CN113683151A - Preparation method of magnetic hydrothermal carbon for purifying aquaculture water - Google Patents
Preparation method of magnetic hydrothermal carbon for purifying aquaculture water Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 55
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- SEBFKMXJBCUCAI-UHFFFAOYSA-N NSC 227190 Natural products C1=C(O)C(OC)=CC(C2C(OC3=CC=C(C=C3O2)C2C(C(=O)C3=C(O)C=C(O)C=C3O2)O)CO)=C1 SEBFKMXJBCUCAI-UHFFFAOYSA-N 0.000 claims abstract description 41
- SEBFKMXJBCUCAI-HKTJVKLFSA-N silibinin Chemical compound C1=C(O)C(OC)=CC([C@@H]2[C@H](OC3=CC=C(C=C3O2)[C@@H]2[C@H](C(=O)C3=C(O)C=C(O)C=C3O2)O)CO)=C1 SEBFKMXJBCUCAI-HKTJVKLFSA-N 0.000 claims abstract description 41
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- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
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- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 22
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- 238000002474 experimental method Methods 0.000 description 14
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 9
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
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- 229910052698 phosphorus Inorganic materials 0.000 description 5
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- 235000015097 nutrients Nutrition 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 244000272459 Silybum marianum Species 0.000 description 2
- 235000010841 Silybum marianum Nutrition 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A preparation method of magnetic hydrothermal carbon for purifying aquaculture water relates to a preparation method of hydrothermal carbon. The invention aims to solve the technical problems of environmental pollution and high sulfur in the existing method for preparing the hydrothermal carbon. The preparation method of the magnetic hydrothermal carbon for purifying the aquaculture water comprises the following steps: FeSO (ferric oxide) is added4·7H2Placing O in a reaction kettle, adding 10mL of distilled water, performing ultrasonic treatment for 10min, adding silymarin extract, performing ultrasonic treatment for 10min, adding 2g of clematis residue into the reaction kettle, performing ultrasonic treatment for 10min, sealing the reaction kettle, heating and cooling to room temperature, centrifuging, and drying to obtain the compound silymarin. The carbon material has the advantages of green and pollution-free raw materials, easily controlled reaction conditions and the like, and realizes that the Fe is prepared by using the plant extract as a reducing agent and a stabilizing agent without adding other chemical reagents3O4And (3) nano materials. The inventionBelongs to the field of magnetic hydrothermal carbon preparation.
Description
Technical Field
The invention relates to a preparation method of hydrothermal carbon.
Background
With the development of social economy and the increasing demand of people on aquatic products, the aquaculture industry is rapidly developed. The problems of culture water body pollution, regional environment deterioration and the like caused by large-scale high-density culture are increasingly prominent. The nitrogen and phosphorus nutrient elements are main pollutants in the aquaculture process and come from baits added in the aquaculture process and excrement of cultured animals. Accumulation of nitrogen and phosphorus nutrient elements can seriously threaten cultivated organisms and water body environment. Therefore, the method for efficiently removing the nitrogen and phosphorus nutrient elements in the water body is significant.
The biochar is a carbon-rich material produced by high-temperature thermal cracking of waste biomass raw materials under the condition of limited oxygen, and has the advantages of high carbon content, large specific surface area, strong adsorption capacity, stable structure and the like, so the biochar is widely applied to the aspects of sewage treatment, water environment restoration and the like. However, the disadvantages of difficult recovery and reuse of biochar, less types of surface active sites, low content and the like limit the further popularization of the biochar. In recent years, the biological carbon-loaded magnetic material not only can improve the adsorption performance of the material, but also is beneficial to the recycling of the catalyst. The magnetic biochar can be recycled through a magnetic field, so that the cost of the adsorbent is further reduced, and the magnetic biochar has a good prospect. However, the existing method for preparing the hydrothermal carbon has the defects of no environmental protection and high sulfur.
Disclosure of Invention
The invention aims to solve the technical problems that the existing method for preparing the hydrothermal carbon is not environment-friendly and high in sulfur, and provides a method for preparing the magnetic hydrothermal carbon for purifying aquaculture water.
