CN111054297A - Preparation of manganese ferrite/porous graphite phase carbon nitride and method for treating low-concentration uranium-containing wastewater - Google Patents
Preparation of manganese ferrite/porous graphite phase carbon nitride and method for treating low-concentration uranium-containing wastewater Download PDFInfo
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- CN111054297A CN111054297A CN201911314831.5A CN201911314831A CN111054297A CN 111054297 A CN111054297 A CN 111054297A CN 201911314831 A CN201911314831 A CN 201911314831A CN 111054297 A CN111054297 A CN 111054297A
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- manganese ferrite
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 128
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 115
- 239000010439 graphite Substances 0.000 title claims abstract description 115
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 87
- 239000011572 manganese Substances 0.000 title claims abstract description 86
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 83
- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 76
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- 238000000034 method Methods 0.000 title claims abstract description 29
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- 238000001179 sorption measurement Methods 0.000 claims abstract description 43
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- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 11
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 8
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- 238000001354 calcination Methods 0.000 claims abstract description 6
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
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- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
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- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
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- 238000003795 desorption Methods 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 41
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- 239000000463 material Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 229910017163 MnFe2O4 Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
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- 229910021389 graphene Inorganic materials 0.000 description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
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- 230000036541 health Effects 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
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- DKZXTOPFCDDGGX-UHFFFAOYSA-N tri-s-triazine Chemical group C1=NC(N23)=NC=NC2=NC=NC3=N1 DKZXTOPFCDDGGX-UHFFFAOYSA-N 0.000 description 1
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0222—Compounds of Mn, Re
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
Abstract
The preparation method of the manganese ferrite/porous graphite phase carbon nitride and the method for treating the low-concentration uranium-containing wastewater by using the same comprises the steps of dissolving melamine and calcium carbonate in deionized water, carrying out ultrasonic treatment, heating and stirring until the mixture is gelatinous, drying, grinding, sieving, calcining, removing a calcium carbonate template, washing with water and drying to obtain the porous graphite phase carbon nitride; adding porous graphite phase carbon nitride into ethylene glycol solution, and sequentially adding FeCl3·6H2O、MnSO4·H2O, sodium acetate and polyvinylpyrrolidone, stirring, heating, cooling and washing to obtain the manganese ferrite/porous graphite phase carbon nitride. When the method is used, the pH value of the uranium-containing wastewater is adjusted to 4-6, manganese ferrite/porous graphite phase carbon nitride is added for adsorption, the addition amount of the manganese ferrite/porous graphite phase carbon nitride is 150-600 mg/L, and the method adoptsAnd (3) oscillating and adsorbing by a water bath oscillator for 20 min. When the manganese ferrite/porous graphite phase carbon nitride is adsorbed and saturated, the manganese ferrite/porous graphite phase carbon nitride adsorbed with uranium is resolved and adsorbed by hydrochloric acid, and then the manganese ferrite/porous graphite phase carbon nitride is washed, dried and reused.
Description
Technical Field
The invention relates to the field of U (VI) -containing wastewater treatment, in particular to a method for preparing manganese ferrite/porous graphite phase carbon nitride and treating low-concentration uranium-containing wastewater by using the manganese ferrite/porous graphite phase carbon nitride as a uranium removal adsorbent.
Background
With the rapid development of nuclear technology and atomic energy industry in China, a large amount of uranium-containing nuclear waste is generated in the processes of uranium ore mining, nuclear energy power generation and the like. Uranium is a toxic and radioactive metal, and wastewater containing U (VI) enters a water environment, which poses serious threats to the ecological environment and the health of human beings. Particularly, the low-concentration uranium-containing leachate formed during uranium ore mining enters the water environment along with hydrologic cycle, and the radioactivity and toxicity of the leachate still have adverse effects on human health. Therefore, the low-concentration uranium-containing wastewater must be treated to avoid radioactive pollution to the water environment.
