CN113860411B - Oil body-polypyrrole solar energy absorbing material and photo-thermal evaporation water purifier - Google Patents
Oil body-polypyrrole solar energy absorbing material and photo-thermal evaporation water purifier Download PDFInfo
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
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- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/211—Solar-powered water purification
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
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Abstract
The invention discloses an oil body-polypyrrole solar energy absorption material, which is prepared by the following method: 1) Adding vegetable oil into pyrrole solution, stirring, and centrifuging; 2) Adding the oil body obtained in the step 1) into a ferric chloride solution, stirring for reaction, and centrifuging to obtain an oil body-polypyrrole solar energy absorbing material; 3) Freeze-drying; by utilizing the method, the recovery rate is high; the synthesized oil body-polypyrrole solar energy absorption material is stable in state and has more cycle times; the result shows that the collected fresh water does not contain bacteria, so that the fresh water is effectively purified and has better water quality; the conductivity is low, and the impurity content is low; according to the invention, by utilizing the characteristic that an oil body is taken as a light carrier, pyrrole molecules are polymerized in situ to form an oil body-polypyrrole solar energy absorption material, so that non-drinking water such as domestic sewage, river water, seawater and the like can be effectively converted into high-quality fresh water resources under the irradiation of solar energy; the low-cost and high-efficiency regeneration of the fresh water resources can be realized.
Description
Technical Field
The invention belongs to the technical field of solar energy and water treatment, and particularly relates to an oil body-polypyrrole solar energy absorbing material and a photo-thermal evaporation water purifier.
Background
At present, the shortage of fresh water resources becomes a global problem, and the shortage problem of fresh water resources becomes more serious due to serious water body pollution caused by industrial, agricultural and domestic wastewater. Statistically, more than one billion people are in the predicament of water shortage worldwide. Although over 70% of the earth's surface is covered by water, fresh water resources account for only about 3%, and the number of fresh water resources that can be directly utilized by humans is even more exponential. Therefore, it is urgent to convert various water sources which cannot be directly utilized into fresh water resources which can be directly utilized. The traditional water desalination technology mainly comprises a distillation method, an ion exchange method, a reverse osmosis method, an electrodialysis method and the like, but has the defects of high cost, large energy consumption, large technical difficulty, frequent replacement of filter materials and the like. Nowadays, solar energy, as a clean energy source, has been widely used in a novel water desalination technology using photo-thermal conversion due to its nearly infinite storage and its characteristics of cleanness and no pollution. Polypyrrole is an organic-based photothermal material, and has huge potential in water desalination treatment due to the advantages of convenience in preparation, good stability, high photothermal conversion efficiency and the like, but the single polypyrrole can be precipitated at the bottom of water, and heat loss is huge in solar water desalination treatment, so that the polypyrrole is required to float on the surface of water to fully utilize the photothermal performance of the polypyrrole. The oil body is an organelle of a spherical structure extracted from plant seeds, the diameter of the organelle is 1.5-2.5 mu m, the inside of the oil body is formed by triacylglycerol wrapped by a phospholipid monomolecular layer, and the outside of the oil body is composed of oil body binding protein embedded into the surface of the oil body.
Disclosure of Invention
The invention aims to provide an oil body-polypyrrole solar energy absorbing material and a photothermal evaporation water purifier.
The oil body-polypyrrole solar energy absorption material is prepared by the following method:
1) Adding vegetable oil into pyrrole solution, stirring, and centrifuging;
2) Adding the oil body obtained in the step 1) into a ferric chloride solution, stirring for reaction, and centrifuging to obtain an oil body-polypyrrole solar energy absorbing material;
3) Freeze-drying;
the vegetable oil body is an artificial oil body, a safflower oil body, a soybean oil body and/or a peanut oil body;
the concentration of the pyrrole solution is 0.1-0.2M, and the concentration of the ferric chloride solution is 0.1-0.2M;
the vegetable oil body is freeze-dried vegetable oil body, added with buffer solution for redissolving and then centrifuged to obtain the vegetable oil body;
the freeze-drying is to freeze-dry after evenly mixing oil body-polypyrrole with a dispersing agent and a buffer solution;
the centrifugation in the step 1) is performed for 5 min at room temperature by slowly stirring for 1h and 12000 rpm;
slowly stirring for 1h at room temperature by the centrifugation of the step 2) to polymerize pyrrole in situ, and centrifuging at 8000rpm for 3 min;
the freeze-drying is that oil body-polypyrrole, mannitol and PBS buffer solution are fully and uniformly mixed according to the mass ratio of 2.
