorbent with magnetic separation performance prepared in example 1 of the present invention. The procedure of the test is as follows.
Taking the red mud raw material, the red mud subjected to acid treatment and then sufficiently washed and the prepared cyclodextrin modified red mud adsorbent with the magnetic separation performance in the example 1, and drying the red mud raw material and the red mud subjected to acid treatment and then sufficiently washed and preparing the red mud into powder for later use.
Preparing a bisphenol A aqueous solution, wherein the concentration of the bisphenol A is 25 mg/L. Each beaker contained 1L of an aqueous bisphenol A solution.
Respectively adding red mud raw material powder, the red mud powder which is subjected to acid treatment and then fully washed and the prepared cyclodextrin modified red mud adsorbent with magnetic separation performance into the three beakers, and then stirring for one hour at room temperature and under the dark condition. The adding amount of the red mud raw material powder, the red mud powder which is subjected to acid treatment and then fully washed and the prepared cyclodextrin modified red mud adsorbent with the magnetic separation performance are all 0.5 g/L.
After a period of time, taking a certain volume of reaction solution for detection, filtering the reaction solution taken out by using a microfiltration membrane with the pore diameter of 0.45 micrometer to obtain a test sample solution, measuring the concentration of the residual bisphenol A in the solution by using liquid chromatography, and calculating the removal rate of pollutants. The performance effect of removing bisphenol A in water is shown in FIG. 2.
The original red mud basically has no adsorption performance, but the acid-soluble part composition in the red mud can be removed in the acidification process, so that the pore structure of the red mud is increased, and the red mud is endowed with magnetism after the co-thermal reaction of carbon-containing organic matters so as to be convenient for later separation, so that as can be seen from figure 2, the acidified magnetic red mud already has adsorption performance, then cyclodextrin polymer is introduced, and in the polymerization reaction process, cyclodextrin is grown in situ on the pore structure and the surface of the red mud, and due to the unique cavity structure of the cyclodextrin, the cyclodextrin magnetic red mud adsorbent has better adsorption performance on bisphenol A, and as can be seen from figure 2, the finally synthesized cyclodextrin magnetic red mud adsorbent has better adsorption performance compared with the previous sample.
After the water purification treatment is finished, separating the red mud adsorbent powder from water by using a magnet, collecting, performing centrifugal washing by using a methanol solvent, performing 3 centrifugal processes, and then performing drying treatment to obtain the regenerated red mud adsorbent. The red mud raw material powder and the red mud powder which is fully washed after acid treatment are difficult to separate from water under the action of an external magnetic field, and the difficulty is high due to the adoption of filtration separation.
Effect test example 2
Referring to effect test example 1, a rhodamine b solution was tested.
And (3) preparing a rhodamine b aqueous solution, wherein the concentration of the rhodamine b is 25mg/L, and 1L of the rhodamine b aqueous solution is contained in each beaker.
Similarly, the red mud raw material powder in effect test example 1, the red mud powder subjected to acid treatment and then sufficiently washed with water, and the cyclodextrin-modified red mud adsorbent having magnetic separation performance prepared in example 1 were all added in an amount of 0.5 g/L.
The performance effect graph of the obtained rhodamine b removal water is shown in figure 3.
As can be seen from fig. 3, the acidified magnetic red mud has already had adsorption performance, but the adsorption effect is not significantly improved due to factors such as the molecular structure of rhodamine b, and a cyclodextrin polymer is introduced later, and cyclodextrin is allowed to grow in situ on the pore structure and the surface of red mud during the course of polymerization reaction, and due to the unique cavity structure of cyclodextrin, cyclodextrin has better adsorption performance for rhodamine b, and as can be seen from fig. 3, the finally synthesized cyclodextrin magnetic red mud adsorbent has better adsorption performance compared with the previous sample.
After the water purification treatment is finished, separating the red mud adsorbent powder from water by using a magnet, collecting, performing centrifugal washing by using a methanol solvent, performing 3 centrifugal processes, and then performing drying treatment to obtain the regenerated red mud adsorbent. In the drying, the drying temperature was controlled to 80 ℃.
Similarly, the methylene blue dye aqueous solution and the tetracycline hydrochloride aqueous solution are also purified, so that a good removal effect is obtained. The performance effect of removing methylene blue dye from water is shown in figure 4. As can be seen from FIG. 4, the synthesized cyclodextrin magnetic red mud adsorbent has good adsorption performance.
Effect test example 3
A water purification treatment test was performed using the regenerated red mud adsorbent obtained in effect test example 2.