The preparation method of the magnetic hydrothermal carbon for purifying the aquaculture water comprises the following steps:
firstly, 1g of silymarin is put into a 50mL conical flask, and 50mL of silymarin with the concentration of 0.4 mol.L is added-1Standing the solution at room temperature for 30min, performing ultrasonic treatment for 30min, and standing at room temperature for 12h to obtain silymarin extractive solution;
secondly, 1g of FeSO4·7H2Placing O in a reaction kettle, and adding 10mL of distilled water into the reaction kettleSounding for 10min, adding 50mL of silymarin extracting solution, performing ultrasonic treatment for 10min, completely mixing, adding 2g of clematis residue into a reaction kettle, performing ultrasonic treatment for 10min, and sealing the reaction kettle;
thirdly, heating the sealed reaction kettle to 180-260 ℃, reacting for 1-4h, cooling to room temperature, opening the reaction kettle, transferring the content to a 100mL centrifuge tube, placing the centrifuge tube in a centrifuge for solid-liquid separation for 10min at 4000r/min, washing the solid-phase product with distilled water and absolute ethyl alcohol until the waste liquid becomes colorless, and drying the residue of the separated product in a vacuum drying box at 60 ℃ for 12h to obtain the magnetic hydrothermal carbon for purifying the aquaculture water.
Step one the ultrasonic frequency is 59 Hz.
Step two, 10mL of distilled water is added into the reaction kettle, and the ultrasonic frequency is 28 Hz.
Step two, adding 50mL of silymarin extracting solution, wherein the ultrasonic frequency is 28 Hz.
And step two, adding 2g of clematis residue, wherein the ultrasonic frequency is 28 Hz.
The reaction temperature in the third step is 180 ℃.
The reaction time in step three is 3 h.
The invention takes waste clematis residue (waste of pharmaceutical factory) as raw material, prepares hydrothermal carbon by hydrothermal synthesis method, and adopts FeSO4·7H2O and silymarin modify the clematis residue hydrothermal carbon to obtain the magnetic hydrothermal carbon which is nontoxic, environment-friendly, low in sulfur, excellent in hydrothermal stability, remarkable in environmental benefit and capable of rapidly adsorbing pollutants in a water body. The carbon material has the advantages of green and pollution-free raw materials, easily controlled reaction conditions and the like, and realizes that the Fe is prepared by using the plant extract as a reducing agent and a stabilizing agent without adding other chemical reagents3O4And (3) nano materials.
In the preparation process of the hydrothermal carbon, FeSO is adopted4·7H2O as iron source, NaOH as alkali source for precipitating and crystallizing iron ions, and silymarin as reducing agent for precipitating and crystallizing Fe3+Partially reduced to Fe2+The function of (1). And preparing the biomass-based magnetic hydrothermal carbon. The existing method for preparing the magnetic hydrothermal carbon is mainly to prepare the hydrothermal carbonOn the basis, the magnetic hydrothermal carbon is prepared by a two-step method through a magnetic activation process, the hydrothermal carbon is prepared in one step, the preparation processes of hydrothermal carbonization and activation magnetization in the past are simplified, the production method is simpler, and the cost is reduced. In addition, silymarin is a natural flavonolignan compound extracted from seed coat of Silybum marianum of Compositae. Silymarin has practical application values in multiple aspects such as oxidation resistance, organism immunity improvement, growth promotion and the like in aquatic products, and is a functional feed additive with important development and application potential. Therefore, the magnetic hydrothermal carbon is prepared by using the silymarin, no additional chemical reagents such as organic solvents and the like are needed to be added in the preparation process, and the prepared hydrothermal carbon material does not cause environmental pollution in the preparation and use processes, so that the method is a green preparation method.