At present, methods for treating uranium-containing wastewater mainly comprise an adsorption method, a membrane separation method, a chemical precipitation method, an electrochemical method and the like. The membrane separation method, the chemical precipitation method, the electrochemical method and the like are not only poor in effect for treating the uranium-containing wastewater with lower concentration, but also too large in energy consumption, and energy waste is caused. The adsorption method has the advantages of low energy consumption, economy, environmental protection, good treatment effect on low-concentration uranium-containing wastewater and the like, and is widely applied to the treatment of radioactive heavy metal wastewater. For example, chinese patent CN106390961A uses cigarette ash as a uranium removing adsorbent to treat low-concentration uranium-containing wastewater, and CN105597698A uses biomass charcoal-based magnetic sludge as a uranium removing adsorbent to remove uranium and the like in low-concentration uranium-containing wastewater.
The graphite-phase carbon nitride is a novel non-metallic material, the actual structure of the graphite-phase carbon nitride is similar to that of graphene, and the graphite-phase carbon nitride has a graphite crystal C-N framework, and the tri-s-triazine ring structure in the structure enables the graphite-phase carbon nitride to have good thermal stability and chemical stability; in addition, the graphite phase carbon nitride structure has alkaline-NH-and-NH at the edge2Functional groups and pyridine groups with strong electron-withdrawing ability, so that the pyridine groups have great application potential in the aspect of adsorption; however, the application of the graphite phase carbon nitride to U (VI) adsorption is limited due to the defects of small specific surface area, small pore volume, difficult separation in water treatment and the like.
The preparation of porous structure material by template method solves the problems of small specific surface area and pore volume of materialSmall and efficient processes and have found widespread use in the field of pollutant adsorption. Using manganese ferrite MnFe2O4The ferrite type composite metal oxide is one of the research hot spots of magnetic materials in recent years, and has the advantages of small particle size, large specific surface area, rich hydroxyl group, high saturation magnetization and Fe3O4、NiFe2O4、CoFe2O4Compared with the prior art, the material has higher biocompatibility, and utilizes MnFe2O4The magnetic characteristics of the adsorbent are beneficial to the separation and recovery efficiency of the adsorbing materials under the action of an external magnetic field, and meanwhile, the synergistic effect of the two materials can enhance the adsorption effect of the adsorbent.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for preparing manganese ferrite/porous graphite phase carbon nitride and treating low-concentration uranium-containing wastewater by using the manganese ferrite/porous graphite phase carbon nitride as a uranium removal adsorbent.
The technical scheme of the invention is as follows: the preparation method of the manganese ferrite/porous graphite phase carbon nitride comprises the following steps:
step one, preparing porous graphite phase carbon nitride: dissolving melamine and calcium carbonate in deionized water, and carrying out ultrasonic treatment for 30 min; and heating and stirring the treated solution at 60-90 ℃ until the solution is gelatinous, drying in vacuum, fully grinding the dried powder, and sieving with a 200-mesh sieve.
And calcining the ground and sieved powder in a muffle furnace at 500-550 ℃ for 2-5 h, grinding the calcined product through a 200-mesh sieve, and removing the calcium carbonate template by using dilute hydrochloric acid until no carbon dioxide bubbles are generated in water. Wherein the mass ratio of melamine to calcium carbonate is 5: 1.
and washing the porous graphite phase carbon nitride obtained after the calcium carbonate template is removed by deionized water for many times until the solution is neutral, and placing the solution in an oven for drying for later use.
Step two, manganese ferrite/porous stonePreparation of ink-phase carbon nitride: weighing porous graphite phase carbon nitride, adding the porous graphite phase carbon nitride into an ethylene glycol solution, and performing ultrasonic dispersion for 30-60 min; then FeCl is added in turn3·6H2O、MnSO4·H2And O, sodium acetate and polyvinylpyrrolidone, and stirring for 30-90 min.