The invention provides an oil body-polypyrrole solar energy absorption material, which is prepared by the following method: 1) Adding vegetable oil into pyrrole solution, stirring, and centrifuging; 2) Adding the oil body obtained in the step 1) into a ferric chloride solution, stirring for reaction, and centrifuging to obtain an oil body-polypyrrole solar energy absorbing material; 3) Freeze-drying; by utilizing the method, the recovery rate is high; the synthesized oil body-polypyrrole solar energy absorption material is stable in state and has more cycle times; the result shows that the collected fresh water does not contain bacteria, so that the fresh water is effectively purified and has better water quality; the conductivity is low, and the impurity content is low; according to the invention, by utilizing the characteristic that an oil body is taken as a light carrier, pyrrole molecules are polymerized in situ to form an oil body-polypyrrole solar energy absorption material, so that non-drinking water such as domestic sewage, river water, seawater and the like can be effectively converted into high-quality fresh water resources under the irradiation of solar energy; the low-cost and high-efficiency regeneration of the fresh water resources can be realized.
Drawings
FIG. 1 is a photograph comparing the state of oil bodies-polypyrrole and polypyrrole solar absorbing materials in water;
FIG. 2 images of oil bodies and oil bodies-polypyrrole solar absorber material under a microscope;
FIG. 3 is a self-made fresh water resource collecting device; 1. an evaporation cover; 2. a container; 3. oil body-polypyrrole solar absorber material;
fig. 4 is a diagram illustrating a fresh water process object picture collected by the self-made fresh water resource collecting device;
FIG. 5 is a graph of the rate of recovery of fresh water using oil bodies-polypyrrole solar absorber material under solar irradiation;
FIG. 6 is a graph of the efficiency of fresh water recovery using oil bodies-polypyrrole solar absorber materials under solar irradiation;
FIG. 7 comparison of the state of an oil body-polypyrrole solar absorber material synthesized with fresh safflower oil bodies before and after desalination;
FIG. 8 is a graph comparing resistivity of natural river water and artificial seawater and fresh water collected using the same;
FIG. 9 is a photograph showing the detection of bacteria contained in natural river water, artificial seawater, and fresh water collected by the application method.
Detailed Description
Example 1 preparation of safflower oil body-polypyrrole solar absorber material
1. Preparation of safflower oil freeze-dried powder
Taking 2 g shelled safflower seeds, adding 20 mL PBS buffer (pH = 7.4), fully grinding, centrifuging at 12000 rpm for 5 min to obtain an oil body layer, adding the PBS buffer again into the oil body layer, uniformly mixing, centrifuging at 12000 rpm for 5 min, repeating the operations until no precipitate is generated, and obtaining the oil body layer, namely the safflower oil body. And fully and uniformly mixing the obtained safflower oil body with mannitol and a PBS buffer solution according to the mass ratio of 2.
2. Preparation of safflower oil body-polypyrrole composite material
1) Re-dissolving 0.5 g fresh safflower oil, adding into 10 mL pyrrole solution (0.15 mol/L), slowly stirring at room temperature for 1h, centrifuging at 12000 rpm for 5 min, and keeping oil layer; and (3) adding the retained oil layer into a 10 mL ferric chloride solution (0.15 mol/L), slowly stirring 1h at room temperature to polymerize the pyrrole in situ, centrifuging at 8000rpm for 3 min, and retaining the oil layer to obtain the oil-polypyrrole solar absorbing material. And (3) fully and uniformly mixing the obtained oil body-polypyrrole with mannitol and a PBS buffer solution according to the mass ratio of 2.
2) Re-dissolving 0.75 g safflower oil lyophilized powder, adding into 10 mL pyrrole solution (0.15 mol/L), slowly stirring at room temperature for 1h, centrifuging at 12000 rpm for 5 min, and keeping oil layer; and (3) adding the retained oil layer into a 10 mL ferric chloride solution (0.15 mol/L), slowly stirring 1h at room temperature to polymerize the pyrrole in situ, centrifuging at 8000rpm for 3 min, and retaining the oil layer to obtain the oil-polypyrrole solar absorbing material. And (3) fully and uniformly mixing the obtained oil body-polypyrrole with mannitol and a PBS buffer solution according to the mass ratio of 2.
