CN110627188A - Method for treating organic pollutants - Google Patents

Method for treating organic pollutants Download PDF

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Publication number
CN110627188A
CN110627188A CN201910895150.6A CN201910895150A CN110627188A CN 110627188 A CN110627188 A CN 110627188A CN 201910895150 A CN201910895150 A CN 201910895150A CN 110627188 A CN110627188 A CN 110627188A
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cumgal
mixed solution
concentration
ldo
persulfate
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闫方友
贾青竹
张鸿敏
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Tianjin University of Science and Technology
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Tianjin University of Science and Technology
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
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Abstract

The embodiment of the invention relates to a method for treating organic pollutants, which comprises the following steps: adding CuMgAl layered oxide and persulfate into an object to be treated; the CuMgAl layered oxide is prepared by the following method: will contain Cu2+Soluble copper salt of (2) containing Mg2+Soluble magnesium salt of (5) and containing Al3+Dissolving the soluble aluminum salt in water to prepare a first mixed solution; mixing NaOH and Na2CO3Dissolving in water to prepare a second mixed solution; under the condition of stirring, simultaneously dripping the first mixed solution and the second mixed solution into water with a certain volume, keeping the pH value of a reaction system stable in the dripping process, and after finishing dripping, carrying out treatment on the obtained mixture to obtain CuMgAl layered hydroxide, wherein the value range of the pH value is 8-9; calcining the CuMgAl layered hydroxideAnd (6) burning treatment. The method can remove organic pollutants efficiently.

Description

Method for treating organic pollutants
Technical Field
The invention belongs to the technical field of environmental protection, relates to a method for treating organic pollutants, and particularly relates to a method for treating organic pollutants by activating persulfate through CuMgAl layered oxide (CuMgAl-LDO).
Background
The persulfate advanced oxidation technology is sulfate radical SO4 -Is an advanced oxidation technology for oxidizing macromolecular refractory organic matters into low-toxicity or non-toxic micromolecular substances for main active substances. In recent years, the technology is widely applied to the field of environmental pollution treatment, such as in-situ remediation of groundwater and the environment. The sulfate radical SO can be obtained by activating persulfate4 -。
At present, the methods for activating persulfate mainly comprise metal ion activation, natural mineral activation, thermal activation and the like. The metal ion activation is easy to generate secondary pollution, natural minerals are limited in practical application due to insufficient concentration of effective components, and energy and cost required by thermal activation are high. Therefore, the research on high-efficiency catalysts for activating persulfates is an important direction of the advanced oxidation technology of persulfates.
Hydrotalcite-like substances are inorganic materials with a layered structure, interlayer water molecules, hydroxyl ions and other anions are lost through high-temperature calcination, and layered oxides (LDO) with high specific surface area are obtained.
The persulfate advanced oxidation technology has a good effect of removing organic pollutants, such as medicines, insecticides, halogenated compounds, antibiotics, organic dyes and the like. Taking organic dyes as an example, such organic pollutants are widely used not only in textile, printing, tanning and coating industries, but also in food technology and agricultural research, most of the organic dyes are dissolved in water in an ionic form, and pose a serious threat to human health due to their toxicity and non-biodegradability, and groundwater is polluted by such pollutants. However, the lack of highly efficient catalysts for activating persulfates in the prior art has resulted in the failure of persulfate advanced oxidation technology to be widely used in the treatment of organic pollutants.
Disclosure of Invention
In order to solve the above technical problems, embodiments of the present invention provide a method for treating organic pollutants.
<1> a method for treating organic pollutants by using CuMgAl layered oxide to activate persulfate, comprising the steps of:
adding CuMgAl layered oxide and persulfate into an object to be treated;
the CuMgAl layered oxide is prepared by the following preparation method:
will contain Cu2+Soluble copper salt of (2) containing Mg2+Soluble magnesium salt of (5) and containing Al3+Dissolving the soluble aluminum salt in water to prepare a first mixed solution;
NaOH and Na2CO3Dissolving in water to prepare a second mixed solution;
under the condition of stirring, simultaneously dropwise adding the first mixed solution and the second mixed solution into a certain volume of water, keeping the pH value of the reaction system stable in the dropwise adding process, and after the dropwise adding is finished, processing the obtained mixture to obtain CuMgAl layered hydroxide, wherein the value range of the pH value is 8-9;
-subjecting said CuMgAl layered hydroxide to a calcination treatment.
<2> the method according to <1>, wherein the CuMgAl layered oxide is added in an amount of 0.05 to 0.3g/L, the persulfate is sodium persulfate, and the amount of the sodium persulfate is added in an amount of 0.3 to 1 mmol/L.
<3> the method as stated in <1>, the object to be treated is wastewater containing sulfadiazine or azo dye AO 7.
<4> the method according to <3>, when the object to be treated is sulfadiazine-containing wastewater, the concentration of sulfadiazine in the wastewater is adjusted to 5 to 20mg/L, the amount of CuMgAl-LDO layered oxide added is 0.05 to 0.3g/L, and the amount of sodium persulfate added is 0.3 to 1 mmol/L.
<5> the method according to <3>, wherein when the object to be treated is wastewater containing azo dye AO7, the concentration of azo dye AO7 in the wastewater is adjusted to 25 to 100mg/L, the amount of CuMgAl layered oxide added is 0.15 to 0.25g/L, and the amount of sodium persulfate added is 0.3 to 0.7 mmol/L.
<6>Such as<1>The method of, the Cu-containing2+The soluble copper salt of (A) is Cu (NO)3)2·3H2O and/or Cu (NO)3)2(ii) a Said containing Mg2+The soluble magnesium salt is MgSO4·7H2O and/or MgSO4And/or Mg (NO)3)2·6H2O and/or Mg (NO)3)2(ii) a Said Al-containing component3+The soluble aluminum salt of (2) is Al (NO)3)3·9H2O and/or Al (NO)3)3。
<7>Such as<1>Or<6>The method, the first mixed solution, Cu2+、Mg2+、Al3+In the molar ratio of (1-4) to 3: 2, in the second mixed solution, NaOH and Na2CO3The molar ratio of (1-3) to 1.
<8>Such as<7>The method, the first mixed solution, Cu2+、Mg2+、Al3+In the second mixed solution, NaOH and Na are added in a molar ratio of 3: 22CO3The molar ratio of (A) to (B) is 2: 1.