Wherein, the porous graphite phase carbon nitride and FeCl3·6H2O、MnSO4·H2The mass ratio of O to sodium acetate to polyvinylpyrrolidone is 1: 0.5-2: 0.2-0.5: 1.5-2.5: 0.1 to 0.5; FeCl3·6H2O and MnSO4·H2The molar mass ratio of O is 2: 1; the ratio of the porous graphite phase carbon nitride to the glycol solution is 20 g/L-50 g/L.
And (3) placing the stirred solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining, heating the solution to 110-180 ℃ for 9-12 h, cooling, washing the black solid obtained after cooling with absolute ethyl alcohol and deionized water for several times until the pH value of the washed supernatant is determined to be neutral, and then placing the washed black solid into a vacuum drying oven for drying at 60-80 ℃ for 5-7 h to obtain the manganese ferrite/porous graphite phase carbon nitride.
The invention provides a technical scheme that: the method for treating the low-concentration uranium-containing wastewater by adopting the manganese ferrite/porous graphite phase carbon nitride comprises the following specific operation steps of:
adjusting the pH value of the uranium-containing wastewater to 4-6, adding manganese ferrite/porous graphite phase carbon nitride for adsorption, wherein the addition amount of the manganese ferrite/porous graphite phase carbon nitride is 150-600 mg/L, and performing oscillation adsorption by using a water bath oscillator for 10-140 min.
The further technical scheme of the invention is as follows: desorbing the saturated manganese ferrite/porous graphite phase carbon nitride, wherein the desorption process is as follows:
firstly, separating saturated manganese ferrite/porous graphite phase carbon nitride from uranium-containing wastewater by using a magnet, then putting the manganese ferrite/porous graphite phase carbon nitride into hydrochloric acid for desorption, separating the desorbed manganese ferrite/porous graphite phase carbon nitride from the hydrochloric acid by using the magnet and washing the desorbed manganese ferrite/porous graphite phase carbon nitride with deionized water for a plurality of times until the washed supernatant is neutral, and drying the desorbed manganese ferrite/porous graphite phase carbon nitride for reuse.
Compared with the prior art, the invention has the following characteristics:
1. the invention adopts the graphite-phase carbon nitride adsorbing material for adsorption, has higher chemical stability and thermal stability compared with the traditional carbon adsorbing materials such as activated carbon, mesoporous carbon and the like, and can effectively adsorb heavy metals and the like.
2. The calcium carbonate adopted by the invention can not generate toxic and harmful gas when the template is removed, can not damage amino in the graphite phase carbon nitride structure, and can avoid the influence of unexpected reaction on the adsorption performance of the adsorbent in the preparation process.
3. The manganese multiferroate/porous graphite phase carbon nitride prepared by the method can effectively remove uranium in low-concentration uranium-containing wastewater, the adsorption efficiency is obviously improved compared with that of pure graphite phase carbon nitride, and MnFe is adopted2O4After compounding, the adsorption rate of the magnetic adsorbent to uranium is further improved, and separation and recovery are facilitated.
The detailed structure of the present invention will be further described with reference to the accompanying drawings and the detailed description.
Drawings
FIG. 1 shows the respective charging of g-C of graphite-phase carbon nitride3N4A graph showing the influence of uranium-containing wastewater with different pH values on the removal rate when the porous graphite phase carbon nitride MCN and the manganese ferrite/porous graphite phase carbon nitride MMCN are used;
FIG. 2 is a graph showing the effect of different manganese ferrite/porous graphite phase carbon nitride additions on removal rate;
FIG. 3 is a graph showing the effect of different adsorption times on removal rate;
FIG. 4 shows the uranium removal rate of manganese ferrite/porous graphite phase carbon nitride repeatedly used five times;
FIG. 5 is a graph showing uranium removal rate after five repetitions of manganese ferrite/porous graphite phase carbon nitride.