Example 2 preparation of Linum usitatissimum oil body-polypyrrole solar absorber material
1. Preparation of flax mustard oil body freeze-dried powder
Preparing solution A (sucrose 273.84 g/L, sodium chloride 40.91 g/L and triaminomethane 12.14 g/L), preparing solution B (sucrose 136.92 g/L, sodium chloride 40.91 g/L and triaminomethane 12.14 g/L), soaking 50 g flax mustard seeds in solution A of 1.5 4234 zxft 5364, crushing the mixture completely by a juice extractor, centrifuging at 12000 rpm for 20 min to obtain an oil body layer, adding the solution B again into the oil body layer, cleaning and uniformly mixing the mixture, centrifuging at 12000 rpm for 20 min, repeating the above operations until no precipitate is generated, and obtaining the oil body layer which is the flax oil mustard body. And (3) fully and uniformly mixing the obtained flax mustard oil body with mannitol and a PBS buffer solution according to the mass ratio of 2.
2. Preparation of flax mustard oil body-polypyrrole composite material
1) Re-dissolving 0.5 g fresh Linum usitatissimum oil body, adding into 10 mL pyrrole solution (0.15 mol/L), slowly stirring at room temperature for 1h, centrifuging at 12000 rpm for 5 min, and keeping oil layer; and (3) adding the retained oil layer into a 10 mL ferric chloride solution (0.15 mol/L), slowly stirring 1h at room temperature to polymerize the pyrrole in situ, centrifuging at 8000rpm for 3 min, and retaining the oil layer to obtain the oil-polypyrrole solar absorbing material. And (3) fully and uniformly mixing the obtained oil body-polypyrrole with mannitol and a PBS buffer solution according to the mass ratio of 2.
2) Re-dissolving 0.75 g oleum Lini lyophilized powder, adding into 10 mL pyrrole solution (0.15 mol/L), slowly stirring at room temperature for 1h, centrifuging at 12000 rpm for 5 min, and keeping oil layer; and (3) adding the retained oil layer into a 10 mL ferric chloride solution (0.15 mol/L), slowly stirring 1h at room temperature to polymerize the pyrrole in situ, centrifuging at 8000rpm for 3 min, and retaining the oil layer to obtain the oil-polypyrrole solar absorbing material. And (3) fully and uniformly mixing the obtained oil body-polypyrrole with mannitol and a PBS buffer solution according to the mass ratio of 2.
Example 3 preparation of Soybean oil body-polypyrrole solar absorber Material
1. Preparation of soybean oil body freeze-dried powder
Preparing solution A (sucrose 273.84 g/L, sodium chloride 40.91 g/L and triaminomethane 12.14 g/L), preparing solution B (sucrose 136.92 g/L, sodium chloride 40.91 g/L and triaminomethane 12.14 g/L), soaking 50 g soybean seeds in solution A of 1.5 4234 zxft 5364, crushing the soybean seeds completely by a juice extractor, centrifuging at 12000 rpm for 20 min to obtain an oil body layer, adding solution B again into the oil body layer, washing the mixture uniformly, centrifuging at 12000 rpm for 20 min, repeating the above operations until no precipitate is generated, and obtaining the oil body layer which is the soybean oil body. And (3) fully and uniformly mixing the obtained soybean oil body with mannitol and a PBS buffer solution according to the mass ratio of 2.
2. Preparation of soybean oil body-polypyrrole composite material
1) Re-dissolving 0.5 g fresh soybean oil, adding into 10 mL pyrrole solution (0.15 mol/L), slowly stirring at room temperature for 1h, centrifuging at 12000 rpm for 5 min, and keeping oil layer; and (3) adding the retained oil layer into a 10 mL ferric chloride solution (0.15 mol/L), slowly stirring 1h at room temperature to polymerize the pyrrole in situ, centrifuging at 8000rpm for 3 min, and retaining the oil layer to obtain the oil-polypyrrole solar absorbing material. And (3) fully and uniformly mixing the obtained oil body-polypyrrole with mannitol and a PBS buffer solution according to the mass ratio of 2.
2) Re-dissolving 0.75 g soybean oil body lyophilized powder, adding into 10 mL pyrrole solution (0.15 mol/L), slowly stirring at room temperature for 1h, centrifuging at 12000 rpm for 5 min, and keeping oil layer; and (3) adding the retained oil layer into a 10 mL ferric chloride solution (0.15 mol/L), slowly stirring 1h at room temperature to polymerize the pyrrole in situ, centrifuging at 8000rpm for 3 min, and retaining the oil layer to obtain the oil-polypyrrole solar absorbing material. And (3) fully and uniformly mixing the obtained oil body-polypyrrole with mannitol and a PBS buffer solution according to the mass ratio of 2.
