CN113968994B - Photo-thermal biomass aerogel for solar interface evaporation and preparation method thereof - Google Patents
Photo-thermal biomass aerogel for solar interface evaporation and preparation method thereof Download PDFInfo
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/02—Treatment of water, waste water, or sewage by heating
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- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
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- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
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- 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
Abstract
The invention relates to a photo-thermal biomass aerogel for solar interface evaporation and a preparation method thereof, belonging to the technical field of functional materials. The preparation method of the solar interface evaporation photo-thermal biomass aerogel sequentially comprises the following steps: soaking a cellulose biomass material in a tannic acid solution, and then adding ferric ions to perform a complex reaction; and (3) freezing and drying the reacted biomass material to obtain the photo-thermal biomass aerogel. The photo-thermal biomass aerogel for solar interface evaporation, which is obtained by the invention, has excellent photo-thermal performance, can continuously and efficiently convert aqueous solution into water vapor under the irradiation of sunlight, and can be used as a photo-thermal interface evaporation material for seawater desalination and wastewater purification.
Description
Technical Field
The invention relates to a photo-thermal biomass aerogel for solar interface evaporation and a preparation method thereof, belonging to the technical field of functional materials.
Background
With the rapid development of industrialization and the rapid growth of the global population, drinking water sources are often destroyed due to pollution caused by energy mining and urban settlement. At the same time, researchers have been working on treating and improving the natural water circulation process due to the uneven distribution of water resources around the world and the presence of large quantities of alternative water resources. Based on inexhaustible seawater and solar energy resources, solar-driven interface evaporation is produced as a strategy for solving the shortage of clean water resources at low cost and is gradually enriched. In order to improve the utilization of solar energy, various photothermal materials (such as carbon-based, metal nanoparticles, polymers, and plasma absorbers) are introduced into the solar evaporation system. In order to reduce the cost of obtaining water resources, an economic and environmentally friendly strategy is being sought to convert renewable biomass into value added materials with a photo-thermal effect.
As a renewable biological energy source abundant in nature, most biomass raw materials have extremely low cost and a porous special structure, and can be conveniently and rapidly obtained from various sources. Surface carbonization techniques of biomass materials are commonly used to produce most solar steam generators. Although great progress is made in biomass solar steam generation devices, the problems of complex manufacturing process, difficult acquisition of synthetic materials and the like still have challenges. Therefore, it is necessary to design a solar interface evaporation material with simple preparation process, excellent photo-thermal performance and low cost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a photothermal biomass aerogel for solar interface evaporation and a preparation method thereof. The preparation method disclosed by the invention is simple in process and easy to scale, and the obtained biomass aerogel has excellent photo-thermal performance and good application prospects in the fields of solar energy utilization, seawater desalination and the like.
The invention provides a photo-thermal biomass aerogel for solar interface evaporation and a preparation method thereof, which sequentially comprise the following steps:
(1) soaking cellulose biomass material blocks in a tannic acid solution, adding ferric ions to perform a complex reaction to generate photo-thermal nano particles, and cleaning after the reaction;
(2) freezing the material prepared in the step (1), and freeze-drying to obtain the photo-thermal biomass aerogel.
As one of embodiments of the present invention, the cellulosic biomass material is at least one of eggplant, luffa, sugar cane, radish, yam, bamboo, and straw. Preferably eggplant, yam and sugarcane. Further preferably an eggplant.
As one embodiment of the present invention, the concentration of tannic acid is 1 to 2000 mg/mL; the concentration of the ferric ions is 1-2000 mg/mL.
Preferably, the concentration of tannic acid is 1 to 1000 mg/mL. Further preferably, the concentration of said tannic acid is 1 to 20 mg/mL.
Preferably, the concentration of the ferric ions is 1-1000 mg/mL. Further preferably, the concentration of the ferric ions is 5 mg/mL.
In one embodiment of the present invention, the ferric ion is at least one of ferric sulfate, ferric chloride, and ferric nitrate.
As one embodiment of the present invention, the reaction conditions in the step (1) are: the temperature is 15-35 ℃ and the time is 2-8 h.
As one embodiment of the present invention, the washing in step (1) includes alcohol washing and water washing, the alcohol washing uses 95% ethanol or absolute ethanol, and the water washing uses deionized water.
As one embodiment of the present invention, the freezing mode in the step (2) is refrigerator freezing or liquid nitrogen freezing.
As one embodiment of the invention, the freezing temperature in the step (2) is-196 ℃ to 0 ℃, and the freezing time is 2 to 180 min.
In one embodiment of the present invention, the freeze-drying time in the step (2) is 12 to 48 hours.