<9>Such as<7>The method, the first mixed solution, Cu2+Has a molar concentration of 0.15mol/L and Mg2+Has a molar concentration of 0.15mol/L and Al3+The molar concentration of (A) is 0.1 mol/L; in the second mixed solution, the molar concentration of NaOH is 1-3mol/L, and Na is added2CO3The molar concentration of (a) is 1 mol/L.
<10> the method as stated in <1>, the treating step includes an aging step in which an aging temperature is 50 ℃, a washing step, and a drying step; in the drying step, the drying temperature is 80 ℃, and the drying time is 12 hours; in the calcination treatment, the calcination temperature is 500 ℃ and the calcination time is 5 h.
The method for treating the organic pollutants, which is provided by the embodiment of the invention, has the advantages that the CuMgAl layered oxide activates persulfate to treat the organic pollutants, so that the concentration removal rate of the organic pollutants is high, the removal efficiency is high, and the cost is low.
Drawings
Fig. 1 is an X-ray diffraction chart of the layered oxide obtained in the first to fourth embodiments and the first comparative example in example 1 of the present invention.
Fig. 2 is a graph showing the change of the SMD concentration removal rate with time in the SMD experiment in the treated water using the layered oxides prepared using different molar ratios of metal ions as catalysts in the first to fourth embodiments and the first comparative example of example 1 of the present invention.
Fig. 3 is an infrared spectrum of the CuMgAl layered oxide obtained in the sixth embodiment of example 1 of the present invention and the CuMgAl layered oxide after repeated use.
Fig. 4 is a graph showing the change of the SMD concentration removal rate with time in the SMD experiment in the treated water using the layered oxides prepared with different alkali liquor ratios as the catalyst in the third, fifth, and seventh embodiments of the present invention in example 1.
Fig. 5 is an SEM image of the layered oxide obtained in the sixth embodiment in example 1 of the present invention.
Fig. 6 is a graph showing the change of the SMD concentration removal rate with time in the SMD experiment in the treated water using the layered oxides prepared at different pH values as the catalyst in the third and seventh embodiments of the present invention in example 1.
FIG. 7 is a graph showing the SD concentration removal rate in different systems with time in SD experiments on treated water of the catalysts obtained in the sixth embodiment of example 1 of the present invention, the first comparative example and the second comparative example 2 of the present invention.
FIG. 8 is a graph showing the SD concentration removal rate with time for different catalyst addition amounts in an SD experiment in treated water using the layered oxide obtained in the sixth embodiment of example 1 of the present invention as a catalyst.
FIG. 9 is a graph showing the temporal change of the SD concentration removal rate in different PS oxidant addition amounts in the SD test in treated water using the layered oxide obtained in the sixth embodiment of example 1 of the present invention as a catalyst.
FIG. 10 is a graph showing the removal rate of SD concentration with time at different catalyst addition amounts in the experiment of treating the azo dye AO7 in water with the layered oxide obtained in the sixth embodiment of example 1 of the present invention as a catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings. Those skilled in the art will appreciate that the present invention is not limited to the drawings and the following examples.
The invention is based on the following research findings: the CuMgAl layered oxide has different microscopic compositions and structures according to different preparation methods, and further has different catalytic properties, thereby playing different catalytic roles in different application environments. At present, CuMgAl layered oxide as a catalyst for activating persulfate to obtain sulfate radical has not been studied. The inventor finds that the CuMgAl layered oxide with a microstructure in a lamellar structure can be obtained by controlling the mixing mode of a salt solution and an alkali solution and strictly controlling the pH value of a reaction system to be stable within a certain range in the reaction process when the CuMgAl layered oxide is prepared, and the product has no agglomeration phenomenon, is suitable for being used as a catalyst for activating persulfate and can be used for treating organic pollutants by a persulfate advanced oxidation technology. The CuMgAl layered oxide obtained under the preparation conditions different from those of the present invention has a microstructure in which an agglomeration phenomenon occurs and cannot be used as a catalyst for activating persulfate.
Example 1
This example proposes a method for preparing a CuMgAl layered oxide for activating persulfates, comprising the following steps:
s1, containing Cu2+Soluble copper salt of (2) containing Mg2+Soluble magnesium salt of (5) and containing Al3+Soluble aluminum of (2)Dissolving salt in water to prepare a first mixed solution;
s2, mixing NaOH and Na2CO3Dissolving in water to prepare a second mixed solution;
s3, simultaneously dripping the first mixed solution and the second mixed solution into water with a certain volume under the condition of stirring, keeping the pH value of the system stable in the dripping process, and after dripping is finished, processing the obtained mixture to obtain CuMgAl layered hydroxide; and monitoring the reaction system by using a pH meter in the dropping process, and keeping the pH of the reaction system stable by adjusting the dropping speed. The pH value is 8-9, and more preferably, the pH value is 9.
And S4, calcining the CuMgAl layered hydroxide.
Preferably, the Cu is contained2+The soluble copper salt of (A) is Cu (NO)3)2·3H2O and/or Cu (NO)3)2(ii) a Said containing Mg2 +The soluble magnesium salt is MgSO4·7H2O and/or MgSO4And/or Mg (NO)3)2·6H2O and/or Mg (NO)3)2(ii) a Said Al-containing component3+The soluble aluminum salt of (2) is Al (NO)3)3·9H2O and/or Al (NO)3)3。
Preferably, in the first mixed solution, Cu2+、Mg2+、Al3+In a molar ratio of (1-4) to 3: 2, and more preferably, in the first mixed solution, Cu2+、Mg2+、Al3+The molar ratio of (A) to (B) is 3: 2.
Preferably, Cu2+Is 0.05 to 0.2mol/L, more preferably 0.15mol/L, Mg2+Has a molar concentration of 0.15mol/L and Al3+The molar concentration of (A) is 0.1 mol/L.
Preferably, in the second mixed solution, NaOH and Na2CO3The molar ratio of (1-3) to 1.
Preferably, the molar concentration of NaOH is 1-3mol/L, Na2CO3The molar concentration of (a) is 1 mol/L.
Preferably, the treating step includes an aging step, a washing step and a drying step.
Preferably, in the aging step, the aging temperature is 50 ℃.
Preferably, in the drying step, the drying temperature is 80 ℃ and the drying time is 12 h.
Preferably, in the calcination treatment, the calcination temperature is 500 ℃ and the calcination time is 5 h.