Example 4 preparation of peanut oil bodies-polypyrrole solar absorber material.
1. Preparation of peanut oil body freeze-dried powder
Taking 5 g peeled peanut seeds, adding 50 mL PBS buffer (pH = 7.4), fully grinding, centrifuging at 12000 rpm for 5 min to obtain an oil body layer, adding the PBS buffer into the oil body layer again, mixing uniformly, centrifuging at 12000 rpm for 5 min, repeating the operations until no precipitate is generated, and obtaining the oil body layer which is the peanut oil body. And (3) fully and uniformly mixing the obtained peanut oil body with mannitol and a PBS buffer solution according to the mass ratio of 2.
2. Preparation of peanut oil body-polypyrrole composite material
1) Re-dissolving 0.5 g fresh peanut oil, adding into 10 mL pyrrole solution (0.15 mol/L), slowly stirring at room temperature for 1h, centrifuging at 12000 rpm for 5 min, and keeping oil layer; and (3) adding the retained oil layer into a 10 mL ferric chloride solution (0.15 mol/L), slowly stirring 1h at room temperature to polymerize the pyrrole in situ, centrifuging at 8000rpm for 3 min, and retaining the oil layer to obtain the oil-polypyrrole solar absorbing material. And (3) fully and uniformly mixing the obtained oil body-polypyrrole with mannitol and a PBS buffer solution according to the mass ratio of 2.
2) Re-dissolving 0.75 g peanut oil body freeze-dried powder, adding into 10 mL pyrrole solution (0.15 mol/L), slowly stirring at room temperature for 1h, centrifuging at 12000 rpm for 5 min, and keeping an oil layer; and (3) adding the retained oil layer into a ferric chloride solution (0.15 mol/L) of 10 mL, slowly stirring 1h at room temperature to polymerize the pyrrole in situ, centrifuging at 8000rpm for 3 min, and retaining the oil layer to obtain the oil body-polypyrrole solar absorbing material. And (3) fully and uniformly mixing the obtained oil body-polypyrrole with mannitol and a PBS buffer solution according to the mass ratio of 2.
Example 5 evaluation of fresh water quality obtained by oil body-polypyrrole solar energy absorption material under solar irradiation
Putting the oil body-polypyrrole solar energy absorbing material into water, and observing the state of the material in the water, wherein the result is shown in figure 1; a comparison photograph of the states of the oil body-polypyrrole and the polypyrrole solar energy absorbing material in water shows that the obtained oil body-polypyrrole solar energy absorbing material is a black composite material which can float on the surface of a water body. Fig. 2 is a microscopic image of an oil body and an oil body-polypyrrole solar absorbing material, the oil body morphology has not changed, indicating that the structure of the oil body is not damaged during the synthesis of the oil body-polypyrrole solar absorbing material.
A fresh water resource collecting device manufactured by utilizing an oil body-polypyrrole solar energy absorbing material is shown in a figure 3; FIG. 4 is a picture of a self-made fresh water resource collecting device collecting fresh water process objects; the figure shows that the recovery speed is high and the fresh water collecting effect is good.
FIGS. 5 and 6 are representations of the ability to collect fresh water from natural river water and artificial seawater, respectively, using an oil body-polypyrrole solar absorber material under solar irradiation; the fresh water recovery rate after irradiation of 8 h is respectively 1.14 kg m-2 h-1 and 1.08 kg m-2 h-1, and the fresh water recovery efficiency is respectively 92.79% and 92.20%;
FIG. 7 is a comparison of the state of the oil body-polypyrrole solar absorbing material synthesized by fresh safflower oil body before and after desalination, wherein the fresh water recovery rate is 0.83 kg m-2 h-1, which is lower than that of the oil body-polypyrrole solar absorbing material synthesized by safflower oil body freeze-dried powder, and the oil body-polypyrrole solar absorbing material synthesized by safflower oil body freeze-dried powder has stable state and more cycle times.
In order to further evaluate the quality of the recovered fresh water, resistivity and bacterial concentration measurements were performed on the natural river water and the artificial seawater and the collected fresh water, respectively. The resistivity is tested by a water quality analyzer, and the bacterial concentration is tested by a coating method, which comprises the following steps:
and (3) coating three untreated water sources (natural river water and artificial seawater) of which the volume is 10 mu L and three recovered fresh waters on an LB solid culture medium, culturing the three water sources in a constant-temperature incubator at 37 ℃ for 24 h, counting colonies formed on the culture medium, and calculating the concentration of bacteria in the water body.
