CN110721655A - Preparation method of heavy metal adsorbent based on red mud - Google Patents

Preparation method of heavy metal adsorbent based on red mud Download PDF

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CN110721655A
CN110721655A CN201910785023.0A CN201910785023A CN110721655A CN 110721655 A CN110721655 A CN 110721655A CN 201910785023 A CN201910785023 A CN 201910785023A CN 110721655 A CN110721655 A CN 110721655A
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red mud
heavy metal
hydrochloric acid
metal adsorbent
sieving
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孙志昂
郭焱
王倩
张越
何小山
席艺慧
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HENAN CHANGXING INDUSTRY Co Ltd
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HENAN CHANGXING INDUSTRY Co Ltd
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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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • 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
    • B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • 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

Abstract

A preparation method of a heavy metal adsorbent based on red mud comprises the following steps: pretreating, namely drying the red mud to ensure that the moisture content of the dried red mud is below 5 percent, crushing the dried red mud, and then grinding; acid treatment, namely placing the pretreated red mud in a closed container, adding hydrochloric acid with the concentration of 2-12 mol/L into the closed container, performing acid treatment at the temperature of 2-105 ℃ for more than or equal to 5min, and performing solid-liquid separation; modifying, preparing from CTAB and FeCl3Mixing with urea to obtain improved solution, adding the improved solution and red mud hydrochloric acid leaching residue into high temperature and high pressure reactor, stirring, reacting for a certain time, filtering and cleaning the modified red mudDrying, grinding and sieving to modify the red mud to generate the heavy metal ion adsorbent. The adsorbent can be used for adsorbing various heavy metal ions, has the advantages of large adsorption capacity, high settling speed, short adsorption time and the like, and can be used for restoring and protecting ecological environment.

