CN114956185A - Manganese oxide material, preparation method and application thereof in petroleum hydrocarbon degradation and heavy metal adsorption - Google Patents

Manganese oxide material, preparation method and application thereof in petroleum hydrocarbon degradation and heavy metal adsorption Download PDF

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CN114956185A
CN114956185A CN202210202656.6A CN202210202656A CN114956185A CN 114956185 A CN114956185 A CN 114956185A CN 202210202656 A CN202210202656 A CN 202210202656A CN 114956185 A CN114956185 A CN 114956185A
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manganese oxide
oxide material
petroleum hydrocarbon
heavy metal
water
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陈乐贻
陆强
张猛
胡晓钧
孟军
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Shanghai Chengyu Environmental Protection Engineering Co ltd
Shanghai Institute of Technology
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Shanghai Chengyu Environmental Protection Engineering Co ltd
Shanghai Institute of Technology
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Abstract

The invention discloses a manganese oxide material, a preparation method and application thereof in degrading petroleum hydrocarbon and adsorbing heavy metal. The invention prepares the manganese oxide material by reducing and boiling the potassium permanganate solution with concentrated hydrochloric acid, and finally prepares the manganese oxide material. The manganese oxide material has the advantages of low charge zero point, large specific surface area, strong active site and high oxidation capacity, and can realize the adsorption oxidation removal of petroleum hydrocarbon organic pollutants. Compared with the prior art, the method has the advantages of simple operation, low cost, high removal efficiency, good safety, conventional and easily obtained chemical reagents and materials, and good practical application value in the field of water treatment.

Description

Manganese oxide material, preparation method and application thereof in petroleum hydrocarbon degradation and heavy metal adsorption
Technical Field
The invention relates to the technical field of water treatment, in particular to a manganese oxide material, a preparation method and application thereof in degrading petroleum hydrocarbon and adsorbing heavy metal.
Background
Petrochemical belongs to the heavy pollution industry. During the development, storage and transportation and refining of petroleum, petroleum hydrocarbon enters the atmosphere, soil and water environment due to accidental leakage, and the petroleum hydrocarbon-heavy metal composite pollution to the soil and underground water environment can be caused. Petroleum hydrocarbon organic pollutants often have 'three-cause' toxicity, and the toxicity is superimposed when the petroleum hydrocarbon organic pollutants are subjected to combined pollution with heavy metals, so that great harm is caused to the health of human beings and the safety of the whole ecological system. Various interactions usually occur between organic matters and heavy metal pollutant components, and influence the migration and transformation processes of the organic matters and the heavy metal pollutants in water, so that the migration and the biodegradation characteristics are changed, and the two pollutants are difficult to be efficiently and synchronously removed.
The water treatment technologies developed at home and abroad aiming at the two pollutants are mainly divided into a physical and chemical method, a chemical method and a biochemical method. The chemical method generally has the advantages of short period and high removal rate, and is concerned with the application in the field of water treatment. At present, the research on heavy metals and organic matters respectively or the research on the compound pollution of various heavy metals and various hydrocarbon organic matters is mostly carried out.
Manganese oxide is a ubiquitous manganese mineral in soil and sediments, and the specific properties of adsorption, oxidation, catalysis and the like shown by the manganese oxide are increasingly paid attention to as a usable and important purifying agent in environmental pollution treatment. Birnessite is a typical manganese oxide mineral with a laminated structure, and the valence state of the structural unit of the birnessite is mostlyMn(Ⅳ)O 6 And also contains a certain amount of Mn (III) O 6 And Mn (II) O 6 . The stable layered structure and the larger interlayer spacing of the birnessite enable the birnessite to have the characteristics of large specific surface area, low charge zero point, high cation exchange capacity, strong oxidation capacity and the like. The catalyst is widely applied to the fields of batteries, supercapacitors, water treatment and catalysis.