The method for producing a CuMgAl layered oxide for activating a persulfate according to the present invention will be described in further detail below with reference to specific embodiments.
< first embodiment >
A method for preparing CuMgAl layered oxide (CuMgAl- -LDO) for activating persulfate, comprising the following steps:
s1, taking 0.005mol of Cu (NO)3)2·3H2O、0.015mol MgSO4·7H2O、0.01mol Al(NO3)3·9H2O was dissolved in 50ml of ultrapure water to obtain a first mixed solution in which Cu (NO) was contained3)2·3H2O、MgSO4·7H2O、Al(NO3)3·9H2The molar ratio of O is 1: 3: 2.
S2, weighing 6g of NaOH and 5.3g of Na2CO3Dissolving in 50ml of ultrapure water to obtain a second mixed solution, NaOH and Na2CO3The molar ratio of (A) to (B) is 3: 1.
S3, simultaneously dripping the first mixed solution and the second mixed solution into 50ml of ultrapure water under the stirring condition, keeping the pH value at 9 in the process of dripping the grains, aging at 50 ℃ for 24 hours after dripping to obtain CuMgAl layered metal hydroxide (CuMgAl-LDH), filtering, washing the CuMgAl-LDH with the ultrapure water until the washing liquid is neutral, and drying at 80 ℃ for 12 hours to obtain dried CuMgAl-LDH.
S4, calcining the CuMgAl-LDH at 500 ℃ for 5 hours to obtain a CuMgAl layered oxide (CuMgAl-LDO), wherein the CuMgAl layered oxide can be used as a catalyst for activating persulfate and can be used for treating organic pollutants by a persulfate advanced oxidation technology, and an X-ray diffraction pattern of the CuMgAl-LDO catalyst is shown in figure 1.
Taking Sulfamethoxydiazine (SMD) in treated water as an example, the obtained CuMgAl-LDO catalyst is used for degrading sulfamethoxydiazine in water by a persulfate advanced oxidation reaction technology, and the method comprises the following steps:
0.2g of CuMgAl-LDO catalyst is weighed and added into 1L of water containing SMD, the initial concentration of SMD is 10mg/L, and then 0.5mmol/L of sodium Persulfate (PS) is added for oxidative degradation. Sampling at preset time intervals, immediately adding a certain amount of ethanol serving as a terminator into the taken sample, standing for a moment, and filtering the sample through a 0.22-micron needle filter. The filtered sample was quantitatively measured for the concentration of SMD at 266nm by high performance liquid chromatography, and a graph of concentration removal rate as a function of time was plotted, see fig. 2.
< second embodiment >
A method for preparing CuMgAl layered oxide (CuMgAl- -LDO) for activating persulfate, comprising the following steps:
s1, weighing 0.01mol of Cu (NO)3)2·3H2O、0.015mol MgSO4·7H2O、0.01mol Al(NO3)3·9H2O was dissolved in 50ml of ultrapure water to obtain a first mixed solution in which Cu (NO) was contained3)2·3H2O、MgSO4·7H2O、Al(NO3)3·9H2The molar ratio of O is 2: 3: 2.
S2, weighing 6g of NaOH and 5.3g of Na2CO3Dissolving in 50ml of ultrapure water to obtain a second mixed solution, NaOH and Na2CO3The molar ratio of (A) to (B) is 3: 1.
S3, simultaneously dripping the first mixed solution and the second mixed solution into 50ml of ultrapure water under the stirring condition, keeping the pH value at 9 in the process of dripping the grains, aging at 50 ℃ for 24 hours after dripping is finished to obtain CuMgAl-LDH, filtering the CuMgAl-LDH, washing the CuMgAl-LDH with the ultrapure water until the washing liquid is neutral, and drying at 80 ℃ for 12 hours to obtain dried CuMgAl-LDH.
S4, calcining the CuMgAl-LDH at 500 ℃ for 5 hours to obtain a CuMgAl layered oxide (CuMgAl-LDO), wherein the CuMgAl layered oxide can be used as a catalyst for activating persulfate and can be used for treating organic pollutants by a persulfate advanced oxidation technology, and an X-ray diffraction pattern of the CuMgAl-LDO catalyst is shown in figure 1.
The obtained CuMgAl-LDO catalyst is used for degrading sulfamethoxydiazine in water by a persulfate advanced oxidation reaction technology, the method is the same as the first embodiment, and the repeated description is omitted, and a curve diagram of the SMD concentration removal rate in water along with the change of time is shown in figure 2.
< third embodiment >
A method for preparing CuMgAl layered oxide (CuMgAl- -LDO) for activating persulfate, comprising the following steps:
s1, weighing 0.015mol of Cu (NO)3)2·3H2O、0.015mol MgSO4·7H2O、0.01mol Al(NO3)3·9H2O was dissolved in 50ml of ultrapure water to obtain a first mixed solution in which Cu (NO) was contained3)2·3H2O、MgSO4·7H2O、Al(NO3)3·9H2The molar ratio of O is 3: 2.
S2, weighing 6g of NaOH and 5.3g of Na2CO3Dissolving in 50ml of ultrapure water to obtain a second mixed solution, NaOH and Na2CO3The molar ratio of (A) to (B) is 3: 1.
S3, simultaneously dripping the first mixed solution and the second mixed solution into 50ml of ultrapure water under the stirring condition, keeping the pH value at 9 in the process of dripping the grains, aging at 50 ℃ for 24 hours after dripping is finished to obtain CuMgAl-LDH, filtering the CuMgAl-LDH, washing the CuMgAl-LDH with the ultrapure water until the washing liquid is neutral, and drying at 80 ℃ for 12 hours to obtain dried CuMgAl-LDH.
S4, calcining the CuMgAl-LDH at 500 ℃ for 5 hours to obtain a CuMgAl layered oxide (CuMgAl-LDO), wherein the CuMgAl layered oxide can be used as a catalyst for activating persulfate and can be used for treating organic pollutants by a persulfate advanced oxidation technology, and an X-ray diffraction pattern of the CuMgAl-LDO catalyst is shown in figure 1.
The obtained CuMgAl-LDO catalyst is used for degrading sulfamethoxydiazine in water by a persulfate advanced oxidation reaction technology, the method is the same as the first embodiment, and the repeated description is omitted, and a curve diagram of the SMD concentration removal rate in water along with the change of time is shown in figure 2.