Drawings
FIG. 1 is an SEM image of hydrothermal charcoal (CC) in experiment four;
FIG. 2 shows Fe in experiment IV3O4SEM images of modified hydrothermal charcoal (TCC);
FIG. 3 is an SEM image of magnetic hydrothermal carbon (GCC) for aquaculture water purification in experiment four;
FIG. 4 shows hydrothermal charcoal (CC) and Fe in experiment IV3O4XRD patterns of modified hydrothermal carbon (TCC) and magnetic hydrothermal carbon (GCC) for purification of aquaculture water;
FIG. 5 shows FeSO obtained in experiment I4·7H2A graph of the influence of the addition of O on the yield and the adsorption of the magnetic hydrothermal carbon;
FIG. 6 is a graph showing the effect of reaction temperature on hydrothermal carbon yield and adsorption amount in experiment two;
FIG. 7 is a graph showing the effect of reaction time on hydrothermal carbon yield and adsorption amount in experiment three.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the magnetic hydrothermal carbon for purifying aquaculture water is carried out according to the following steps:
firstly, 1g of silymarin is put into a 50mL conical flask, and 50mL of silymarin with the concentration of 0.4 mol.L is added-1Standing the solution at room temperature for 30min, performing ultrasonic treatment for 30min, and standing at room temperature for 12h to obtain silymarin extractive solution;
secondly, 1g of FeSO4·7H2Placing O in a reaction kettle, adding 10mL of distilled water into the reaction kettle, performing ultrasonic treatment for 10min, adding 50mL of silymarin extracting solution, performing ultrasonic treatment for 10min, completely mixing, adding 2g of clematis residue into the reaction kettle, performing ultrasonic treatment for 10min, and sealing the reaction kettle;
thirdly, heating the sealed reaction kettle to 180-260 ℃, reacting for 1-4h, cooling to room temperature, opening the reaction kettle, transferring the content to a 100mL centrifuge tube, placing the centrifuge tube in a centrifuge for solid-liquid separation for 10min at 4000r/min, washing the solid-phase product with distilled water and absolute ethyl alcohol until the waste liquid becomes colorless, and drying the residue of the separated product in a vacuum drying box at 60 ℃ for 12h to obtain the magnetic hydrothermal carbon for purifying the aquaculture water.
The second embodiment is as follows: the difference between the present embodiment and the first embodiment is that the ultrasonic frequency in the first step is 59 Hz. The rest is the same as the first embodiment.
The third concrete implementation mode: the difference between the first embodiment and the second embodiment is that 10mL of distilled water is added into the reaction kettle in the second step, and the ultrasonic frequency is 28 Hz. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between the second embodiment and the first to the third embodiment is that 50mL of silymarin extract is added in the second step, and the ultrasonic frequency is 28 Hz. The rest is the same as one of the first to third embodiments.
The fifth concrete implementation mode: the difference between the embodiment and one of the first to the fourth embodiments is that 2g of clematis residue is added in the second step, and the ultrasonic frequency is 28 Hz. The rest is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: this embodiment differs from one of the first to fifth embodiments in that the reaction temperature in step three is 180 ℃. The rest is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is that the reaction time in step three is 3 hours. The rest is the same as one of the first to sixth embodiments.
The following experiments are adopted to verify the effect of the invention:
experiment one:
the preparation method of the magnetic hydrothermal carbon for purifying the aquaculture water comprises the following steps:
firstly, 1g of silymarin is put into a 50mL conical flask, and 50mL of silymarin with the concentration of 0.4 mol.L is added-1Standing the solution at room temperature for 30min, performing ultrasonic treatment for 30min, and standing at room temperature for 12h to obtain silymarin extractive solution;
secondly, mixing 0.2g, 0.4g, 0.6g, 0.8g and 1.0g of FeSO4·7H2Placing O in a reaction kettle, adding 10mL of distilled water into the reaction kettle, performing ultrasonic treatment for 10min, adding 50mL of silymarin extracting solution, performing ultrasonic treatment for 10min, completely mixing, adding 2g of clematis residue into the reaction kettle, performing ultrasonic treatment for 10min, and sealing the reaction kettle;
and thirdly, heating the sealed reaction kettle to 180 ℃, reacting for 3 hours, cooling to room temperature, opening the reaction kettle, transferring the content to a 100mL centrifuge tube, placing the centrifuge tube in a centrifuge for solid-liquid separation for 10 minutes at 4000r/min, washing the solid-phase product with distilled water and absolute ethyl alcohol until the waste liquid becomes colorless, and drying the residue of the separated product in a vacuum drying oven at 60 ℃ for 12 hours to obtain the magnetic hydrothermal carbon (GCC) for purifying the aquaculture water.