Chinese patent CN 112892548A discloses a preparation method of a manganese-based catalyst for sewage treatment and the manganese-based catalyst. The manganese-based catalyst takes a solution containing manganese ions as a precursor solution, one or more solutions containing iron ions, cobalt ions, cerium ions and copper ions as an auxiliary agent precursor solution, takes organic acid as a reductive complexing agent solution, is mixed to obtain a prefabricated mixed solution, the pretreated activated carbon is soaked into the prefabricated mixed solution, the manganese-based catalyst which takes manganese oxide as a main catalyst and takes the pretreated activated carbon as a carrier and is used for sewage treatment is obtained through high-temperature calcination, and the specific surface area of the manganese-based catalyst is 500-1200 m 2 Per g, pore volume of 0.35-0.8 cm 3 And/g, the activity of catalyzing and oxidizing organic matters in the sewage is high, the stability is good, and the capability is strong. The preparation method provided by the invention is simple to operate, mild in condition, short in period and environment-friendly. Although the invention discloses that the manganese-based catalyst can be used for sewage treatment, one of manganese acetate, manganese nitrate, manganese sulfate and manganese chloride is used as a precursor solution, and active carbon is used as a carrier, so that the manganese-based catalyst is mainly used for degrading organic matters in sewage.
Chinese patent CN 108176345 a discloses a preparation method of granular MnSb adsorbent, a product and an application thereof in removing radioactive Sr, Co and Ag, which comprises: particles containing a MnSb composite oxide; and a polymer material layer coating the particles. The adsorbent is in a particle form and has high crushing strength, so the adsorbent is suitable for industrial scale, can be filled into a fixed bed reactor to realize high-efficiency removal of radionuclide, has good adsorption removal performance on Sr, Co and Ag particles, can be applied to radioactive waste liquid treatment in nuclear accident emergency, and can selectively remove main fissile nuclide 90 Sr; meanwhile, the adsorbent can also be applied to civil water treatmentAnd removing metal ions Ag, Sr and Co. The invention discloses that Sb (III) is oxidized and converted into Sb (V) by potassium permanganate, and Mn (VII) is reduced into Mn (IV) at the same time, and the Mn (VII) and the Mn (IV) generate MnSb composite oxides, but the preparation process is more complex and mainly aims at heavy metal ions such as Ag, Sr, Co and the like in sewage. Therefore, the material which has simple preparation process and environmental protection, does not generate toxic by-products and can simultaneously treat organic pollutants and heavy metal ions in the sewage is very important.
Disclosure of Invention
In view of the above defects in the prior art, the technical problem to be solved by the present invention is to provide a preparation method and application of manganese oxide material for degrading and adsorbing petroleum hydrocarbon-heavy metal combined pollution. The birnessite type manganese oxide material prepared by the invention has the effects of adsorption and oxidative degradation, takes the octahedral cation cavity with negative electricity in the layer as a heavy metal ion adsorption site, and utilizes the Mn (IV) redox property to remove petroleum hydrocarbon pollutants by oxidation, thereby forming an adsorption-oxidative degradation system in a water system. Simple steps, environment-friendly property and no toxic by-products.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the manganese oxide material for adsorbing and oxidizing petroleum hydrocarbon-heavy metal pollutants comprises the following steps:
s1, dissolving potassium permanganate in water, and stirring to be emulsion;
s2, oil-bath boiling the emulsion-shaped potassium permanganate aqueous solution at 130-135 ℃ for 20-30 min, dropwise adding concentrated hydrochloric acid under stirring and continuously reacting for 1-1.5 h, and removing generated gas by using 0.25-0.3 mol/L sodium thiosulfate; the dropping rate of the concentrated hydrochloric acid is 0.5-0.7 mL/min;
s3, naturally cooling to 55-60 ℃ after the reaction is finished, and carrying out condensation reflux at 55-60 ℃ for aging at constant temperature for 10-12 h;
s4, centrifuging the aged mixture, removing the supernatant to obtain a solid, and fully washing the solid with pure water until the conductivity of the supernatant is lower than 18-20 mu S/cm;
s5, freeze-drying the product obtained in the step S4 at-60 to-55 ℃ for 2 to 3 days, grinding, sealing and storing to obtain the manganese oxide material.
Further, in the step S1, the ratio of potassium permanganate to water is (3.16-4): 100 g/mL.
Further, the concentration of concentrated hydrochloric acid in step S2 is 6-7 mol/L.
Further, the reaction ratio of the concentrated hydrochloric acid to the potassium permanganate in the step S2 is 2: 1.