The second purpose of the invention is to provide the solar interface evaporation photothermal biomass aerogel prepared by the method.
The third purpose of the invention is to provide the application of the solar interface evaporation biomass photothermal aerogel in water evaporation, seawater desalination and wastewater purification.
The invention has the beneficial effects that:
(1) the preparation method has the advantages of simple process, easy operation and low cost, and can realize large-scale batch production.
(2) The biomass aerogel disclosed by the invention has excellent photo-thermal properties: can rapidly raise the temperature and convert water into water vapor under the irradiation of sunlight, realizes high-efficiency interface evaporation, and the interface evaporation rate can reach 1.61Kg m-2h-1。
(3) The biomass aerogel disclosed by the invention can be used as a high-quality and high-efficiency photothermal interface evaporation material and is used for seawater desalination and wastewater purification.
Drawings
Fig. 1 is SEM photographs of the biomass aerogel products prepared in example 1 and comparative example 1, wherein fig. 1(a) is a raw biomass aerogel and (b) is a photothermal biomass aerogel.
FIG. 2 shows the results of example 1, comparative example 1 and comparative example 2 in the presence of sunlight (1000W m)-2) Temperature rise contrast of the irradiated lower surface.
FIG. 3 shows the results of example 1, comparative example 1 and comparative example 2 in the presence of sunlight (1000W m)-2) Water evaporation rate in the beaker under irradiation was compared.
FIG. 4 shows the results of example 1, comparative example 1 and comparative example 2 in the presence of sunlight (1000W m)-2) The temperature of the sample surface in the beaker under irradiation was raised in contrast.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
The test method comprises the following steps:
1. and (3) morphology testing: the morphology of the biomass aerogel samples was characterized by scanning electron microscopy (SEM, Hitachi Su1510 co., ltd., Japan).
2. Testing the photo-thermal heating performance: the surface temperature change of the aerogel samples under light conditions was recorded by a thermal imager (Testo 871, Testo Se & co.
3. Water evaporation test: the aerogel was placed in a beaker containing a large amount of water and irradiated with simulated sunlight using a xenon lamp (Cel-S500) equipped with an AM 1.5 filter. Meanwhile, a Solar energy meter (SM206-Solar) is used for calibrating the sunlight intensity to maintain at a sunlight intensity (1000W m)-2) An electronic balance (AX224ZH/E) records the mass loss of water in the beaker to measure the interfacial evaporation capacity of the aerogel sample, a thermal imager (Testo 871, Testo Se&Kgaa) the surface temperature change of the aerogel sample in the beaker was recorded.
Example 1
A preparation method of photo-thermal biomass aerogel for solar interface evaporation comprises the following steps:
(1) cutting fresh eggplants into blocks, weighing 2g of fresh eggplants, placing the fresh eggplants into a beaker containing 50mL of aqueous solution, then adding 250mg of tannic acid, adding 250mg of ferric sulfate into the solution under the condition of room temperature magnetic stirring, taking out the eggplants after reacting for 6 hours, and cleaning;
(2) and (2) placing the eggplants reacted in the step (1) in liquid nitrogen for freezing for 2min, and after freezing, placing the frozen eggplants in a freeze dryer for drying for 36h to obtain the photo-thermal biomass aerogel.
Comparative example 1
Cutting fresh eggplants into blocks, weighing 2g of fresh eggplants, placing the fresh eggplants in liquid nitrogen for freezing for 2min, and placing the frozen eggplants in a freeze dryer for drying for 36h after freezing is finished to obtain the original biomass aerogel.
Comparative example 2
A preparation method of a photo-thermal biomass material for solar interface evaporation comprises the following steps:
cutting fresh eggplants into blocks, weighing 2g of fresh eggplants, placing the blocks into a beaker containing 50mL of aqueous solution, then adding 250mg of tannic acid, adding 250mg of ferric sulfate into the solution under the condition of room temperature magnetic stirring, taking out the eggplants after reacting for 6h, and cleaning to obtain the photo-thermal biomass material.
First, morphology comparison
The morphology test of the biomass aerogel products prepared in example 1 and comparative example 1 is performed, and the results are sequentially shown in fig. 1, wherein fig. 1(a) is the original biomass aerogel of comparative example 1, and fig. 1(b) is the photothermal biomass aerogel of example 1.