Detailed Description
In a first embodiment, a method for preparing manganese ferrite/porous graphite phase carbon nitride comprises the steps of:
step one, preparing porous graphite phase carbon nitride: dissolving 5g of melamine and 1g of calcium carbonate in deionized water, and carrying out ultrasonic treatment for 30 min; heating and stirring the treated solution at 60 ℃ to form gel, drying in vacuum, fully grinding the dried powder, and sieving with a 200-mesh sieve; and calcining the ground and sieved powder in a muffle furnace at 500 ℃ for 5 hours, grinding the calcined product, sieving the ground product with a 200-mesh sieve, and removing the calcium carbonate template by using dilute hydrochloric acid until no carbon dioxide bubbles are generated in water. And washing the porous graphite phase carbon nitride obtained after the calcium carbonate template is removed by deionized water for many times until the solution is neutral, and placing the solution in an oven for drying for later use.
In the embodiment, calcium carbonate is used as a template agent, and diluted hydrochloric acid is used for removing the calcium carbonate, so that harmful hydrogen fluoride gas is not generated in the process of removing the calcium carbonate by using the diluted hydrochloric acid compared with the existing method of removing the calcium carbonate by using silicon dioxide as a template agent and hydrofluoric acid. In addition, hydrofluoric acid protonates the amino groups contained in the graphite-phase carbon nitride, reducing the adsorption sites for uranium.
Step two, preparing manganese ferrite/porous graphite phase carbon nitride: weighing 1g of porous graphite phase carbon nitride, adding into 50ml of glycol solution, and performing ultrasonic dispersion for 30 min; then 0.5g of FeCl was weighed3·6H2O, 0.2g of MnSO4·H2Adding O, 1.5g of sodium acetate and 0.1g of polyvinylpyrrolidone into the solution in sequence, and stirring for 30 min; the FeCl3·6H2O and MnSO4·H2The molar mass ratio of O is 2: 1. and (3) placing the stirred solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining, heating the solution to 110 ℃ for 12h, cooling the solution, washing the black solid obtained after cooling the solution for a plurality of times by using absolute ethyl alcohol and deionized water until the pH value of the washed supernatant is determined to be neutral, and then placing the washed black solid into a vacuum drying oven for drying for 7h at the temperature of 60 ℃ to obtain the manganese ferrite/porous graphite phase carbon nitride.
This example utilizes sodium acetate (NaAc) hydrolysis for conditioningpH of the solution so that MnSO is added4·H2O and FeCl3·6H2The molar mass ratio of O to Mn is 1:2 to realize MnFe2O4The synthesis of (2):
Mn2++2Fe3++80H-→Mn(OH)2↓+2Fe(OH)3↓
→MnFe 204+4H 20
example two, the preparation of manganese ferrite/porous graphite phase carbon nitride, comprises the following steps:
step one, preparing porous graphite phase carbon nitride: dissolving 10g of melamine and 2g of calcium carbonate in deionized water, and carrying out ultrasonic treatment for 30 min; heating and stirring the treated solution at 70 ℃ to form gel, drying in vacuum, fully grinding the dried powder, and sieving with a 200-mesh sieve; and calcining the ground and sieved powder in a muffle furnace at 530 ℃ for 4 hours, grinding the calcined product, sieving the product with a 200-mesh sieve, and removing the calcium carbonate template by using dilute hydrochloric acid until no carbon dioxide bubbles are generated in water. And washing the porous graphite phase carbon nitride obtained after the calcium carbonate template is removed by deionized water for many times until the solution is neutral, and placing the solution in an oven for drying for later use.