As a result: fig. 8 is a resistivity contrast diagram of natural river water and artificial seawater and fresh water collected by using the same, which shows that the resistivity of the natural river water and the resistivity of the artificial seawater are 0.1389 and 0.0594M Ω respectively, while the resistivity of the collected fresh water is 3.75 and 3.20M Ω respectively, which are both much larger than the resistivity of the wastewater, and thus, the conductivity of the collected fresh water is low and the impurity content is low;
FIG. 9 is a photograph showing the bacteria content of natural river water and artificial seawater and fresh water collected by using the same by the coating method, which shows that the bacteria content of the natural river water and the artificial seawater are 8.7 x 10^3 and 5.76 x 10^4 CFU mL-1 respectively, and the collected fresh water does not contain bacteria, so that the fresh water is effectively purified and has good water quality.
Claims (8)
1. The oil body-polypyrrole solar energy absorption material is prepared by the following method:
1) Adding vegetable oil into pyrrole solution, stirring, and centrifuging;
2) Adding the oil body obtained in the step 1) into a ferric chloride solution, stirring for reaction, and centrifuging to obtain an oil body-polypyrrole solar energy absorbing material;
3) And (5) freeze-drying.
2. The oil body-polypyrrole solar absorbing material of claim 1, wherein: the vegetable oil body is artificial oil body, safflower oil body, soybean oil body and/or peanut oil body.
3. The oil body-polypyrrole solar absorbing material of claim 2, wherein: the concentration of the pyrrole solution is 0.1-0.2M, and the concentration of the ferric chloride solution is 0.1-0.2M.
4. The oil body-polypyrrole solar absorbing material of claim 1, 2 or 3, wherein: the vegetable oil body is obtained by adding a buffer solution to redissolve the vegetable oil body which is freeze-dried and then centrifuging.
5. The oil body-polypyrrole solar absorbing material of claim 4, wherein: and 3) freeze-drying, namely freeze-drying after uniformly mixing the oil body-polypyrrole with a dispersing agent and a buffer solution.
6. The oil body-polypyrrole solar absorbing material of claim 5, wherein: the centrifugation in the step 1) is performed for 5 min at room temperature by slowly stirring for 1h and 12000 rpm.
7. The oil body-polypyrrole solar absorbing material of claim 6, wherein: and 2) the centrifugation is slowly stirred for 1h at room temperature to polymerize the pyrrole in situ, and is centrifuged for 3 min at 8000 rpm.
8. The oil body-polypyrrole solar absorbing material of claim 5, 6 or 7, wherein: the freeze-drying in the step 3) is that oil bodies, namely polypyrrole, mannitol and a PBS buffer solution are fully and uniformly mixed according to the mass ratio of 2.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110123448A1 (en) * | 2009-11-25 | 2011-05-26 | China Medical University | Oil body carriers, uses in target therapy and/or detection of the same, and fusion proteins comprised therein |
| CN107384582A (en) * | 2017-09-06 | 2017-11-24 | 吉林农业大学 | A kind of extracting method of safflower oil bodies |
| CN110734575A (en) * | 2019-10-25 | 2020-01-31 | 桂林电子科技大学 | Preparation method and application of aerogel-polypyrrole photothermal conversion materials |
| CN111892742A (en) * | 2020-07-22 | 2020-11-06 | 湖北大学 | Photo-thermal conversion polymer solar energy absorption material and preparation method and application thereof |
| CN112552553A (en) * | 2020-12-09 | 2021-03-26 | 桂林理工大学 | Composite foam porous material and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110123448A1 (en) * | 2009-11-25 | 2011-05-26 | China Medical University | Oil body carriers, uses in target therapy and/or detection of the same, and fusion proteins comprised therein |
| CN107384582A (en) * | 2017-09-06 | 2017-11-24 | 吉林农业大学 | A kind of extracting method of safflower oil bodies |
| CN110734575A (en) * | 2019-10-25 | 2020-01-31 | 桂林电子科技大学 | Preparation method and application of aerogel-polypyrrole photothermal conversion materials |
| CN111892742A (en) * | 2020-07-22 | 2020-11-06 | 湖北大学 | Photo-thermal conversion polymer solar energy absorption material and preparation method and application thereof |
| CN112552553A (en) * | 2020-12-09 | 2021-03-26 | 桂林理工大学 | Composite foam porous material and preparation method and application thereof |
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