The scanning electron microscope image of fig. 1(a) shows that the original biomass (eggplant) aerogel prepared by freeze-drying exhibits a unique spongy porous morphology. The original biomass aerogel was a porous structure consisting of hundreds to thousands of fibrous sheets/tubes with 3D interconnected pores of about 20-60 μm. As can be seen from fig. 1(b), the photo-thermal biomass aerogel prepared by soaking eggplants in the aqueous solution containing tannic acid and ferric iron has a large number of nanoparticles on the surface on the basis of maintaining the original structure, which proves the successful combination of the nanoparticles (photo-thermal material). From the viewpoint of solar interface evaporation, the spongy biological porous material has a plurality of macropores with different sizes, and can promote the rapid transportation of water molecules to evaporate water.
Second, comparison of photo-thermal heating performance test
The products obtained in example 1, comparative example 1 and comparative example 2 were subjected to photothermal temperature increase performance test in one sun (1000W m)-2) The results of the surface temperature changes of different samples with the time of solar irradiation are shown in fig. 2.
As can be seen from fig. 2, the surface temperatures of the original biomass aerogel, the photothermal biomass aerogel, and the photothermal biomass material gradually increased within several tens of seconds. After 120s of irradiation, the photo-thermal biomass aerogel obtains higher and uniform surface temperature (48.2 ℃), and meanwhile, with the closing of sunlight, the surface temperature of the photo-thermal aerogel changes dynamically and is gradually restored to the room temperature, so that good photo-thermal response performance is displayed. Compared with the original biomass aerogel, the photothermal biomass aerogel and the photothermal biomass material have higher heating rate, the surface temperature under illumination is higher than that of the original biomass aerogel (32.1 ℃), and the reaction of tannic acid and ferric ions is proved to be capable of successfully introducing the photothermal material nanoparticles, so that the photothermal heating performance can be improved. And the temperature rise effect (42.2 ℃) of the photothermal biomass material prepared by omitting the freeze drying technology is lower than that of the photothermal biomass aerogel.
Comparison of Water Evaporation test
The aerogel products obtained in example 1 and comparative example 1, the photothermal biomass material obtained in comparative example 2, and a blank (pure water to which the photothermal material was not added) were subjected to water evaporation tests, respectively, and the results of the change in the mass of water in a beaker with the time of solar irradiation for various samples under one solar irradiation are shown in fig. 3, in which pure water (representing the blank) is illustrated.
As shown in fig. 3, the quality of water in the beaker varies with the exposure time of pure water and different samples under one sun exposure. Wherein the water evaporation rate of the photo-thermal biomass aerogel can reach 1.61kg m-2h-1Respectively, pure water (0.33kg m)-2h-1) Original biomass aerogel (0.7kg m)-2h-1) And photothermal biomass material (1.01kg m)-2h-1) 4.8 times, 2.3 times and 1.59 times. The photothermal biomass aerogel disclosed by the invention is proved to have an excellent water evaporation effect.
Fourth, comparison of water evaporation and temperature rise test
The photothermal heating performance test was performed on the products obtained in example 1, comparative example 1, and comparative example 2, respectively, in the water evaporation test, and the results of the surface temperature changes in the beaker containing the aqueous solution of the different samples under one sun light irradiation are shown in fig. 4.
It was found that the surface temperature of the product obtained in example 1 was significantly different even when sunlight was irradiated on the surface of the biomass aerogel floating in the aqueous solution.
As can be seen from FIG. 4, when the photothermal biomass aerogel is placed in an aqueous solution and treated under a sun light for 10min, the surface temperature of the photothermal biomass aerogel can reach about 40 ℃, which is much higher than the surface temperature (28 ℃) of the original biomass aerogel and the photothermal biomass material (32 ℃). The excellent photothermal effect of the photothermal biomass aerogel can be used for heating water to generate steam when the photothermal biomass aerogel is used for a water evaporation test.
Example 2 Effect of different tannin content on photo-thermal Properties
Referring to example 1, except for adjusting the amount of tannic acid to 100mg, photothermal biomass aerogels (denoted as photothermal biomass aerogel #1) having different tannic acid contents were prepared.
Referring to example 1, except for adjusting the amount of tannic acid to 50mg, photothermal biomass aerogels (denoted as photothermal biomass aerogel #2) having different tannic acid contents were prepared.
Referring to example 1, except for adjusting the amount of tannic acid to 10mg, photothermal biomass aerogels (denoted as photothermal biomass aerogel #3) having different tannic acid contents were prepared.
Referring to example 1, except for adjusting the amount of tannic acid to 500mg, photothermal biomass aerogels (denoted as photothermal biomass aerogel #4) having different tannic acid contents were prepared.
Referring to example 1, except for adjusting the amount of tannic acid to 1000mg, photothermal biomass aerogels (denoted as photothermal biomass aerogel #5) having different tannic acid contents were prepared.