The invention also provides application of the manganese oxide material in degrading petroleum hydrocarbon and adsorbing heavy metals, which comprises the following steps:
the method comprises the following steps: preparing the manganese oxide material into a mineral suspension, and then carrying out ultrasonic treatment on the mineral suspension; the ultrasonic treatment condition is ultrasonic for 15-20 min under 35-40 KHz;
step two: in the presence of Na containing petroleum hydrocarbon and heavy metal 2 SO 4 Adding the mineral suspension into the solution, adjusting the pH value, oscillating, uniformly mixing, centrifuging, removing supernatant, and removing petroleum hydrocarbon and heavy metal in water to obtain mixed solution;
step three: and D, filtering the mixed solution prepared in the step two by using a filter membrane, so that the degradation of petroleum hydrocarbon and the adsorption of heavy metals are realized.
Further, the concentration of the mineral suspension in the first step is 4-7 g/L.
Further, the second step contains Na of petroleum hydrocarbon and heavy metal 2 SO 4 The solution is petroleum hydrocarbon, heavy metal and Na 2 SO 4 Mixing the water and the water uniformly to obtain the product; the concentration of the petroleum hydrocarbon is 0.01-100 mg/L; na (Na) 2 SO 4 The concentration of (A) is 0.1 mol/L; the concentration of heavy metal is 0.01-100 mg/L; the heavy metal is Cd.
Further, in the second step, the pH is adjusted to 3-9.
Further, the oscillation rate of the oscillation and uniform mixing in the step two is 150-200 rpm, and the oscillation time is 10 min-30 h.
Further, the oscillation temperature of the oscillation and uniform mixing in the step two is 20-25 ℃.
Further, the rotating speed of the centrifugation in the step two is 4000-5000 rpm, and the centrifugation time is 15-30 min.
Further, Na containing petroleum hydrocarbon and heavy metal 2 SO 4 The dosage ratio of the solution to the mineral suspension after ultrasonic treatment is (2-4): 1.
further, in the third step, the filter membrane is 0.22 μm.
The method utilizes concentrated hydrochloric acid to reduce and boil a potassium permanganate solution to prepare the manganese oxide material, and finally prepares the birnessite type manganese oxide material. The birnessite has considerable octahedral cation cavities (with negative electricity) in the layer, and the cavities are regarded as strong active adsorption sites and can efficiently adsorb and remove heavy metals and organic pollutants.
Compared with the prior art, the invention has the beneficial effects that:
1. the method can rapidly reduce the content of petroleum hydrocarbon-heavy metal in the water body by utilizing the manganese oxide material, has the effect of removing the heavy metal cadmium of more than 99 percent, can completely adsorb and remove the heavy metal cadmium, can effectively adsorb and oxidize to remove the petroleum hydrocarbon pollutants, and has synchronous removal effect and high mineralization degree on the two pollutants.
2. The method has the advantages of simple operation, easy control of reaction conditions and easy realization of engineering application, and in addition, the used chemical reagents and materials are conventional products for water treatment, other toxic and harmful substances are not introduced, and the safety is particularly outstanding.
3. The reaction environment is easy to realize, the reaction can be processed at room temperature, and the feasibility and operability of the method are effectively improved.
Drawings
FIG. 1 is an X-ray diffraction pattern of a manganese oxide material prepared in example 1 of the present invention.
FIG. 2 is a Fourier transform infrared absorption spectrum of the manganese oxide material prepared in example 1 of the present invention.
FIG. 3 is a graph showing the adsorption effect of heavy metal cadmium in water according to example 4 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples. The procedures, conditions, experimental methods and the like for carrying out the present invention are common knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
For the sake of brevity, the drugs used in the following examples are all commercially available products unless otherwise specified, and the methods used are conventional methods unless otherwise specified.