Step two, preparing manganese ferrite/porous graphite phase carbon nitride: weighing 2g of porous graphite-phase carbon nitride, adding the porous graphite-phase carbon nitride into 60mL of glycol solution, and performing ultrasonic dispersion for 50 min; then 0.8g of FeCl was weighed3·6H2O, 0.3g of MnSO4·H2O, 2.0g of sodium acetate and 0.3g of polyvinylpyrrolidone are sequentially added into the solution and stirred for 60min, and the FeCl3·6H2O and MnSO4·H2The molar mass ratio of O is 2: 1. and (3) placing the stirred solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining, heating the solution to 140 ℃ for 10 hours, cooling the solution, washing the black solid obtained after cooling the solution for a plurality of times by using absolute ethyl alcohol and deionized water until the pH value of the washed supernatant is determined to be neutral, and then placing the washed black solid into a vacuum drying oven to dry the black solid for 6 hours at 70 ℃ to obtain the manganese ferrite/porous graphite phase carbon nitride.
This example utilizes sodium acetate (NaAc) hydrolysisAdjusting the pH of the solution so that MnSO is added4·H2O and FeCl3·6H2The molar mass ratio of O to Mn is 1:2 to realize MnFe2O4The synthesis of (2):
Mn2++2Fe3++80H-→Mn(OH)2↓+2Fe(OH)3↓
→MnFe 204+4H 20
example three, preparation of manganese ferrite/porous graphite phase carbon nitride, comprising the steps of:
step one, preparing porous graphite phase carbon nitride: dissolving 15g of melamine and 3g of calcium carbonate in deionized water, and carrying out ultrasonic treatment for 30 min; heating and stirring the treated solution at 90 ℃ to form gel, drying in vacuum, fully grinding the dried powder, and sieving with a 200-mesh sieve; and calcining the ground and sieved powder in a muffle furnace at 550 ℃ for 2 hours, grinding the calcined product, sieving the product with a 200-mesh sieve, and removing the calcium carbonate template by using dilute hydrochloric acid until no carbon dioxide bubbles are generated in water. And washing the porous graphite phase carbon nitride obtained after the calcium carbonate template is removed by deionized water for many times until the solution is neutral, and placing the solution in an oven for drying for later use.
Step two, preparing manganese ferrite/porous graphite phase carbon nitride: weighing 10g of porous graphite-phase carbon nitride, adding the porous graphite-phase carbon nitride into 200mL of glycol solution, and performing ultrasonic dispersion for 60 min; then 20g of FeCl was weighed3·6H2O, 5g of MnSO4·H2Adding O, 25g of sodium acetate and 5g of polyvinylpyrrolidone into the solution in sequence, and stirring for 90 min; the FeCl3·6H2O and MnSO4·H2The molar mass ratio of O is 2: 1. and (3) placing the stirred solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining, heating the solution to 180 ℃ for 9 hours, cooling the solution, washing the black solid obtained after cooling the solution for a plurality of times by using absolute ethyl alcohol and deionized water until the pH value of the washed supernatant is determined to be neutral, and then placing the washed black solid into a vacuum drying oven to dry the black solid for 5 hours at the temperature of 80 ℃ to obtain the manganese ferrite/porous graphite phase carbon nitride.
This example utilizes sodium acetate (NaAc) hydrolysisAdjusting the pH of the solution so that MnSO is added4·H2O and FeCl3·6H2The molar mass ratio of O to Mn is 1:2 to realize MnFe2O4The synthesis of (2):
Mn2++2Fe3++80H-→Mn(OH)2↓+2Fe(OH)3↓
→MnFe 204+4H 20
the embodiment four is a method for treating low-concentration uranium-containing wastewater by adopting manganese ferrite/porous graphite phase carbon nitride, the concentration of uranium in the low-concentration uranium-containing wastewater is 10mg/L, the pH value is 2-8, and the method comprises the following specific operation steps:
adjusting the pH value of the uranium-containing wastewater to 2-7, adding manganese ferrite/porous graphite phase carbon nitride for adsorption, wherein the addition amount of the manganese ferrite/porous graphite phase carbon nitride is 30-600 mg/L, and performing oscillation adsorption by using a water bath oscillator for 10-140 min.