Description

Preparation method of heavy metal adsorbent based on red mud
Technical Field
The invention relates to the field of inorganic materials, in particular to a preparation method of a heavy metal adsorbent based on red mud.
Background
The red mud is a polluting waste discharged from the industrial production of alumina, and the mineral composition of the red mud is very complex and does not conform to the mineral composition of natural soil. Generally, 1.0-2.0 tons of red mud is discharged when 1 ton of alumina is produced. Because a large amount of red mud can not be effectively and comprehensively utilized, a direct stacking method is adopted by many aluminum production enterprises, and the red mud is stacked by a large-area yard, so that a large amount of land is occupied, and the ecological environment is seriously polluted. The generation of a large amount of red mud has direct and indirect influence on human life in many aspects. Therefore, the discharge of the red mud is reduced, the harm of the red mud is reduced to the maximum extent, and the resource, harm-reducing treatment and utilization of a large amount of red mud are realized in many aspects.
Heavy metal pollution refers to environmental pollution caused by heavy metals or compounds thereof, heavy metals can interact strongly with proteins and various enzymes in human bodies to cause them to lose activity, and can also be enriched in certain organs of human bodies, if the heavy metals exceed the tolerance limit of the human bodies, acute poisoning, subacute poisoning, chronic poisoning and the like of the human bodies can be caused, and great harm can be caused to the human bodies.
Most of the current methods for treating heavy metal pollution are chemical precipitation, biochemical treatment, ion exchange and adsorption. The adsorption method is a method for adsorbing pollutants in water by using porous solid substances, the specific surface area of red mud is increased by 5-15 times after acid modification, then the temperature and pressure are controlled, and the red mud is specially modified to have a good effect on adsorption of heavy metals in wastewater, and particularly has good adsorption performance on high-concentration heavy metals.
The red mud is strong alkaline, so the comprehensive utilization of the red mud is a worldwide problem. The red mud is also quite complex in components, mainly consists of oxides and salts of calcium, iron, aluminum, silicon, titanium and the like, and also contains other rare earth metal oxides and the like, and the utilization value of the red mud is very high, so that the red mud is the basis for recycling.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the preparation method of the heavy metal adsorbent based on the red mud, which utilizes the red mud as the adsorbent to solve the problem of heavy metal pollution, can achieve the aim of treating waste by waste, effectively utilizes the red mud, reduces the pollution of the heavy metal to the ecological environment, and can create a certain value for enterprises.
In order to solve the technical problems, the invention adopts the following scheme:
a preparation method of a heavy metal adsorbent based on red mud comprises the following steps:
(1) pretreating, namely drying the red mud to ensure that the moisture content of the dried red mud is below 5 percent, crushing the dried red mud, grinding, and finally sieving by a sieve of 80 meshes;
(2) acid treatment, namely placing the pretreated red mud in a closed container, adding hydrochloric acid with the concentration of 2-12 mol/L into the closed container, performing acid treatment at the temperature of 2-105 ℃ for more than or equal to 5min, performing solid-liquid separation, and collecting red mud filter residues; washing the red mud filter residue with water, and drying, crushing and sieving the washed red mud filter residue;
(3) modifying, preparing from CTAB and FeCl3And (2) mixing the improved solution with urea to prepare an improved solution, putting the improved solution and red mud hydrochloric acid leaching residues into a high-temperature high-pressure reactor, uniformly stirring, reacting for a certain time, and filtering, cleaning, drying, grinding and sieving the modified red mud to obtain the heavy metal adsorbent.
Preferably, the sieve in step (2) is a 40 mesh and above sieve.
Preferably, the volume ratio of the red mud to the concentrated hydrochloric acid in the step (2) is 1: 10 to 1: 2.
The invention has the beneficial effects that: the invention takes red mud as a substrate, uses acid for pretreatment, uses Cetyl Trimethyl Ammonium Bromide (CTAB), urea, ferric trichloride and the like as modifiers, and modifies the red mud by controlling temperature and pressure to generate the heavy metal ion adsorbent. The adsorbent can be used for adsorbing various heavy metal ions, has the advantages of large adsorption capacity, high settling speed, short adsorption time and the like, and can be used for restoring and protecting ecological environment.
The red mud has the characteristics of high strong basicity and iron mineral content, good particle dispersibility, large specific surface area, good settling property, easy coating, good stability in solution and the like, and has wide application prospect in the field of environmental remediation. The red mud is used for treating the pollution problem of the heavy metals, the aim of treating waste by waste can be achieved, the red mud is effectively utilized, the pollution of the red mud is reduced, meanwhile, the pollution of the heavy metals to the ecological environment is reduced, and the red mud can create certain value for enterprises.
Drawings
In fig. 1, the left, middle and right are scanning electron micrographs of original bayer process red mud magnified 5000 times, 20000 times and 50000 times respectively.
In fig. 2, the left, middle and right are scanning electron micrographs of bayer process red mud hydrochloric acid leaching residue which are respectively magnified 5000 times, 20000 times and 50000 times.
In fig. 3, the left, middle and right are scanning electron micrographs of the bayer process red mud hydrochloric acid leaching residue comprehensive modified sample magnified 5000 times, 20000 times and 50000 times respectively.