Example 1
The preparation of the manganese oxide material comprises the following steps:
the S1 reaction is carried out in a three-neck flask, 3.16g of potassium permanganate is dissolved in 100mL of distilled water and is uniformly mixed at room temperature, and the mixture is stirred at the rotating speed of 250rpm until the mixture is emulsion;
s2, oil-bath boiling the uniformly mixed potassium permanganate solution at 135 ℃ for 30min, dropwise adding 18mL of 6mol/L concentrated hydrochloric acid at 0.7mL/min at the rotating speed of 500rpm, and continuously reacting for 1.5h, wherein the reaction ratio of potassium permanganate to concentrated hydrochloric acid is 1:2, and removing generated gas by using 0.3mol/L sodium thiosulfate;
s3, naturally cooling to 60 ℃ after the reaction is finished, and carrying out condensation reflux and constant temperature aging for 12 h;
s4, placing the aged mixture into a centrifuge, centrifuging the suspension for 20min at 4000rpm, discarding the supernatant to obtain a solid, and fully washing the solid for 5 times by pure water until the conductivity of the supernatant is lower than 20 mu S/cm;
s5, freeze-drying the product obtained in the step S4 at-60 ℃ for 2 days, grinding the product in an agate mortar, and sealing and storing the product to obtain the manganese oxide material.
Example 2
The determination of the performance of the manganese oxide material for adsorbing and removing heavy metals in water comprises the following steps:
s1, preparing 5g/L mineral suspension from the birnessite type manganese oxide obtained in the example 1, and carrying out ultrasonic treatment on the mineral suspension at the ultrasonic frequency of 40kHz for 15 min;
s2 to a 50mL centrifuge tube was added 5mL Na in sequence 2 SO 4 Solution, 10mLCdCl 2 The solution and 5mL of mineral suspension were mixed and the reaction pH was adjusted to 7, where Na 2 SO 4 The solution concentration is 0.1mol/L, CdCl 2 The concentration of the solution is 5 mg/L;
s3, placing the mixture obtained in the step S2 in a constant temperature oscillator for constant temperature oscillation, keeping the temperature at 25 ℃, and reacting for 30 hours under the condition that the rotation speed of the oscillator is 200 rpm;
and (3) placing the mixture after the reaction time of S4 in a centrifuge, centrifuging the suspension for 20min at 4000rpm, filtering the supernatant through a 0.22-micron microporous filter membrane, and measuring the content of cadmium ions in the supernatant.
The cadmium ion content in the water sample before and after the reaction is measured to be 5mg/L and 0.1mg/L, the adsorption system for the heavy metal cadmium polluted water sample can adsorb and remove 98% of cadmium ions in the water sample, and the test results are shown in Table 1.
Example 3
The performance test of removing heavy metals in water by absorbing the manganese oxide material comprises the following steps:
s1, preparing 5g/L mineral suspension from the birnessite type manganese oxide obtained in the example 1, and carrying out ultrasonic treatment on the mineral suspension at the ultrasonic frequency of 40kHz for 15 min;
s2 to a 50mL centrifuge tube was added 5mL Na in sequence 2 SO 4 Solution, 10mL CdCl 2 The solution and 5mL of mineral suspension were mixed and the reaction pH was adjusted to 7, where Na 2 SO 4 The solution concentration is 0.1mol/L, CdCl 2 The concentration of the solution is 8 mg/L;
s3, placing the mixture obtained in the step S2 in a constant temperature oscillator for constant temperature oscillation, keeping the temperature at 25 ℃, and reacting for 30 hours under the condition that the rotation speed of the oscillator is 200 rpm;
and (3) placing the mixture after the reaction time of S4 in a centrifuge, centrifuging the suspension for 20min at 4000rpm, filtering the supernatant through a 0.22-micron microporous filter membrane, and measuring the content of cadmium ions in the supernatant.
The cadmium ion content in the water sample before and after the reaction is measured to be 8mg/L and 0.1mg/L, the adsorption system for the heavy metal cadmium polluted water sample can adsorb and remove 98% of cadmium ions in the water sample, and the test results are shown in Table 1.
Example 4
The performance test of the manganese oxide material for adsorbing heavy metals in water comprises the following steps:
the method comprises the following steps: preparing 5g/L mineral suspension from the birnessite type manganese oxide obtained in the example 1, and carrying out ultrasonic treatment on the mineral suspension at the ultrasonic frequency of 40kHz for 15 min;
step two: 5mL of Na was sequentially added to a 50mL centrifuge tube 2 SO 4 Solution, 10mL CdCl 2 The solution and 5mL of mineral suspension were mixed and the reaction pH was adjusted to 7, where Na 2 SO 4 The solution concentration is 0.1mol/L, CdCl 2 The concentration of the solution is 70 mg/L;
step three: placing the centrifugal tube in the second step into a constant-temperature oscillator for constant-temperature oscillation, keeping the temperature at 25 ℃, and reacting for 30 hours under the condition that the rotation speed of the oscillator is 200 rpm;
step four: and (3) placing the mixture after the reaction time is over in a centrifuge, centrifuging the suspension for 20min at 4000rpm, filtering the supernatant through a 0.22-micron microporous filter membrane, and measuring the content of cadmium ions in the supernatant.