And (3) preparing a rhodamine b aqueous solution, wherein the concentration of the rhodamine b is 50mg/L, and 1L of the rhodamine b aqueous solution is contained in each beaker.
The regenerated red mud adsorbent obtained in the effect test example 2 was used for purifying rhodamine b aqueous solution, and the addition amount was 0.5 g/L.
The effect graph of the regenerated adsorption performance for removing rhodamine b from water obtained by repeatedly washing and drying the regenerated red mud adsorbent obtained in the effect test example 2 for 5 times is shown in fig. 5.
As can be seen from figure 5, after 5 times of repeated washing, drying and recycling, the adsorption effect of the cyclodextrin magnetic red mud adsorbent is kept at a higher level, and the adsorption capacity of each time is not greatly different, which proves that the material has stable regeneration adsorption performance.
The above description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention as described in the specification and other related fields can be directly or indirectly applied thereto.
Claims (10)
1. A magnetically separable modified red mud adsorbent is characterized in that red mud generated in alumina production is used as a raw material of the adsorbent, the red mud is subjected to acid treatment, then the red mud subjected to acid treatment is impregnated with a carbon-containing organic solution, and then the red mud is dried and calcined to obtain the red mud with magnetic separation performance; and performing cyclodextrin modification on the red mud with the magnetic separation performance to obtain the magnetically separable modified red mud adsorbent.
2. The adsorbent according to claim 1, wherein the carbon-containing organic solution is a solution containing any one or more of urea, melamine, glucose, chitosan, starch, oxalic acid and citric acid, and preferably the mass ratio of the effective components in the carbon-containing organic solution to the red mud after acid treatment is as follows: red mud after acid treatment: the effective component in the carbon-containing organic solution is 1 (0.3 to 3), and more preferably 1 (0.5 to 1.8).
3. The adsorbent according to claim 1 or 2, wherein the calcination is carried out under the protection of inert gas, and the calcination temperature is 400-900 ℃; preferably, the heating rate of calcination is 4-8 ℃/min.
4. The adsorbent according to any one of claims 1 to 3, wherein a cyclodextrin monomer used for cyclodextrin modification is any one of or a mixture of a plurality of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin; preferably, the weight ratio of the cyclodextrin monomer to the red mud with magnetic separation performance is 1 (1-5).
5. The adsorbent according to claim 4, wherein a cross-linking agent and/or an initiator is further added when the cyclodextrin is modified; the cross-linking agent is any one or a mixture of epoxy chloropropane, tetrafluoroterephthalonitrile and citric acid; the initiator is one or a mixture of potassium dihydrogen phosphate, potassium carbonate, calcium carbonate and sodium chloride.
6. The sorbent according to claim 5, wherein the cyclodextrin modification comprises the steps of: putting the red mud with the magnetic separation performance, the cyclodextrin monomer and the cross-linking agent and/or the initiator into a polar solvent for mixing, and carrying out a concurrent thermal cross-linking reaction to prepare a magnetically separable modified red mud adsorbent; the reaction temperature is controlled to be 30-140 ℃, and the reaction time is 12-60 hours.
7. The adsorbent according to claim 6, wherein the polar solvent is any one or a mixture of water, tetrahydrofuran, N-dimethylformamide and dimethyl sulfoxide.
8. Use of the magnetically separable modified red mud sorbent of any one of claims 1 to 7 in a water or gas purification process, preferably a wastewater purification process.
9. The use according to claim 8, wherein the contaminated water is contaminated water containing organic contaminants including dye molecules, antibiotics, fluorine-containing compounds, endocrine disruptors.
10. Use according to claim 8 or 9, characterized in that said sewage purification treatment comprises the steps of:
placing the adsorbent into the sewage to be purified;
stirring for reaction, and enriching the organic pollutants in the sewage by the adsorbent;
after the content of the organic pollutants in the sewage is stable, carrying out magnetic separation and recovery on the adsorbent enriched with the organic pollutants through an external magnetic field to obtain purified water;
preferably, the sewage purification treatment further comprises the steps of:
the method comprises the steps of carrying out regeneration and utilization on an adsorbent recovered through magnetic separation, wherein the regeneration method comprises the steps of carrying out centrifugal washing on the adsorbent by using a regeneration solvent, and drying to obtain a recyclable regeneration adsorbent;
the regeneration solvent is any one of methanol, ethanol, tetrahydrofuran, a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution;
the drying temperature is controlled to be 30-100 ℃.
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