Referring to example 1, except for adjusting the amount of tannic acid to 2000mg, photothermal biomass aerogels (denoted as photothermal biomass aerogel #6) having different tannic acid contents were prepared.
Photo-thermal temperature rise performance tests were performed on the photo-thermal biomass aerogels with different tannin contents in example 1 and example 2, and the surface temperatures of different samples irradiated for 120s under the sunlight irradiation are shown in table 1.
Table 1 photothermal temperature increase performance test of photothermal biomass aerogels prepared in example 1 and example 2
As can be seen from table 1, after being irradiated by sunlight, the photothermal biomass aerogels of examples 1 and 2 both have a certain photothermal effect, and the surface temperature can be continuously increased within 120 s. The photothermal biomass aerogel can be warmed up to 48.2 ℃, and under the same conditions, photothermal biomass aerogel #1, photothermal biomass aerogel # 2, photothermal biomass aerogel # 3, photothermal biomass aerogel #4, photothermal biomass aerogel # 5 and photothermal biomass aerogel #6 are respectively warmed up to 44.6 ℃, 38.7 ℃, 28.7 ℃, 46.8 ℃, 37.8 ℃ and 36.4 ℃. Proved that the photothermal biomass aerogel can realize different photothermal heating effects by changing the content of the tannic acid, has good photothermal effects in the ranges of the concentrations of the tannic acid and the ferric ions (1-1000 mg/L), and takes the embodiment 1 as the optimal dosage.
Example 3 Effect of different preparation methods on photo-thermal Properties
Referring to example 1, a different photothermal biomass aerogel (denoted as carbonized photothermal biomass aerogel #1) was prepared except that fresh eggplant was changed to eggplant after high temperature carbonization at 500 ℃.
Referring to example 1, a different photothermal biomass aerogel (denoted as carbonized photothermal biomass aerogel #2) was prepared except that fresh eggplant was changed to eggplant after high temperature carbonization at 600 ℃.
Referring to example 1, a different photothermal biomass aerogel (denoted as carbonized photothermal biomass aerogel #3) was prepared except that fresh eggplant was changed to eggplant after high temperature carbonization at 700 ℃.
Referring to example 1, a different photothermal biomass aerogel (denoted as carbonized photothermal biomass aerogel #4) was prepared except that fresh eggplant was adjusted to be eggplant carbonized at a high temperature of 800 ℃.
Referring to example 1, a different photothermal biomass aerogel (denoted as carbonized photothermal biomass aerogel #5) was prepared except that fresh eggplant was changed to eggplant after high-temperature carbonization at 900 ℃.
The photo-thermal heating performance test was performed on the different carbonized photo-thermal biomass aerogels described above in example 1 and example 3, and the surface temperature of the different samples irradiated for 120s under the sunlight irradiation is shown in table 2.
Table 2 photothermal temperature increase performance test of photothermal biomass aerogel and carbonized photothermal biomass aerogel prepared in example 1 and example 3
| Sample (I) | Surface temperature (. degree. C.) |
| Photo-thermal biomass aerogel | 48.2 |
| Carbonized photothermal biomass aerogel #1 | 45.5 |
| Carbonized photothermal |
42.8 |
| Carbonized photothermal |
43.3 |
| Carbonized photothermal biomass aerogel #4 | 44.7 |
| Carbonized photothermal |
46.2 |
As can be seen from table 2, both the photothermal biomass aerogel (example 1) and the carbonized photothermal biomass aerogel have a certain photothermal effect after the irradiation of sunlight, and the surface temperature can be continuously increased within 120 s. The photothermal biomass aerogel can be warmed up to 48.2 ℃, and under the same condition, the carbonized photothermal biomass aerogel #1, the carbonized photothermal biomass aerogel # 2, the carbonized photothermal biomass aerogel # 3, the carbonized photothermal biomass aerogel #4 and the carbonized photothermal biomass aerogel # 5 are respectively warmed up to 44.6 ℃, 38.7 ℃ and 46.8 ℃. It is demonstrated that the carbonization process does not additionally improve the photothermal properties of the photothermal biomass material.
Example 4 Effect of different Biomass materials on photothermal Properties
Referring to example 1, a different photothermal biomass aerogel (denoted as luffa biomass aerogel) was prepared, except that fresh eggplant was changed to luffa.
Referring to example 1, a different photothermal biomass aerogel (denoted as sugar cane biomass aerogel) was made, with the only difference being that fresh eggplant was adjusted to sugar cane.
Referring to example 1, a different photothermal biomass aerogel (denoted as radish biomass aerogel) was prepared, except that fresh eggplant was changed to radish.
Referring to example 1, a different photothermal biomass aerogel (denoted as yam biomass aerogel) was prepared, except that fresh eggplant was changed to yam.