The cadmium ion content in the water sample before and after the reaction is measured to be 70mg/L and 1.5mg/L, 98% of cadmium ions in the water sample can be removed by the adsorption system of the heavy metal cadmium polluted water sample, and the test results are shown in table 1.
Example 5
The performance test of removing petroleum hydrocarbon in water by absorbing manganese oxide material comprises the following steps:
the method comprises the following steps: preparing 5g/L mineral suspension from the birnessite type manganese oxide obtained in the example 1, and carrying out ultrasonic treatment on the mineral suspension at the ultrasonic frequency of 40kHz for 15 min;
step two: 5mL of Na was sequentially added to a 50mL centrifuge tube 2 SO 4 Solution, 10mL crude oil in acetone and 5mL mineral suspension in which Na is present 2 SO 4 The concentration of the solution is 0.1mol/L, and the concentration of hydrocarbon compounds of petroleum hydrocarbon in the crude oil is 100 mg/L;
step three: placing the mixture of the sealed transparent centrifugal tube in a constant-temperature oscillator for constant-temperature oscillation, keeping the temperature at 25 ℃, and reacting for 30 hours under the condition that the rotation speed of the oscillator is 200 rpm;
step four: and (3) placing the mixture after the reaction time is over in a centrifuge, centrifuging the suspension for 20min at 4000rpm, filtering the supernatant through a 0.22-micron microporous filter membrane, and measuring the content of petroleum hydrocarbon hydrocarbons in the supernatant.
Example 6
The performance test of removing petroleum hydrocarbon-heavy metal in water by absorbing the manganese oxide material comprises the following steps:
the method comprises the following steps: preparing 5g/L mineral suspension from the birnessite type manganese oxide obtained in the example 1, and carrying out ultrasonic treatment on the mineral suspension at the ultrasonic frequency of 40kHz for 15 min;
step two: 5mL of Na was sequentially added to a 50mL centrifuge tube 2 SO 4 Solution, 5mL CdCl 2 Solution, 5mL crude oil in acetone and 5mL mineral suspension in which Na is present 2 SO 4 The solution concentration is 0.1mol/L, CdCl 2 The concentration of the solution is 100 mg/L; the concentration of hydrocarbon compounds in petroleum hydrocarbon in the crude oil is 100 mg/L;
step three: placing the mixture of the sealed transparent centrifugal tube in a constant-temperature oscillator for constant-temperature oscillation, keeping the temperature at 25 ℃, and reacting for 30 hours under the condition that the rotation speed of the oscillator is 200 rpm;
step four: and placing the mixture after the reaction time is over in a centrifuge, centrifuging the suspension for 20min at 4000rpm, filtering the supernatant by a 0.22 mu m microporous filter membrane, and measuring the content of cadmium ions and petroleum hydrocarbon hydrocarbons in the supernatant.
TABLE 1 adsorption effect of birnessite type manganese oxide on heavy metal cadmium in water
Figure BDA0003527979360000091
Example 7
The preparation of the manganese oxide material comprises the following steps:
the S1 reaction is carried out in a three-neck flask, 3.16g of potassium permanganate is dissolved in 100mL of distilled water and is uniformly mixed at room temperature, and the mixture is stirred at the rotating speed of 250rpm until the mixture is emulsion;
s2, oil-bath boiling the uniformly mixed potassium permanganate solution at 135 ℃ for 30min, dropwise adding 18mL of 6mol/L concentrated hydrochloric acid at 0.7mL/min at the rotation speed of 500rpm, continuously reacting for 1.5h, wherein the reaction ratio of the potassium permanganate to the concentrated hydrochloric acid is 1:2, and removing generated gas by using 0.3mol/L sodium thiosulfate;
s3, naturally cooling to 60 ℃ after the reaction is finished, and carrying out condensation reflux and constant temperature aging for 12 h;
s4, placing the aged mixture into a centrifuge, centrifuging the suspension for 20min at 4000rpm, discarding the supernatant to obtain a solid, and fully washing the solid for 5 times by pure water until the conductivity of the supernatant is lower than 20 mu S/cm;
s5, freeze-drying the product obtained in the step S4 at-60 ℃ for 2 days, grinding the product in an agate mortar, and sealing and storing the product to obtain the manganese oxide material.