FeSO4·7H2The addition of O not only directly influences the yield of the hydrothermal carbon, but also can change the adsorption capacity of the hydrothermal carbon. Under otherwise identical conditions, FeSO4·7H2The more the amount of O added, the more Fe is generated in the hydrothermal carbonization reaction process3O4The greater the amount, the higher the hydrothermal char yield (fig. 5). Methylene blue is used for treating certain fish diseases or used as a disinfectant in aquatic product culture. The adsorption performance of the carbon material was evaluated using Methylene Blue (MB) as an adsorbate. When FeSO4·7H2The highest GCC carbon yield and methylene blue adsorption were achieved at 1.0g of O (FIG. 5).
Experiment two:
the preparation method of the magnetic hydrothermal carbon for purifying the aquaculture water comprises the following steps:
firstly, 1g of silymarin is put into a 50mL conical flask, and 50mL of silymarin with the concentration of 0.4 mol.L is added-1Standing the solution at room temperature for 30min, performing ultrasonic treatment for 30min, and standing at room temperature for 12h to obtain silymarin extractive solution;
secondly, 1g of FeSO4·7H2Placing O in a reaction kettle, adding 10mL of distilled water into the reaction kettle, performing ultrasonic treatment for 10min, adding 50mL of silymarin extracting solution, performing ultrasonic treatment for 10min, completely mixing, adding 2g of clematis residue into the reaction kettle, performing ultrasonic treatment for 10min, and sealing the reaction kettle;
thirdly, heating the sealed reaction kettle to 180 ℃, 200 ℃, 220 ℃, 240 ℃ and 260 ℃, reacting for 3h, cooling to room temperature, opening the reaction kettle, transferring the content to a 100mL centrifuge tube, placing the centrifuge tube in a centrifuge for solid-liquid separation for 10min at 4000r/min, washing the solid-phase product with distilled water and absolute ethyl alcohol until the waste liquid becomes colorless, and drying the residue of the separated product in a vacuum drying oven at 60 ℃ for 12h to obtain the magnetic hydrothermal carbon for purifying the aquaculture water.
Temperature is an important factor influencing hydrothermal carbonization reaction, and the increase of temperature can reduce the viscosity of subcritical water, so that the subcritical water can enter pores of biomass more easily, and the degradation of organic matters is accelerated. Under the same reaction time, the yield of the hydrothermal carbon is reduced along with the increase of the reaction temperature, and the method completely accords with the rule that lignin and cellulose organic matters are more easily degraded and converted when the temperature is higher in the hydrothermal carbonization process, so that the quality of the hydrothermal carbon is reduced. Between 180 ℃ and 260 ℃, the unit adsorption amount of the GCC prepared at different reaction temperatures to the MB is reduced along with the increase of the preparation reaction temperature. The method is characterized in that the reaction temperature is increased, the types of functional groups on the surface of clematis chinensis slag are changed (the biological carbon surface functional groups are continuously reduced along with the increase of the pyrolysis temperature, the dehydration and decarboxylation reaction is accelerated, the carbon content of the biological carbon is increased along with the increase of the carbonization temperature, the aromaticity is enhanced, the oxygen and hydrogen content is reduced, the polarity and the hydrophilicity are weakened, the number of acidic functional groups is gradually reduced along with the increase of the pyrolysis temperature of the biological carbon, and the number of basic functional groups is increased). Considering the carbon yield (figure 6) and the adsorption amount, 180 ℃ is the optimal temperature for preparing different hydrothermal carbons.
Experiment three:
the preparation method of the magnetic hydrothermal carbon for purifying the aquaculture water comprises the following steps:
firstly, 1g of silymarin is put into a 50mL conical flask, and 50mL of silymarin with the concentration of 0.4 mol.L is added-1Standing the solution at room temperature for 30min, performing ultrasonic treatment for 30min, and standing at room temperature for 12h to obtain silymarin extractive solution;
secondly, 1g of FeSO4·7H2Placing O in a reaction kettle, adding 10mL of distilled water into the reaction kettle, performing ultrasonic treatment for 10min, adding 50mL of silymarin extracting solution, performing ultrasonic treatment for 10min, completely mixing, adding 2g of clematis residue into the reaction kettle, performing ultrasonic treatment for 10min, and sealing the reaction kettle;
and thirdly, heating the sealed reaction kettle to 180 ℃, reacting for 1, 2, 3 and 4 hours, cooling to room temperature, opening the reaction kettle, transferring the content to a 100mL centrifuge tube, placing the centrifuge tube in a centrifuge for solid-liquid separation for 10 minutes at 4000r/min, washing the solid-phase product with distilled water and absolute ethyl alcohol until the waste liquid becomes colorless, and drying the residue of the separated product in a vacuum drying oven at 60 ℃ for 12 hours to obtain the magnetic hydrothermal carbon for purifying the aquaculture water.