< fourth embodiment >
A method for preparing CuMgAl layered oxide (CuMgAl- -LDO) for activating persulfate, comprising the following steps:
s1, weighing 0.02mol of Cu (NO)3)2·3H2O、0.015mol MgSO4·7H2O、0.01mol Al(NO3)3·9H2O was dissolved in 50ml of ultrapure water to obtain a first mixed solution in which Cu (NO) was contained3)2·3H2O、MgSO4·7H2O、Al(NO3)3·9H2The molar ratio of O is 4: 3: 2.
S2, weighing 6g of NaOH and 5.3g of Na2CO3Dissolving in 50ml of ultrapure water to obtain a second mixed solution, NaOH and Na2CO3The molar ratio of (A) to (B) is 3: 1.
S3, simultaneously dripping the first mixed solution and the second mixed solution into 50ml of ultrapure water under the stirring condition, keeping the pH value at 9 in the process of dripping the grains, aging at 50 ℃ for 24 hours after dripping is finished to obtain CuMgAl-LDH, filtering the CuMgAl-LDH, washing the CuMgAl-LDH with the ultrapure water until the washing liquid is neutral, and drying at 80 ℃ for 12 hours to obtain dried CuMgAl-LDH.
S4, calcining the CuMgAl-LDH at 500 ℃ for 5 hours to obtain a CuMgAl layered oxide (CuMgAl-LDO), wherein the CuMgAl layered oxide can be used as a catalyst for activating persulfate and can be used for treating organic pollutants by a persulfate advanced oxidation technology, and an X-ray diffraction pattern of the CuMgAl-LDO catalyst is shown in figure 1.
The obtained CuMgAl-LDO catalyst is used for degrading sulfamethoxydiazine in water by a persulfate advanced oxidation reaction technology, the method is the same as the first embodiment, and the repeated description is omitted, and a curve diagram of the SMD concentration removal rate in water along with the change of time is shown in figure 2.
< first comparative example >
The preparation of MgAl layered oxide (MgAl- -LDO) includes the following steps:
s1, weighing 0.015mol MgSO4·7H2O、0.01mol Al(NO3)3·9H2O was dissolved in 50ml of ultrapure water to obtain a first mixed solution in which Cu (NO) was contained3)2·3H2O、MgSO4·7H2O、Al(NO3)3·9H2The molar ratio of O is 0: 3: 2.
S2, weighing 6g of NaOH and 5.3g of Na2CO3Dissolving in 50ml of ultrapure water to obtain a second mixed solution, NaOH and Na2CO3The molar ratio of (A) to (B) is 3: 1.
S3, simultaneously dripping the first mixed solution and the second mixed solution into 50ml of ultrapure water under the stirring condition, keeping the pH value at 9 in the process of dripping the grains, aging at 50 ℃ for 24 hours after dripping is finished to obtain MgAl-LDH, filtering the MgAl-LDH, washing the MgAl-LDH with ultrapure water until the washing liquid is neutral, and drying at 80 ℃ for 12 hours to obtain dried MgAl-LDH.
S4, calcining the MgAl-LDH at 500 ℃ for 5 hours to obtain MgAl layered oxide (MgAl-LDO), wherein the X-ray diffraction pattern of the MgAl-LDO is shown in figure 1.
The obtained MgAl-LDO is used for degrading sulfamethoxydiazine in water by a persulfate advanced oxidation reaction technology, the method is the same as that of the first embodiment, and the repeated description is omitted, and a curve diagram of the SMD concentration removal rate in water along with the change of time is shown in figure 2.
< fifth embodiment >
A method for preparing CuMgAl layered oxide (CuMgAl- -LDO) for activating persulfate, comprising the following steps:
s1, weighing 0.015mol of Cu (NO)3)2·3H2O、0.015mol MgSO4·7H2O、0.01mol Al(NO3)3·9H2O was dissolved in 50ml of ultrapure water to obtain a first mixed solution in which Cu (NO) was contained3)2·3H2O、MgSO4·7H2O、Al(NO3)3·9H2The molar ratio of O is 3: 2.
S2, weighing 2g NaOH and 5.3g Na2CO3Dissolving in 50ml of ultrapure water to obtain a second mixed solution, NaOH and Na2CO3The molar ratio of (A) to (B) is 1: 1.
S3, simultaneously dripping the first mixed solution and the second mixed solution into 50ml of ultrapure water under the stirring condition, keeping the pH value at 9 in the process of dripping the grains, aging at 50 ℃ for 24 hours after dripping is finished to obtain CuMgAl-LDH, filtering the CuMgAl-LDH, washing the CuMgAl-LDH with the ultrapure water until the washing liquid is neutral, and drying at 80 ℃ for 12 hours to obtain dried CuMgAl-LDH.
And S4, calcining the CuMgAl-LDH at 500 ℃ for 5 hours to obtain a CuMgAl layered oxide (CuMgAl-LDO), wherein the CuMgAl layered oxide can be used as a catalyst for activating persulfate and can be used for treating organic pollutants by a persulfate advanced oxidation technology.
Taking Sulfamethoxydiazine (SMD) in treated water as an example, the obtained CuMgAl-LDO catalyst is used for degrading sulfamethoxydiazine in water by a persulfate advanced oxidation reaction technology, and the method comprises the following steps:
the obtained CuMgAl-LDO catalyst is used for degrading sulfamethoxydiazine in water by a persulfate advanced oxidation reaction technology, the method is the same as the first embodiment, the description is omitted, and a curve diagram of the SMD concentration removal rate in water along with the change of time is shown in fig. 4.
< sixth embodiment >
A method for preparing CuMgAl layered oxide (CuMgAl- -LDO) for activating persulfate, comprising the following steps:
s1, weighing 0.015mol of Cu (NO)3)2·3H2O、0.015mol MgSO4·7H2O、0.01mol Al(NO3)3·9H2O was dissolved in 50ml of ultrapure water to obtain a first mixed solution in which Cu (NO) was contained3)2·3H2O、MgSO4·7H2O、Al(NO3)3·9H2The molar ratio of O is 3: 2.
S2, weighing 4g of NaOH and 5.3g of Na2CO3Dissolving in 50ml of ultrapure water to obtainObtaining a second mixed solution of NaOH and Na2CO3The molar ratio of (A) to (B) is 2: 1.