In fig. 4, the left, middle and right are scanning electron micrographs of 5000 times, 20000 times and 50000 times of amplification of heavy metal solution test samples absorbed by the combined modified bayer process red mud hydrochloric acid leaching residues respectively.
FIG. 5 is an X-ray diffraction pattern of red mud and its modified material.
FIG. 6 is the X-ray fluorescence spectrum of red mud from original Bayer process.
FIG. 7 is a Bayer process red mud hydrochloric acid leaching residue X-ray fluorescence spectrogram.
FIG. 8 is a suction and desorption curve of Bayer process red mud acid leaching residue.
Detailed Description
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Example 1
A preparation method of a heavy metal adsorbent based on red mud comprises the following steps:
(1) pretreating, namely drying the red mud to ensure that the moisture content of the dried red mud is below 5 percent, crushing the dried red mud, grinding, and finally sieving by a sieve of 80 meshes;
(2) acid treatment, namely placing the pretreated red mud in a closed container, adding hydrochloric acid with the concentration of 2-12 mol/L into the closed container, performing acid treatment at the temperature of 2-105 ℃ for more than or equal to 5min, performing solid-liquid separation, and collecting red mud filter residues; washing the red mud filter residue with water, and drying, crushing and sieving the washed red mud filter residue;
(3) modifying, preparing from CTAB and FeCl3And (2) mixing the improved solution with urea to prepare an improved solution, putting the improved solution and red mud hydrochloric acid leaching residues into a high-temperature high-pressure reactor, uniformly stirring, reacting for a certain time, and filtering, cleaning, drying, grinding and sieving the modified red mud to obtain the heavy metal adsorbent.
The sieve in the step (2) is a 40-mesh sieve or more.
In the step (2), the volume ratio of the red mud to the concentrated hydrochloric acid is 1: 10 to 1: 2.
Example 2
(1) Taking 1g FeCl3Adding the solid, 1g of CTAB solid and 2g of urea solid particles into a 1L volumetric flask, adding distilled water to a constant volume of 1L, shaking up until the solid is dissolved to obtain a modified solution;
(2) weighing 10g of red mud acid leaching residue, adding the red mud acid leaching residue into 1L of the modified solution in the volume 1, putting the mixture into a pressure container, heating the mixture to 107-111 ℃, preserving heat for 1h, cooling the mixture along with the container, filtering the solution, drying filter residue at 105 ℃ for 12h, grinding and sieving the filter residue, and storing the filter residue in a sealed manner to prevent the filter residue from being affected with damp;
(3) 0.02g and 0.04g of the modified red mud of (2) are added with 10mL of CuSO of 1g/L4Solution, Pb (NO)3)2Solution and CdCl2And (3) vibrating the solution on a shaking table for 3 hours at room temperature, taking out the solution, performing solid-liquid separation, and keeping the liquid.
Example 3
(1) Taking 1g FeCl3Adding the solid, 1g of CTAB solid and 1g of urea solid particles into a 1L volumetric flask, adding distilled water to a constant volume of 1L, shaking up until the solid is dissolved to obtain a modified solution;
(2) weighing 10g of red mud acid leaching residue, adding the red mud acid leaching residue into 1L of the modified solution in the volume 1, putting the mixture into a pressure container, heating the mixture to 107-111 ℃, preserving heat for 1h, cooling the mixture along with the container, filtering the solution, drying filter residue at 105 ℃ for 12h, grinding and sieving the filter residue, and storing the filter residue in a sealed manner to prevent the filter residue from being affected with damp;
(3) 0.02g and 0.04g of the modified red mud of (2) are added with 10mL of CuSO of 1g/L4Solution, Pb (NO)3)2Solution and CdCl2And (3) vibrating the solution on a shaking table for 3 hours at room temperature, taking out the solution, performing solid-liquid separation, and keeping the liquid.
Example 4
(1) 2g of FeCl is taken3Adding the solid, 1g of CTAB solid and 4g of urea solid particles into a 1L volumetric flask, adding distilled water to a constant volume of 1L, shaking up until the solid is dissolved to obtain a modified solution;
(2) weighing 10g of red mud acid leaching residue, adding the red mud acid leaching residue into 1L of the modified solution in the volume 1, putting the mixture into a pressure container, heating the mixture to 107-111 ℃, preserving heat for 1h, cooling the mixture along with the container, filtering the solution, drying filter residue at 105 ℃ for 12h, grinding and sieving the filter residue, and storing the filter residue in a sealed manner to prevent the filter residue from being affected with damp;
(3) 0.02g and 0.04g of the modified red mud of (2) are added with 10mL of CuSO of 1g/L4Solution, Pb (NO)3)2Solution and CdCl2And (3) vibrating the solution on a shaking table for 3 hours at room temperature, taking out the solution, performing solid-liquid separation, and keeping the liquid.
Example 5
(1) 2g of FeCl is taken3Solids, 1g CTAB solids and 2g urea solids were added in 1L volumeAdding distilled water into a bottle to a constant volume of 1L, shaking up until the solid is dissolved to obtain a modified solution;
(2) weighing 10g of red mud acid leaching residue, adding the red mud acid leaching residue into 1L of the modified solution in the volume 1, putting the mixture into a pressure container, heating the mixture to 107-111 ℃, preserving heat for 1h, cooling the mixture along with the container, filtering the solution, drying filter residue at 105 ℃ for 12h, grinding and sieving the filter residue, and storing the filter residue in a sealed manner to prevent the filter residue from being affected with damp;
(3) 0.02g and 0.04g of the modified red mud of (2) are added with 10mL of CuSO of 1g/L4Solution, Pb (NO)3)2Solution and CdCl2And (3) vibrating the solution on a shaking table for 3 hours at room temperature, taking out the solution, performing solid-liquid separation, and keeping the liquid.
Results and analysis
(1) Analysis by scanning Electron microscope