S6, taking 2 parts by weight of the manganese oxide material prepared in the step S5, dispersing the manganese oxide material into 15 parts by weight of absolute ethyl alcohol at room temperature, adding 5 parts by weight of stearic acid into the absolute ethyl alcohol, stirring uniformly, transferring the solution into a reaction kettle, reacting at 100 ℃ for 24 hours, cooling, filtering, washing with water, drying to obtain a solid, dispersing the solid into 80-100 parts by weight of polyvinylpyrrolidone, performing ultrasonic treatment at 100W and 25kHz for 80min, and performing rotary evaporation to remove the solvent to obtain the modified manganese oxide material.
The application of the manganese oxide material in adsorbing heavy metals in water comprises the following steps:
the method comprises the following steps: preparing the obtained modified manganese oxide material into 5g/L mineral suspension, and carrying out ultrasonic treatment on the mineral suspension at the ultrasonic frequency of 40kHz for 15 min;
step two: 5mL of Na was sequentially added to a 50mL centrifuge tube 2 SO 4 Solution, 10mL CdCl 2 The solution and 5mL of mineral suspension were mixed and the reaction pH was adjusted to 7, where Na 2 SO 4 The solution concentration is 0.1mol/L, CdCl 2 The concentration of the solution is 70 mg/L;
step three: placing the centrifugal tube in the second step into a constant-temperature oscillator for constant-temperature oscillation, keeping the temperature at 25 ℃, and reacting for 30 hours under the condition that the rotation speed of the oscillator is 200 rpm;
step four: and (3) placing the mixture after the reaction time is over in a centrifuge, centrifuging the suspension for 20min at 4000rpm, filtering the supernatant through a 0.22-micron microporous filter membrane, and measuring the content of cadmium ions in the supernatant.
The application of the manganese oxide material in removing petroleum hydrocarbon in water comprises the following steps:
the method comprises the following steps: preparing the obtained manganese oxide material into 5g/L mineral suspension, and carrying out ultrasonic treatment on the mineral suspension at the ultrasonic frequency of 40kHz for 15 min;
step two: 5mL of Na was sequentially added to a 50mL centrifuge tube 2 SO 4 Solution, 10mL crude oil in acetone and 5mL mineral suspension in Na 2 SO 4 The concentration of the solution is 0.1mol/L, and the concentration of hydrocarbon compounds of petroleum hydrocarbons in the crude oil is 100 mg/L;
step three: placing the mixture of the sealed transparent centrifugal tube in a constant-temperature oscillator for constant-temperature oscillation, keeping the temperature at 25 ℃, and reacting for 30 hours under the condition that the rotation speed of the oscillator is 200 rpm;
step four: and placing the mixture after the reaction time is over in a centrifuge, centrifuging the suspension for 20min at 4000rpm, filtering the supernatant through a 0.22 mu m microporous filter membrane, and measuring the content of petroleum hydrocarbon hydrocarbons in the supernatant.
The application of the manganese oxide material in the adsorption removal of petroleum hydrocarbon-heavy metal in water comprises the following steps:
the method comprises the following steps: preparing the obtained manganese oxide material into 5g/L mineral suspension, and carrying out ultrasonic treatment on the mineral suspension at the ultrasonic frequency of 40kHz for 15 min;
step two: 5mL of Na was sequentially added to a 50mL centrifuge tube 2 SO 4 Solution, 5mL CdCl 2 Solution, 5mL of crude oil in acetone and 5mL of a mineral suspension in which Na is present 2 SO 4 The solution concentration is 0.1mol/L, CdCl 2 The concentration of the solution is 100 mg/L; the concentration of hydrocarbon compounds in petroleum hydrocarbon in the crude oil is 100 mg/L;
step three: placing the mixture of the sealed transparent centrifugal tube in a constant-temperature oscillator for constant-temperature oscillation, keeping the temperature at 25 ℃, and reacting for 30 hours under the condition that the rotation speed of the oscillator is 200 rpm;
step four: and placing the mixture after the reaction time is over in a centrifuge, centrifuging the suspension for 20min at 4000rpm, filtering the supernatant by a 0.22 mu m microporous filter membrane, and measuring the content of cadmium ions and petroleum hydrocarbon hydrocarbons in the supernatant.