S3, simultaneously dripping the first mixed solution and the second mixed solution into 50ml of ultrapure water under the stirring condition, keeping the pH value at 9 in the process of dripping the grains, aging at 50 ℃ for 24 hours after dripping is finished to obtain CuMgAl-LDH, filtering the CuMgAl-LDH, washing the CuMgAl-LDH with the ultrapure water until the washing liquid is neutral, and drying at 80 ℃ for 12 hours to obtain dried CuMgAl-LDH.
And S4, calcining the CuMgAl-LDH at 500 ℃ for 5 hours to obtain a CuMgAl layered oxide (CuMgAl-LDO), wherein the CuMgAl layered oxide can be used as a catalyst for activating persulfate and can be used for treating organic pollutants by a persulfate advanced oxidation technology. The infrared spectrum of the CuMgAl-LDO catalyst is shown in figure 3, the SEM image of the CuMgAl-LDO catalyst is shown in figure 5, and the scanning electron microscope shows that the product is in a lamellar structure.
Taking Sulfamethoxydiazine (SMD) in treated water as an example, the obtained CuMgAl-LDO catalyst is used for degrading sulfamethoxydiazine in water by a persulfate advanced oxidation reaction technology, and the method comprises the following steps:
the obtained CuMgAl-LDO catalyst is used for degrading sulfamethoxydiazine in water by a persulfate advanced oxidation reaction technology, the method is the same as the first embodiment, the description is omitted, and a curve diagram of the SMD concentration removal rate in water along with the change of time is shown in fig. 4.
< seventh embodiment >
A method for preparing CuMgAl layered oxide (CuMgAl- -LDO) for activating persulfate, comprising the following steps:
s1, weighing 0.015mol of Cu (NO)3)2·3H2O、0.015mol MgSO4·7H2O、0.01mol Al(NO3)3·9H2O was dissolved in 50ml of ultrapure water to obtain a first mixed solution in which Cu (NO) was contained3)2·3H2O、MgSO4·7H2O、Al(NO3)3·9H2The molar ratio of O is 3: 2.
S2, weighing 4g of NaOH and 5.3g of Na2CO3Dissolving in 50ml of ultrapure water to obtain a second mixed solution, NaOH and Na2CO3The molar ratio of (A) to (B) is 2: 1.
S3, simultaneously dripping the first mixed solution and the second mixed solution into 50ml of ultrapure water under the stirring condition, keeping the pH value at 8 in the process of dripping the grains, aging at 50 ℃ for 24 hours after dripping is finished to obtain CuMgAl-LDH, filtering the CuMgAl-LDH, washing the CuMgAl-LDH with the ultrapure water until the washing liquid is neutral, and drying at 80 ℃ for 12 hours to obtain dried CuMgAl-LDH.
And S4, calcining the CuMgAl-LDH at 500 ℃ for 5 hours to obtain a CuMgAl layered oxide (CuMgAl-LDO), wherein the CuMgAl layered oxide can be used as a catalyst for activating persulfate and can be used for treating organic pollutants by a persulfate advanced oxidation technology.
Taking Sulfamethoxydiazine (SMD) in treated water as an example, the obtained CuMgAl-LDO catalyst is used for degrading sulfamethoxydiazine in water by a persulfate advanced oxidation reaction technology, and the method comprises the following steps:
the obtained CuMgAl-LDO catalyst is used for degrading sulfamethoxydiazine in water by a persulfate advanced oxidation reaction technology, the method is the same as the first embodiment, and the repeated description is omitted, and a curve diagram of the SMD concentration removal rate in water along with the change of time is shown in fig. 6.
From the experimental results of the above embodiments and the first comparative example, it can be seen that:
(1) according to the first to fourth embodiments and the first comparative example, when Cu (NO)3)2·3H2O、MgSO4·7H2O、Al(NO3)3·9H2When the molar ratio of O is 0: 3: 2, the degradation efficiency of sulfamethoxydiazine is very low when the MgAl-LDO/PS is 120min, which indicates that the MgAl-LDO can not activate the PS to generate sulfate radicals. When Cu (NO)3)2·3H2O、MgSO4·7H2O、Al(NO3)3·9H2When the molar ratio of O is increased from 0: 3: 2 to 3: 2, the removal rate of CuMgAl-LDO/PS to the concentration of sulfamethoxydiazine is increased, the effect is obvious, which shows that the CuMgAl-LDO obtained by the preparation method of the embodiment of the invention can activate persulfate,the mechanism is Cu2+Substitution of Mg2+Copper metal is uniformly dispersed, active sites are increased, and the catalytic performance is enhanced; when Cu (NO)3)2·3H2O、MgSO4·7H2O、Al(NO3)3·9H2When the molar ratio of O is continuously increased to 4: 3: 2, the removal rate of CuMgAl-LDO/PS to the concentration of sulfamethoxydiazine is slightly reduced, and the mechanism is that along with the increase of the molar ratio of copper metal, a hydrotalcite-like laminate is twisted, the catalytic activity is reduced, and the removal rate of SMD concentration is reduced.
(2) According to the third, fifth and sixth embodiments, when the mixed alkali solution is NaOH: Na2CO3At a ratio of 2: 1, precipitating agent Na2CO3The carbonate ion can balance positive charges on a laminate formed by metal ions and a precipitator NaOH, and the prepared catalyst is kept in electric neutrality. When the CuMgAl-LDO obtained from the sixth embodiment is subjected to infrared spectrum analysis, as shown in FIG. 3, the infrared spectrum (shown by a dotted line) of the CuMgAl-LDO prepared according to the sixth embodiment after repeated use is not significantly changed from that of the newly prepared product (shown by a solid line), which indicates that the CuMgAl-LDO catalyst prepared according to the method has stable structure and the metal ion Cu-LDO has no obvious change2+And Al3+With Na2CO3During coprecipitation, composite carbonate metal is formed, and the uniformity of the composition of the precipitate is further improved. Referring to FIG. 4, NaOH and Na are mixed in alkali solution2CO3When the ratio is 2: 1, the SMD concentration removal rate is highest.
(3) According to the sixth to seventh embodiments, when the pH is 8, the precipitation of the metal ions is incomplete, the precipitated particles are large, and the distribution of the components is slightly poor. SEM test is carried out on the CuMgAl-LDO obtained in the sixth embodiment, and as shown in FIG. 5, a scanning electron microscope of the CuMgAl-LDO shows that the product is in a lamellar structure, all components are uniformly distributed, and the CuMgAl-LDO has the catalytic performance of activating persulfate. Referring to fig. 6, the SMD removal rate is highest and the rate constant is greatest at pH 9.