Under the same conditions, the charcoal yield of the hydrothermal charcoal (FIG. 7) showed an overall decreasing trend with increasing reaction time in the reaction time range of 1-4h, and all gave the lowest charcoal yield results under the reaction time condition of 4 h. The carbon yield then increased somewhat with increasing reaction time. The adsorption of MB by GCC all tended to increase over the shorter reaction time, and declined slightly and remained at a certain level after 3h (fig. 7). 3h, the optimal time for preparing the hydrothermal carbon.
Experiment four:
the preparation method of the magnetic hydrothermal carbon for purifying the aquaculture water comprises the following steps:
firstly, 1g of silymarin is put into a 50mL conical flask, and 50mL of silymarin with the concentration of 0.4 mol.L is added-1Standing the solution at room temperature for 30min, performing ultrasonic treatment for 30min, and standing at room temperature for 12h to obtain silymarin extractive solution;
secondly, 1g of FeSO4·7H2Placing O in a reaction kettle, adding 10mL of distilled water into the reaction kettle, performing ultrasonic treatment for 10min, adding 50mL of silymarin extracting solution, performing ultrasonic treatment for 10min, completely mixing, adding 2g of clematis residue into the reaction kettle, performing ultrasonic treatment for 10min, and sealing the reaction kettle;
and thirdly, heating the sealed reaction kettle to 180 ℃, reacting for 3 hours, cooling to room temperature, opening the reaction kettle, transferring the content to a 100mL centrifuge tube, placing the centrifuge tube in a centrifuge for solid-liquid separation for 10 minutes at 4000r/min, washing the solid-phase product with distilled water and absolute ethyl alcohol until the waste liquid becomes colorless, and drying the residue of the separated product in a vacuum drying oven at 60 ℃ for 12 hours to obtain the magnetic hydrothermal carbon (GCC) for purifying the aquaculture water.
Fe3O4The preparation method of the modified hydrothermal carbon (TCC) comprises the following steps:
weighing 8g of NaOH in a 500mL volumetric flask, and fixing the volume to the scale with distilled water to prepare 0.4 mol.L-1The NaOH solution of (1). Then 1g of FeSO was weighed4·7H2And O, putting the mixture into a reaction kettle, adding 10mL of distilled water into the reaction kettle, and performing ultrasonic treatment for 10min to completely dissolve the mixture. Then 50mL of NaOH solution is measured and added into the reaction kettle, ultrasonic treatment is carried out for 10min, 2g of clematis residue is added into the reaction kettle after complete mixing, and the reaction kettle is sealed after ultrasonic treatment for 10 min. Heating the reaction kettle to 180 ℃, reacting for 3h, taking out after the reaction time is over, and cooling to room temperature. The reaction kettle is opened, the content is transferred to a 100mL centrifuge tube, and the centrifuge tube is placed in a centrifuge for solid-liquid separation for 10min at 4000 r/min. And washing the solid phase product with distilled water and absolute ethyl alcohol until the waste liquid becomes colorless. The separated product is dried in a vacuum drying oven at 60 ℃ for 12 hours to obtain Fe3O4The modified hydrothermal carbon product, called TCC.
Scanning electron microscope SEM for hydrothermal carbon (CC) and Fe3O4The characterization of three materials of modified hydrothermal carbon (TCC) and GCC shows that the CC surface has more irregular mesopores and is smoother, and the TCC and GCC have changed shapes and are rough. Because of Fe attached to TCC and GCC3O4The rough surface provides more adsorption to the adsorbate without the appearance of a pore structureA site. The analysis of three hydrothermal carbons of CC, TCC and GCC by XRD shows that magnetic Fe is successfully loaded on the surfaces of TCC and GCC3O4Nanoparticles. Fe3O4The adhesion of the modified hydrothermal carbon enables the hydrothermal carbon to have the magnetic recovery function, and the adsorption performance of the modified hydrothermal carbon is obviously improved.