Claims (10)

1. The preparation method of the manganese oxide material is characterized by comprising the following steps of:
s1, dissolving potassium permanganate in water, and stirring to be emulsion;
s2, boiling the emulsion-shaped potassium permanganate aqueous solution in oil bath at 130-135 ℃ for 20-30 min, dripping concentrated hydrochloric acid under stirring and continuously reacting for 1-1.5 h;
s3, naturally cooling to 55-60 ℃ after the reaction is finished, and condensing, refluxing and aging at constant temperature for 10-12 h at 55-60 ℃;
s4, centrifuging the aged mixture, discarding the supernatant to obtain a solid, and fully washing the solid with pure water until the conductivity of the supernatant is lower than 18-20 mus/cm;
s5, freeze-drying the product obtained in the step S4 at-60 to-55 ℃ for 2-3 days, grinding, sealing and storing to obtain the manganese oxide material.
2. The method of preparing a manganese oxide material according to claim 1, wherein: the ratio of potassium permanganate to water in the step S1 is (3.16-4): 100 g/mL.
3. The method of preparing a manganese oxide material according to claim 1, wherein: the concentration of the concentrated hydrochloric acid in the step S2 is 6-7 mol/L.
4. The method of preparing a manganese oxide material according to claim 1, wherein: the reaction ratio of the concentrated hydrochloric acid to the potassium permanganate in the step S2 is 2: 1.
5. A manganese oxide material characterized by: prepared by the method of any one of claims 1 to 4.
6. The use of the manganese oxide material of claim 5 for degrading petroleum hydrocarbons and adsorbing heavy metals, comprising the steps of:
the method comprises the following steps: preparing the manganese oxide material into a mineral suspension, and then carrying out ultrasonic treatment on the mineral suspension;
step two: in the presence of Na containing petroleum hydrocarbons and heavy metals 2 SO 4 Adding the mineral suspension subjected to ultrasonic treatment into the solution, adjusting the pH value, oscillating, uniformly mixing and centrifuging, removing supernatant, and removing petroleum hydrocarbon and heavy metal in water to obtain mixed solution;
step three: and D, filtering the mixed solution prepared in the step two by using a filter membrane, so that the degradation of petroleum hydrocarbon and the adsorption of heavy metals are realized.
7. The use of the manganese oxide material of claim 6 for degrading petroleum hydrocarbons and adsorbing heavy metals, wherein: the concentration of the mineral suspension in the first step is 4-7 g/L.
8. The use of the manganese oxide material of claim 6 for degrading petroleum hydrocarbons and adsorbing heavy metals, wherein: in the second step, Na containing petroleum hydrocarbon and heavy metal is contained 2 SO 4 The solution is petroleum hydrocarbon, heavy metal and Na 2 SO 4 Mixing the water and the water uniformly to obtain the product; the concentration of the petroleum hydrocarbon is 0.01-100 mg/L; na (Na) 2 SO 4 The concentration of (A) is 0.1 mol/L; the concentration of heavy metal is 0.01-100 mg/L; the heavy metal is Cd.
9. The use of the manganese oxide material of claim 6 for degrading petroleum hydrocarbons and adsorbing heavy metals, wherein: in the second step, the pH is adjusted to be 3-9; the oscillation rate of the oscillation and uniform mixing is 150-200 rpm; the oscillation time is 10-30 h; the oscillation temperature is 20-25 ℃; the centrifugal rotating speed is 4000-5000 rpm; the centrifugation time is 15-30 min.
10. The use of the manganese oxide material of claim 6 for degrading petroleum hydrocarbons and adsorbing heavy metals, wherein: the filter membrane in the third step is 0.22 mu m.
CN202210202656.6A 2022-07-13 2022-07-13 Manganese oxide material, preparation method and application thereof in petroleum hydrocarbon degradation and heavy metal adsorption Pending CN114956185A (en)

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