According to another aspect of the present invention, the present embodiment also proposes a CuMgAl layered oxide for activating a persulfate, which is prepared using the preparation method as described above.
According to another aspect of the present invention, the present example also proposes the use of a CuMgAl layered oxide prepared by the preparation method as described above for activating a persulfate.
Example 2
This example presents a method for treating organic pollutants by activating persulfate with CuMgAl layered oxide (CuMgAl-LDO), comprising the following steps:
adding CuMgAl-LDO and persulfate into an object to be treated; the CuMgAl-LDO was obtained according to the preparation method of the foregoing example 1.
Preferably, the adding amount of the CuMgAl-LDO catalyst is 0.05-0.3 g/L.
Preferably, the persulfate is sodium persulfate, and the addition amount of the sodium persulfate is 0.3-1 mmol/L.
Preferably, the object to be treated is wastewater containing sulfadiazine or azo dye AO 7.
Preferably, when the object to be treated is wastewater containing sulfadiazine, the concentration of sulfadiazine in the wastewater is adjusted to be 5-20mg/L, preferably 10mg/L, the adding amount of the CuMgAl-LDO catalyst is 0.05-0.3g/L, and the adding amount of the sodium persulfate oxidant is 0.3-1 mmol/L.
More preferably, when the object to be treated is wastewater containing sulfadiazine, the sulfadiazine concentration of the wastewater is adjusted to be 10mg/L, the addition amount of the CuMgAl-LDO catalyst is 0.2g/L, and the addition amount of the sodium persulfate oxidant is 0.7 mmol/L.
Preferably, when the object to be treated is wastewater containing azo dye AO7, the concentration of azo dye AO7 in the wastewater is adjusted to be 25-100mg/L, preferably 50mg/L, the dosage of CuMgAl-LDO catalyst is 0.15-0.25g/L, and the dosage of sodium persulfate oxidant is 0.3-0.7mmol/L, preferably 0.5 mmol/L.
The method for activating persulfate to treat organic pollutants by using CuMgAl layered oxide (CuMgAl-LDO) according to the present invention will be described in further detail by the following embodiments.
< eighth embodiment >
A method for activating persulfate to treat Sulfadiazine (SD) in wastewater by using a CuMgAl layered oxide (CuMgAl-LDO, which is a product of the aforementioned sixth embodiment, used in this embodiment), comprising the steps of: CuMgAl-LDO and sodium Persulfate (PS) are added into the wastewater containing 10mg/L Sulfadiazine (SD), the concentration of the CuMgAl-LDO is 0.2g/L, the concentration of the sodium persulfate is 0.5mmol/L, stirring is carried out, and reaction is carried out for 45 min.
1L of wastewater is taken for treatment, sampling is carried out at certain time intervals during the reaction period, a certain amount of ethanol is added into the taken sample at once as a terminator, standing is carried out for a moment, and the sample is filtered by a 0.22 mu m needle filter. The filtered sample was quantitatively measured for sulfadiazine concentration at 269nm using high performance liquid chromatography, and the concentration removal rate was plotted as a function of time, see fig. 7.
< second comparative example >
CuMgAl-LDO is added into the wastewater containing 10mg/L Sulfadiazine (SD), the concentration of the CuMgAl-LDO is 0.2g/L, and the mixture is stirred and reacted for 45 min. The method for detecting the concentration removal rate is the same as that in the eighth embodiment, and a graph of the concentration removal rate changing with time is drawn, as shown in fig. 7.
< third comparative example >
Sodium Persulfate (PS) was added to the wastewater containing 10mg/L Sulfadiazine (SD) at a concentration of 0.5mmol/L, and the mixture was stirred and reacted for 45 min. The method for detecting the concentration removal rate is the same as that in the eighth embodiment, and a graph of the concentration removal rate changing with time is drawn, as shown in fig. 7.
< fourth comparative example >
Adding MgAl-LDO and sodium Persulfate (PS) into wastewater containing 10mg/L Sulfadiazine (SD), wherein the concentration of the MgAl-LDO is 0.2g/L, and the concentration of the sodium persulfate is 0.5mmol/L, stirring, and reacting for 45 min. The method for detecting the concentration removal rate is the same as that in the eighth embodiment, and a graph of the concentration removal rate changing with time is drawn, as shown in fig. 7.
< fifth comparative example >
Cu-LDO (prepared by the same method as the sixth embodiment except that no magnesium salt or aluminum salt is added) and sodium Persulfate (PS) are added to wastewater containing 10mg/L Sulfadiazine (SD), the concentration of Cu-LDO is 0.2g/L, the concentration of sodium persulfate is 0.5mmol/L, and the mixture is stirred and reacted for 45 min. The method for detecting the concentration removal rate is the same as that in the eighth embodiment, and a graph of the concentration removal rate changing with time is drawn, as shown in fig. 7.
< ninth embodiment >
A method for activating persulfate in wastewater by using CuMgAl layered oxide (product of the aforementioned sixth embodiment) to treat Sulfadiazine (SD) comprising the steps of: CuMgAl-LDO and sodium Persulfate (PS) are added into the wastewater containing 10mg/L Sulfadiazine (SD), the concentration of the CuMgAl-LDO is 0.05g/L, and the concentration of the sodium persulfate is 0.5mmol/L, and the mixture is stirred and reacted for 45 min. The method for detecting the concentration removal rate is the same as that in the eighth embodiment, and a graph of the concentration removal rate changing with time is drawn, as shown in fig. 8.
< tenth embodiment >
A method for activating persulfate in wastewater by using CuMgAl layered oxide (product of the aforementioned sixth embodiment) to treat Sulfadiazine (SD) comprising the steps of: CuMgAl-LDO and sodium Persulfate (PS) are added into the wastewater containing 10mg/L Sulfadiazine (SD), the concentration of the CuMgAl-LDO is 0.1g/L, the concentration of the sodium persulfate is 0.5mmol/L, stirring is carried out, and reaction is carried out for 45 min. The method for detecting the concentration removal rate is the same as that in the eighth embodiment, and a graph of the concentration removal rate changing with time is drawn, as shown in fig. 8.