Scanning electron microscope tests were carried out on the samples for testing the adsorption of heavy metal solution by the original bayer red mud, bayer red mud hydrochloric acid leaching residue comprehensive modification samples and combined modified bayer red mud hydrochloric acid leaching residue in example 1, and the results were analyzed as follows;
as shown in figure 1, the red mud component in the prior Bayer process is very loose, the surface fine particles wrap crystals, so that the porosity of the red mud component is greatly reduced, the crystalline glass structure presented on the phase can be found only when the crystalline glass structure is 50000 times, and the surface of the red mud component is still covered by impurity particle layers, so that the specific surface area of the red mud component is very small.
As can be seen from fig. 2, the bayer process red mud after hydrochloric acid leaching has obviously reduced surface impurities, uniform components, prominent crystal structure, and increased porosity, so that the mutual adhesion and water absorption characteristics of the bayer process red mud are greatly reduced, and the specific surface area is increased.
As can be seen from fig. 3, under the treatment of high temperature and high pressure and the comprehensive modification agent, the surfaces of the bayer process red mud hydrochloric acid leaching residues become very loose, and compared with the bayer process red mud hydrochloric acid leaching residues which are not comprehensively modified, the porosity is reduced, the mutual adhesive force is increased, and the adhesive structure is obvious.
As can be seen from fig. 4, after the heavy metals are adsorbed and fixed, the surface structure of the red mud becomes very loose, the connection between the red mud particles becomes tighter by adsorbing the heavy metals, and the adsorption effect is obvious.
(2) X-ray diffraction pattern analysis
FIG. 5 shows that from the X-ray diffraction pattern, the red mud of the original Bayer process is relatively complex in composition and is a mixture of various substances, and the main component is silicon dioxide (SiO)2) Iron oxide (Fe)2O3) Perovskite (CaTiO)3) Dicalcium silicate (Ca)2SiO4) And calcite (CaCO)3) (ii) a After hydrochloric acid pickling, Ca contained in red mud2+、Fe3+、Al3+、Ti4+And other rare earth elements are leached, so that the red mud after acid leaching mainly comprises silicon dioxide and a small amount of aluminum oxide; the modified red mud-like components are basically unchanged.
(3) X-ray fluorescence spectrogram analysis
FIG. 6 is an X-ray fluorescence spectrum of Bayer process red mud, which shows that Bayer process red mud contains a large amount of calcium oxide (CaO) and ferric oxide (Fe)2O3) Silicon dioxide (SiO)2) Titanium dioxide (TiO)2) Alumina (Al)2O3) And small amounts of zirconium, scandium, rare earth elements, and the like. FIG. 7 is a red mud hydrochloric acid leaching residue X-ray fluorescence spectrogram of Bayer process, in which the main component is silicon dioxide (SiO)2) Alumina (Al)2O3) And titanium dioxide (TiO)2) A large amount of calcium, aluminum, iron and zirconium, scandium, rare earth elements, etc. are leached.
FIG. 8 illustrates: according to the absorption and desorption curve of the Bayer process red mud acid leaching residue, the specific surface area is 444.3m2/g, the pore volume is 391.85 m2/g, and the specific surface area is enlarged by nearly 20 times compared with the original Bayer process red mud, so that the adsorption capacity of the red mud acid leaching residue on heavy metal ions is greatly improved.
(4) Adsorption analysis of heavy metal ions
Adding CuSO into modified red mud4Solution, Pb (NO)3)2Solution and CdCl2Oscillating in the solution for more than 3h, and adding the solutionAnd (4) performing solid-liquid separation, and measuring the concentration of the residual heavy metal ions in the liquid to obtain the adsorption rate of the modified red mud.
When the modified red mud obtained in example 2 was added in an amount of 0.02g, Cu in the liquid was measured2+The concentration is 245.44mg/L, Pb2+The concentration is 194.0mg/L, Cd2+The concentration was 177 mg/L. Cu in the liquid measured at an amount of 0.04g2+The concentration is 239.88mg/L, Pb2+The concentration is 56.40mg/L, Cd2+The concentration was 34 mg/L.
When the modified red mud obtained in example 3 was added in an amount of 0.02g, Cu in the liquid was measured2+The concentration is 252.87mg/L, Pb2+The concentration is 121mg/L, Cd2+The concentration was 187.0 mg/L. Cu in the liquid measured at an amount of 0.04g2+The concentration is 251.54mg/L, Pb2+The concentration is 74.1mg/L, Cd2+The concentration was 92.9 mg/L.
When the modified red mud obtained in example 4 was added in an amount of 0.02g, Cu in the liquid was measured2+The concentration is 252.81mg/L, Pb2+The concentration is 182.0mg/L, Cd2+The concentration was 173 mg/L. Cu in the liquid measured at an amount of 0.04g2+The concentration is 239.64mg/L, Pb2+The concentration is 52.0mg/L, Cd2+The concentration was 28 mg/L.
When the modified red mud obtained in example 5 was added in an amount of 0.02g, Cu in the liquid was measured2+The concentration is 248.64mg/L, Pb2+Concentration of 137.0mg/L, Cd2+The concentration was 193 mg/L. Cu in the liquid measured at an amount of 0.04g2+The concentration is 238.95mg/L, Pb2+The concentration is 76.70mg/L, Cd2+The concentration was 99.8 mg/L.
The specific surface area of the red mud is increased to 400 m by taking the red mud as a raw material and carrying out acid treatment2More than g, prepared by CTAB, urea and FeCl3Is a mixed modifier composed of raw materials, and is treated for 1h at high temperature and high pressure to obtain modified red mud, and the modified red mud is used for treating Cu in water2+The removal amount of the catalyst reaches 120-135 mg/g; for Pb2+The adsorption capacity of the catalyst is 85-120 mg/g, and the catalyst is used for Cd2+The removal amount of the red mud reaches more than 40 mg/g, and almost no secondary leaching exists, so that the heavy metal ions are inactivated and the modified red mudFirmly fixing and adsorbing to prepare the heavy metal adsorbent with excellent effect.
The above-mentioned embodiments do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention by those skilled in the art should be included in the protection scope defined by the claims of the present invention without departing from the design concept of the present invention.