Detecting the treated uranium-containing wastewater, wherein the detection comprises the following steps:
A. carrying out adsorption detection on uranium-containing wastewater with different pH values: weighing aqueous solution containing U (VI) with concentration of 10mg/L in a conical flask, respectively adjusting the pH of the uranium solution to 2, 3, 4, 5, 6 and 7, and respectively adding graphite-phase carbon nitride g-C according to 200mg/L3N4And the porous graphite phase carbon nitride MCN and the manganese ferrite/porous graphite phase carbon nitride MMCN are subjected to oscillation adsorption for 120min at the speed of 200r/min, filtered, and the supernatant is taken and used for measuring the residual uranium concentration in the uranium-containing wastewater by using a spectrophotometer. The results show that the manganese ferrite/porous graphite phase carbon nitride MMCN is compared with the graphite phase carbon nitride g-C3N4And the porous graphite phase carbon nitride MCN has better uranium adsorption, and the removal rates of uranium are respectively 16.35%, 84.80%, 86.70%, 93.10%, 91.60% and 80.30%.
Graphite phase carbon nitride g-C3N4The trend of the removal rate of the porous graphite phase carbon nitride MCN and the manganese ferrite/porous graphite phase carbon nitride MMCN on U (VI) in the aqueous solution along with the change of the pH value is shown in the attached figure 1, and the graph shows that when the pH value is 5, the manganese ferrite/porous graphite phase carbon nitride MMCN on the U (VI) in the aqueous solution) The removal efficiency of (2) is best, and the removal rate begins to decrease with increasing pH.
B. Carrying out adsorption detection on uranium-containing wastewater with different manganese ferrite/porous graphite phase carbon nitride adding amounts: measuring a U (VI) containing aqueous solution with the concentration of 10mg/L into a conical flask, adjusting the pH value of the U (VI) containing aqueous solution to 5, respectively measuring the adding amount of manganese ferrite/porous graphite phase carbon nitride to 30mg/L, 50mg/L, 60mg/L, 100mg/L, 150mg/L, 200mg/L, 300mg/L, 400mg/L, 500mg/L and 600mg/L, oscillating and adsorbing at the speed of 200r/min for 120min, filtering, taking a supernatant, and measuring the residual uranium concentration in the uranium-containing wastewater by using a spectrophotometer. The results showed uranium removal rates of 66.3%, 74.1%, 82.9%, 87.9%, 88.35%, 89.49%, 92.89%, 95.49%, 95.55%, 95.56%, respectively.
The adsorption rate and adsorption capacity of the manganese ferrite/porous graphite phase carbon nitride to U (VI) in the aqueous solution change with the addition amount are shown in the attached figure 2, and it can be seen from the figure that when the addition amount is 400mg/L, the adsorption rate of the manganese ferrite/porous graphite phase carbon nitride to U (VI) in the aqueous solution reaches the maximum.
C. Carrying out adsorption detection on the uranium-containing wastewater with different adsorption times: measuring a U (VI) containing aqueous solution with the concentration of 10mg/L into a conical flask, adjusting the pH value of the U (VI) containing aqueous solution to 5, adjusting the addition of the manganese ferrite/porous graphite phase carbon nitride to 400mg/L, respectively setting the adsorption time to be 2min, 5min, 10min, 20min, 30min, 40min, 1h, 1.5h and 2h, oscillating and adsorbing at the speed of 200r/min for 120min, filtering, taking a supernatant, and measuring the residual uranium concentration in the uranium-containing wastewater by using a spectrophotometer. The results show that the removal rates of uranium are 70%, 74.2%, 85.6%, 95.46%, 95.56%, 95.23%, 95.82%, 96% and 95.95%, respectively.
The trend of the change of the adsorption rate of the manganese ferrite/porous graphite phase carbon nitride to U (VI) in the aqueous solution along with the adsorption time is shown in the attached figure 3, and as can be seen from the figure, the reaction process is a rapid reaction process within 0-20 min, and after the reaction time is 20min, the whole adsorption process reaches the equilibrium.