< eleventh embodiment >
A method for activating persulfate in wastewater by using CuMgAl layered oxide (product of the aforementioned sixth embodiment) to treat Sulfadiazine (SD) comprising the steps of: CuMgAl-LDO and sodium Persulfate (PS) are added into the wastewater containing 10mg/L Sulfadiazine (SD), the concentration of the CuMgAl-LDO is 0.3g/L, and the concentration of the sodium persulfate is 0.5mmol/L, and the mixture is stirred and reacted for 45 min. The method for detecting the concentration removal rate is the same as that in the eighth embodiment, and a graph of the concentration removal rate changing with time is drawn, as shown in fig. 8.
< twelfth embodiment >
A method for activating persulfate in wastewater by using CuMgAl layered oxide (product of the aforementioned sixth embodiment) to treat Sulfadiazine (SD) comprising the steps of: CuMgAl-LDO and sodium Persulfate (PS) are added into the wastewater containing 10mg/L Sulfadiazine (SD), the concentration of the CuMgAl-LDO is 0.2g/L, and the concentration of the sodium persulfate is 0.3mmol/L, and the mixture is stirred and reacted for 45 min. The method for detecting the concentration removal rate is the same as that in the eighth embodiment, and a graph of the concentration removal rate changing with time is drawn, as shown in fig. 9.
< thirteenth embodiment >
A method for activating persulfate in wastewater by using CuMgAl layered oxide (product of the aforementioned sixth embodiment) to treat Sulfadiazine (SD) comprising the steps of: CuMgAl-LDO and sodium Persulfate (PS) are added into the wastewater containing 10mg/L Sulfadiazine (SD), the concentration of the CuMgAl-LDO is 0.2g/L, and the concentration of the sodium persulfate is 0.7mmol/L, and the mixture is stirred and reacted for 45 min. The method for detecting the concentration removal rate is the same as that in the eighth embodiment, and a graph of the concentration removal rate changing with time is drawn, as shown in fig. 9.
< fourteenth embodiment >
A method for activating persulfate in wastewater by using CuMgAl layered oxide (product of the aforementioned sixth embodiment) to treat Sulfadiazine (SD) comprising the steps of: CuMgAl-LDO and sodium Persulfate (PS) are added into the wastewater containing 10mg/L Sulfadiazine (SD), the concentration of the CuMgAl-LDO is 0.2g/L, the concentration of the sodium persulfate is 1mmol/L, stirring is carried out, and the reaction is carried out for 45 min. The method for detecting the concentration removal rate is the same as that in the eighth embodiment, and a graph of the concentration removal rate changing with time is drawn, as shown in fig. 9.
< fifteenth embodiment >
A method for activating persulfate salt to treat azo dye AO7 in wastewater by using a CuMgAl layered oxide (product of the foregoing sixth embodiment), comprising the steps of: CuMgAl-LDO and sodium Persulfate (PS) are added into the wastewater containing 50mg/L of azo dye AO7, the concentration of the CuMgAl-LDO is 0.15g/L, the concentration of the sodium persulfate is 0.5mmol/L, stirring is carried out, and reaction is carried out for 50 min.
1L of wastewater is taken for treatment, sampling is carried out at certain time intervals during the reaction period, a certain amount of ethanol is added into the taken sample at once as a terminator, standing is carried out for a moment, and the sample is filtered by a 0.22 mu m needle filter. The concentration of the azo dye AO7 was quantitatively determined by high performance liquid chromatography on the filtered sample at 480nm and the removal rate of the concentration was plotted as a function of time, see FIG. 10.
< sixteenth embodiment >
A method for activating persulfate salt to treat azo dye AO7 in wastewater by using a CuMgAl layered oxide (product of the foregoing sixth embodiment), comprising the steps of: CuMgAl-LDO and sodium Persulfate (PS) are added into the wastewater containing 50mg/L of azo dye AO7, the concentration of the CuMgAl-LDO is 0.15g/L, the concentration of the sodium persulfate is 0.5mmol/L, stirring is carried out, and reaction is carried out for 50 min. The method for detecting the concentration removal rate is the same as that in the fifteenth embodiment, and a graph of the concentration removal rate changing with time is drawn, as shown in fig. 10.
< seventeenth embodiment >
A method for activating persulfate salt to treat azo dye AO7 in wastewater by using a CuMgAl layered oxide (product of the foregoing sixth embodiment), comprising the steps of: CuMgAl-LDO and sodium Persulfate (PS) are added into the wastewater containing 50mg/L of azo dye AO7, the concentration of the CuMgAl-LDO is 0.2g/L, the concentration of the sodium persulfate is 0.5mmol/L, stirring is carried out, and reaction is carried out for 50 min. The method for detecting the concentration removal rate is the same as that in the fifteenth embodiment, and a graph of the concentration removal rate changing with time is drawn, as shown in fig. 10.
< seventeenth embodiment >
A method for activating persulfate salt to treat azo dye AO7 in wastewater by using a CuMgAl layered oxide (product of the foregoing sixth embodiment), comprising the steps of: CuMgAl-LDO and sodium Persulfate (PS) are added into the wastewater containing 50mg/L of azo dye AO7, the concentration of the CuMgAl-LDO is 0.22g/L, and the concentration of the sodium persulfate is 0.5mmol/L, and the mixture is stirred and reacted for 50 min. The method for detecting the concentration removal rate is the same as that in the fifteenth embodiment, and a graph of the concentration removal rate changing with time is drawn, as shown in fig. 10.
< eighteenth embodiment >
A method for activating persulfate salt to treat azo dye AO7 in wastewater by using a CuMgAl layered oxide (product of the foregoing sixth embodiment), comprising the steps of: CuMgAl-LDO and sodium Persulfate (PS) are added into the wastewater containing 50mg/L of azo dye AO7, the concentration of the CuMgAl-LDO is 0.25g/L, the concentration of the sodium persulfate is 0.5mmol/L, stirring is carried out, and reaction is carried out for 50 min. The method for detecting the concentration removal rate is the same as that in the fifteenth embodiment, and a graph of the concentration removal rate changing with time is drawn, as shown in fig. 10.