The silymarin functionalized magnetic hydrothermal carbon has adsorption performance obviously superior to that of single pure hydrothermal carbon and Fe3O4Modified hydrothermal charcoal. In the nanometer Fe3O4In the formation process, silymarin acts as a reducing agent to react Fe3+Partially reduced to Fe2+The NaOH is used as a precipitator in the system to precipitate and crystallize iron ions. The precondition for synthesizing magnetic materials in experiments is that the iron element needs to exist in the form of ionic or non-stable compounds, when Fe3+With stabilized Fe2O3When present, the composition of the crystalline phase cannot be changed by hydrothermal processes. Fe was used in this experiment2+As an iron source, but Fe2+Is very easy to be oxidized into Fe3+Silymarin can act as a reducing agent, making Fe2+/Fe3+Kept at the proper ratio. The modification process of the hydrothermal carbon improves the adsorption capacity of the carbon to MB, particularly GCC, and after silybum marianum is functionalized, the maximum adsorption capacity of the hydrothermal carbon is 2.3 times that of CC and 1.5 times that of TCC. The magnetic particles are loaded on the carbon surface, so that adsorption sites and magnetism are increased. When the carbon dosage in the MB solution is 50mg, the optimum adsorption quantity of GCC is 98.88mg g-1. GCC increases rapidly 30min before adsorbing MB, reaches equilibrium after 4h, the adsorption process is mainly multi-molecular layer adsorption, and van der Waals force and hydrogen bond interaction force exist among adsorption molecules.
The GCC is subjected to constant temperature oscillation adsorption test at the temperature of 25 ℃, the rotating speed of 120r/min, the initial ammonia nitrogen concentration of 1.0mg/L and the phosphorus concentration of 0.5 mg/L. After constant temperature oscillation for 4h, the removal rate of ammonia nitrogen by GCC is 91%, and the removal rate of phosphorus is 89%.
Claims (7)
1. The preparation method of the magnetic hydrothermal carbon for aquaculture water purification is characterized by comprising the following steps:
firstly, 1g of silymarin is put into a 50mL conical flask, and 50mL of silymarin with the concentration of 0.4 mol.L is added-1Standing the solution at room temperature for 30min, performing ultrasonic treatment for 30min, and standing at room temperature for 12h to obtain silymarin extractive solution;
secondly, 1g of FeSO4·7H2Placing O in a reaction kettle, adding 10mL of distilled water into the reaction kettle, performing ultrasonic treatment for 10min, adding 50mL of silymarin extracting solution, performing ultrasonic treatment for 10min, completely mixing, adding 2g of clematis residue into the reaction kettle, performing ultrasonic treatment for 10min, and sealing the reaction kettle;
thirdly, heating the sealed reaction kettle to 180-260 ℃, reacting for 1-4h, cooling to room temperature, opening the reaction kettle, transferring the content to a 100mL centrifuge tube, placing the centrifuge tube in a centrifuge for solid-liquid separation for 10min at 4000r/min, washing the solid-phase product with distilled water and absolute ethyl alcohol until the waste liquid becomes colorless, and drying the residue of the separated product in a vacuum drying box at 60 ℃ for 12h to obtain the magnetic hydrothermal carbon for purifying the aquaculture water.
2. The method for preparing the magnetic hydrothermal carbon for aquaculture water purification according to claim 1, wherein the ultrasonic frequency in the first step is 59 Hz.
3. The method for preparing the magnetic hydrothermal carbon for purifying aquaculture water according to claim 1, wherein 10mL of distilled water is added into the reaction kettle in the step two, and the ultrasonic frequency is 28 Hz.
4. The preparation method of the magnetic hydrothermal carbon for aquaculture water purification according to claim 1, characterized in that 50mL of silymarin extract is added in the second step, and the ultrasonic frequency is 28 Hz.
5. The preparation method of the magnetic hydrothermal carbon for aquaculture water purification according to claim 1, characterized in that 2g of clematis residue is added in the second step, and the ultrasonic frequency is 28 Hz.
6. The method for preparing the magnetic hydrothermal carbon for purifying aquaculture water according to claim 1, wherein the reaction temperature in the third step is 180 ℃.
7. The preparation method of the magnetic hydrothermal carbon for aquaculture water purification according to claim 1, characterized in that the reaction time in the third step is 3 h.
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