Referring to example 1, a different photothermal biomass aerogel (denoted as bamboo biomass aerogel) was prepared except that fresh eggplant was changed to bamboo.
Referring to example 1, a different photothermal biomass aerogel (denoted as straw biomass aerogel) was produced, except that fresh eggplant was changed to straw.
Photothermal temperature rise performance tests were performed on photothermal biomass aerogels of the different biomass materials described above in example 1 and example 4, and the surface temperatures of the different samples irradiated for 120s under sunlight irradiation are shown in table 3.
Table 3 photothermal heating performance test of photothermal biomass aerogels prepared in example 1 and example 4
| Sample (I) | Surface temperature (. degree. C.) |
| Eggplant biomass aerogel | 48.2 |
| Loofah biomass aerogel | 38.1 |
| Sugarcane biomass aerogel | 40.2 |
| Radish biomass aerogel | 37.7 |
| Chinese yam biomass aerogel | 44.6 |
| Bamboo biomass aerogel | 32.8 |
| Straw biomass aerogel | 30.1 |
As can be seen from table 3, after sunlight irradiation, the photothermal biomass aerogel prepared based on different biomass materials has a certain photothermal effect, and the surface temperature can be continuously increased within 120 s. The photothermal biomass aerogel (eggplant biomass aerogel) can be warmed up to 48.2 ℃, and under the same conditions, the luffa biomass aerogel, the sugarcane biomass aerogel, the radish biomass aerogel, the yam biomass aerogel, the bamboo biomass aerogel and the straw biomass aerogel are respectively warmed up to 38.1 ℃, 40.2 ℃, 37.7 ℃, 44.6 ℃, 32.8 ℃ and 30.1 ℃. It was demonstrated that photothermal biomass aerogels made based on natural porous cellulosic biomass materials (e.g., eggplant, loofah, sugarcane, radish, yam, bamboo, and straw) can achieve different photothermal warming effects by modifying the biomass material. Wherein the preferred eggplant biomass aerogel, chinese yam biomass aerogel, the intensification effect of sugarcane biomass aerogel is better, and bamboo biomass aerogel and the intensification effect of straw biomass aerogel are relatively poor.
In summary, the photothermal biomass aerogel for solar interface evaporation and the preparation method thereof provided by the invention have the characteristics of simple preparation, low cost and easy scale production, and also have excellent photothermal properties: the surface temperature can be rapidly raised under the irradiation of sunlight, and the solar energy interface evaporation material can be used as an efficient solar energy interface evaporation material for seawater desalination and wastewater purification.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by one skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The preparation method of the photo-thermal biomass aerogel for solar interface evaporation is characterized by sequentially comprising the following steps of:
(1) soaking natural porous cellulose biomass material blocks in a tannic acid solution, adding ferric ions to perform a complex reaction to generate photo-thermal nano particles, and cleaning after the reaction; the natural porous cellulose biomass material is at least one of eggplant, towel gourd, sugarcane, radish, Chinese yam, bamboo and straw;
(2) freezing the material prepared in the step (1), and freeze-drying to obtain the photo-thermal biomass aerogel.
2. The preparation method of the photothermal biomass aerogel for solar interfacial evaporation according to claim 1, wherein the concentration of the tannic acid is 1-2000 mg/mL; the concentration of the ferric ions is 1-2000 mg/mL.
3. The preparation method of the photothermal biomass aerogel for solar interfacial evaporation according to claim 1, wherein the ferric ions are at least one of ferric sulfate, ferric chloride and ferric nitrate.
4. The method for preparing photothermal biomass aerogel for solar interfacial evaporation according to claim 1, wherein the reaction conditions in step (1) are: the temperature is 15-35 ℃, and the time is 2-8 h.
5. The method for preparing the photothermal biomass aerogel for solar interface evaporation according to claim 1, wherein the washing in the step (1) comprises alcohol washing and water washing, wherein the alcohol washing is 95% ethanol or absolute ethanol, and the water washing is deionized water.
6. The preparation method of the photothermal biomass aerogel for solar interface evaporation according to claim 1, wherein the freezing temperature in the step (2) is-196 ℃ to 0 ℃, and the freezing time is 2 to 180 min.
7. The preparation method of the photothermal biomass aerogel for solar interfacial evaporation according to claim 1, wherein the freeze-drying time in the step (2) is 12-48 h.
8. A photothermal biomass aerogel produced by the method of any one of claims 1-7.
9. Use of the photothermal biomass aerogel according to claim 8 in solar interfacial evaporation, seawater desalination, wastewater purification.
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