By detecting the treated uranium-containing wastewater, the removal rate of uranium by the adsorbent is related to the pH value of the uranium-containing wastewater, the adding amount of manganese ferrite/porous graphite phase carbon nitride and the adsorption time, and the uranium removal effect is best when the pH value is 5, the adding amount of manganese ferrite/porous graphite phase carbon nitride is 400mg/L and the adsorption time is 20 min.
For further explaining the adsorption effect of the manganese ferrite/porous graphite phase carbon nitride, the currently commonly used magnetic silicon dioxide, iron oxide hydrosulfide, magnetic graphene, biochar-chitosan, nano porous alumina and manganese ferrite/porous graphite phase carbon nitride are respectively selected as adsorbents to be applied to adsorption treatment of uranium-containing U (VI) wastewater with the same initial concentration, and the adsorption amount of uranium under the optimal adsorption condition of each adsorbent is calculated, and the results are shown in the following table.
TABLE 1 comparison of the adsorption capacities of different adsorbents for uranium U (VI)
As can be seen from table 1, the adsorption capacity of the manganese ferrite/porous graphite phase carbon nitride is larger than that of the existing common adsorbent, and is 3 times that of the magnetic graphene, 10 times that of the magnetic silica, and 30 times that of the nano porous alumina, so that the manganese ferrite/porous graphite phase carbon nitride prepared by the method has strong treatment capacity on uranium-containing U (vi) wastewater.
And after the manganese ferrite/porous graphite phase carbon nitride is adsorbed and saturated, putting the manganese ferrite/porous graphite phase carbon nitride adsorbed with uranium into a hydrochloric acid solution, analyzing the uranium in the manganese ferrite/porous graphite phase carbon nitride, washing the mixture for several times by using deionized water until the pH value of the washed supernatant is determined to be neutral, and drying the analyzed manganese ferrite/porous graphite phase carbon nitride for repeated use.
And (3) detecting the reusability of the manganese ferrite/porous graphite phase carbon nitride in uranium-containing wastewater treatment:
a. five parts of 50ml of aqueous solution containing U (VI) with the concentration of 10mg/L are respectively weighed in a conical flask, and the pH value of the aqueous solution containing U (VI) is adjusted to 5.
b. Adding the manganese ferrite/porous graphite phase carbon nitride into a first U (VI) containing aqueous solution according to the adding amount of 400mg/L, placing the solution into a water bath oscillator for oscillation and adsorption, wherein the adsorption and oscillation time is 20min, filtering, taking supernate, measuring the concentration of residual uranium in uranium-containing wastewater by using a spectrophotometer, and calculating the removal rate of uranium in the first U (VI) containing aqueous solution.
c. Putting the manganese ferrite/porous graphite phase carbon nitride in the first U (VI) -containing aqueous solution into 0.1mol/L hydrochloric acid, oscillating for 2h, measuring the uranium concentration of a supernatant to determine that uranium adsorbed by the manganese ferrite/porous graphite phase carbon nitride is resolved, washing the resolved manganese ferrite/porous graphite phase carbon nitride for a plurality of times by using deionized water until the pH value of the washed supernatant is determined to be neutral, and drying the washed manganese ferrite/porous graphite phase carbon nitride.
d. And repeating the step b to the step c, respectively adding the dried manganese ferrite/porous graphite phase carbon nitride into the second to the fifth parts of the aqueous solution containing the U (VI), and calculating the removal rate of uranium in the second to the fifth parts of the aqueous solution containing the U (VI).
The results of the adsorption-desorption of the uranium-containing wastewater by the manganese ferrite/porous graphite phase carbon nitride are shown in the attached figures 4-5, and the results show that the adsorption rate of the manganese ferrite/porous graphite phase carbon nitride to U (VI) is still more than 89% after the manganese ferrite/porous graphite phase carbon nitride is repeatedly used for five times, so that the manganese ferrite/porous graphite phase carbon nitride has good repeated utilization rate for treating low-concentration U (VI) -containing wastewater.