From the experimental results of the above embodiments and the second to fifth comparative examples, it can be seen that:
(1) referring to fig. 7, according to the eighth embodiment and the second to fifth comparative examples, the SD concentration removal rates in different systems were: PS is more than MgAl-LDO/PS and more than CuMgAl-LDO and more than Cu-LDO/PS and more than CuMgAl-LDO/PS. When only CuMgAl-LDO or PS exists and a MgAl-LDO/PS system, the SD removing effect is poor, which indicates that the MgAl-LDO can not activate the PS to generate sulfate radicals; the concentration removal rate for SD by adding Cu-LDO/PS system was about 49.51%, while that for CuMgAl-LDO/PS system was 97.56%, indicating that the active metal was Cu instead of Mg or Al. In addition, the layered metal oxide can well disperse metals, so that the metals are uniformly distributed, have larger surface area and can effectively interact in the degradation process.
(2) Referring to FIG. 8, according to the eighth to eleventh embodiments, as the CuMgAl-LDO catalyst is increased from 0.05g/L to 0.2g/L, the concentration removal rate of SD is from 92.95% to 98.37%. The contact probability of the catalyst and the sodium persulfate oxidant is increased and the number of catalytic active sites is increased along with the increase of the adding amount of the CuMgAl-LDO catalyst.
The adding amount of the CuMgAl-LDO catalyst is increased to 0.3g/L, the concentration removal rate of SD is slightly reduced to 97.94 percent, and excessive Cu is added2+Leading to quenching of the sulfate radical.
(3) Referring to FIG. 9, according to the eighth, twelfth to fourteenth embodiments, the addition amount of the oxidizing agent PS is increased from 0.3mM/L to 1mM/L, and the removal rate of the final concentration of sulfadiazine is not greatly changed. When the oxidant PS addition was increased from 0.3mM/L to 0.7mM/L, the concentration removal rate of SD was slightly increased from 96.97% to 98.62%. As the amount of PS added increases, the catalyst utilization also increases, producing more sulfate radicals, thereby promoting degradation of the target contaminant. Overdosing of PS results in competition and consumption of free radicals.
(4) Referring to FIG. 10, according to the fifteenth to eighteenth embodiments, as the CuMgAl-LDO catalyst is increased from 0.15g/L to 0.25g/L, the concentration removal rate of the azo dye AO7 is increased from 42.1% to 96.8%. With the increase of the addition amount of the CuMgAl-LDO catalyst, the contact probability of the catalyst and the oxidant is increased, and the number of catalytic active sites is increased.
The invention shows that the CuMgAl-LDO catalyst obtained by the preparation method of the embodiment 1 can effectively activate persulfate to generate sulfate radical, so that sulfamethoxydiazine, sulfadiazine and azo dye AO7 can be degraded. The oxidability of sulfate radicals is not selective, and the sulfate radicals can degrade various organic pollutants without being limited to three organic pollutants in the embodiment, so that the CuMgAl-LDO catalyst obtained by the preparation method can be used for activating persulfate to treat the organic pollutants.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for treating organic pollutants by activating persulfate with a layered oxide of CuMgAl, comprising the steps of:
adding CuMgAl layered oxide and persulfate into an object to be treated;
the CuMgAl layered oxide is prepared by the following preparation method:
will contain Cu2+Soluble copper salt of (2) containing Mg2+Soluble magnesium salt of (5) and containing Al3+Dissolving the soluble aluminum salt in water to prepare a first mixed solution;
NaOH and Na2CO3Dissolving in water to prepare a second mixed solution;
under the condition of stirring, simultaneously dropwise adding the first mixed solution and the second mixed solution into a certain volume of water, keeping the pH value of the reaction system stable in the dropwise adding process, and after the dropwise adding is finished, processing the obtained mixture to obtain CuMgAl layered hydroxide, wherein the value range of the pH value is 8-9;
-subjecting said CuMgAl layered hydroxide to a calcination treatment.
2. The method according to claim 1, wherein the CuMgAl layered oxide is added in an amount of 0.05 to 0.3g/L, the persulfate is sodium persulfate, and the sodium persulfate is added in an amount of 0.3 to 1 mmol/L.
3. The method according to claim 1, wherein the object to be treated is wastewater containing sulfadiazine or azo dye AO 7.
4. The method according to claim 3, wherein when the object to be treated is a waste water containing sulfadiazine, the concentration of sulfadiazine in the waste water is adjusted to 5 to 20mg/L, the amount of CuMgAl-LDO layered oxide added is 0.05 to 0.3g/L, and the amount of sodium persulfate added is 0.3 to 1 mmol/L.
5. The method according to claim 3, wherein when the object to be treated is wastewater containing azo dye AO7, the concentration of azo dye AO7 in the wastewater is adjusted to 25 to 100mg/L, the amount of CuMgAl layered oxide added is 0.15 to 0.25g/L, and the amount of sodium persulfate added is 0.3 to 0.7 mmol/L.
6. The method of claim 1,the Cu-containing2+The soluble copper salt of (A) is Cu (NO)3)2·3H2O and/or Cu (NO)3)2(ii) a Said containing Mg2+The soluble magnesium salt is MgSO4·7H2O and/or MgSO4And/or Mg (NO)3)2·6H2O and/or Mg (NO)3)2(ii) a Said Al-containing component3+The soluble aluminum salt of (2) is Al (NO)3)3·9H2O and/or Al (NO)3)3。
7. The method of claim 1 or 6, wherein in the first mixed solution, Cu2+、Mg2+、Al3+In the molar ratio of (1-4) to 3: 2, in the second mixed solution, NaOH and Na2CO3The molar ratio of (1-3) to 1.
8. The method of claim 7, wherein in the first mixed solution, Cu2+、Mg2+、Al3+In the second mixed solution, NaOH and Na are added in a molar ratio of 3: 22CO3The molar ratio of (A) to (B) is 2: 1.
9. The method of claim 7, wherein in the first mixed solution, Cu2+Has a molar concentration of 0.15mol/L and Mg2+Has a molar concentration of 0.15mol/L and Al3+The molar concentration of (A) is 0.1 mol/L; in the second mixed solution, the molar concentration of NaOH is 1-3mol/L, and Na is added2CO3The molar concentration of (a) is 1 mol/L.
10. The method according to claim 1, wherein the treating step comprises an aging step in which an aging temperature is 50 ℃, a washing step, and a drying step; in the drying step, the drying temperature is 80 ℃, and the drying time is 12 hours; in the calcination treatment, the calcination temperature is 500 ℃ and the calcination time is 5 h.
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