Claims (3)

1. A preparation method of a heavy metal adsorbent based on red mud comprises the following steps:
(1) pretreating, namely drying the red mud to ensure that the moisture content of the dried red mud is below 5 percent, crushing the dried red mud, grinding, and finally sieving by a sieve of 80 meshes;
(2) acid treatment, namely placing the pretreated red mud in a closed container, adding hydrochloric acid with the concentration of 2-12 mol/L into the closed container, performing acid treatment at the temperature of 2-105 ℃ for more than or equal to 5min, performing solid-liquid separation, and collecting red mud filter residues; washing the red mud filter residue with water, and drying, crushing and sieving the washed red mud filter residue;
(3) modifying, preparing from CTAB and FeCl3And (2) mixing the improved solution with urea to prepare an improved solution, putting the improved solution and red mud hydrochloric acid leaching residues into a high-temperature high-pressure reactor, uniformly stirring, reacting for a certain time, and filtering, cleaning, drying, grinding and sieving the modified red mud to obtain the heavy metal adsorbent.
2. The method for preparing the red mud-based heavy metal adsorbent according to claim 1, wherein the screening in the step (2) is 40-mesh or more.
3. The method for preparing the red mud-based heavy metal adsorbent according to claim 1, wherein the volume ratio of the red mud to the concentrated hydrochloric acid in the step (2) is 1: 10 to 1: 2.
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CN113477639A (en) * 2021-06-25 2021-10-08 武钢集团昆明钢铁股份有限公司 Method for cleaning ferric trichloride stains
CN113522222A (en) * 2021-08-20 2021-10-22 中南大学 Preparation method of iron-modified red mud-based magnetic adsorbent and application of iron-modified red mud-based magnetic adsorbent in composite heavy metal wastewater

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