Claims (3)
1. The preparation method of the manganese ferrite/porous graphite phase carbon nitride is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
step one, preparing porous graphite phase carbon nitride: dissolving melamine and calcium carbonate in deionized water, and carrying out ultrasonic treatment for 30 min; heating and stirring the treated solution at 60-90 ℃ until the solution is gelatinous, drying the solution in vacuum, fully grinding the dried powder, and sieving the powder by a 200-mesh sieve;
calcining the ground and sieved powder in a muffle furnace at 500-550 ℃ for 2-5 h, grinding the calcined product through a 200-mesh sieve, and removing a calcium carbonate template by using dilute hydrochloric acid until no carbon dioxide bubbles are generated in water; wherein the mass ratio of melamine to calcium carbonate is 5: 1;
washing the porous graphite-phase carbon nitride obtained after the calcium carbonate template is removed with deionized water for multiple times until the solution is neutral, and placing the solution in an oven for drying for later use;
step two, preparing manganese ferrite/porous graphite phase carbon nitride: weighing porous graphite phase carbon nitride, adding the porous graphite phase carbon nitride into an ethylene glycol solution, and performing ultrasonic dispersion for 30-60 min; then FeCl is added in turn3·6H2O、MnSO4·H2O, sodium acetate and polyvinylpyrrolidone, and stirring for 30-90 min;
wherein, the porous graphite phase carbon nitride and FeCl3·6H2O、MnSO4·H2The mass ratio of O to sodium acetate to polyvinylpyrrolidone is 1: 0.5-2: 0.2-0.5: 1.5-2.5: 0.1 to 0.5; FeCl3·6H2O and MnSO4·H2The molar mass ratio of O is 2: 1; the ratio of the porous graphite phase carbon nitride to the glycol solution is 20 g/L-50 g/L;
and (3) placing the stirred solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining, heating the solution to 110-180 ℃ for 9-12 h, cooling, washing the black solid obtained after cooling with absolute ethyl alcohol and deionized water for several times until the pH value of the washed supernatant is determined to be neutral, and then placing the washed black solid into a vacuum drying oven for drying at 60-80 ℃ for 5-7 h to obtain the manganese ferrite/porous graphite phase carbon nitride.
2. The method for treating low-concentration uranium-containing wastewater by adopting the manganese ferrite/porous graphite phase carbon nitride according to claim 1, wherein the concentration of uranium in the low-concentration uranium-containing wastewater is 10mg/L, and the pH value is 2-8, and the method is characterized in that: comprises the following specific operation steps of,
adjusting the pH value of the uranium-containing wastewater to 4-6, adding manganese ferrite/porous graphite phase carbon nitride for adsorption, wherein the addition amount of the manganese ferrite/porous graphite phase carbon nitride is 150-600 mg/L, and performing oscillation adsorption by using a water bath oscillator for 10-140 min.
3. The method of treating low-concentration uranium-containing wastewater with manganese ferrite/porous graphite-phase carbon nitride according to claim 2, wherein: desorbing the saturated manganese ferrite/porous graphite phase carbon nitride, wherein the desorption process is as follows:
firstly, separating saturated manganese ferrite/porous graphite phase carbon nitride from uranium-containing wastewater by using a magnet, then putting the manganese ferrite/porous graphite phase carbon nitride into hydrochloric acid for desorption, separating the desorbed manganese ferrite/porous graphite phase carbon nitride from the hydrochloric acid by using the magnet and washing the desorbed manganese ferrite/porous graphite phase carbon nitride with deionized water for a plurality of times until the washed supernatant is neutral, and drying the desorbed manganese ferrite/porous graphite phase carbon nitride for reuse.
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