CN115651274A - Preparation method of clay-based composite hydrogel for solar seawater desalination - Google Patents
Preparation method of clay-based composite hydrogel for solar seawater desalination Download PDFInfo
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- CN115651274A CN115651274A CN202211342135.7A CN202211342135A CN115651274A CN 115651274 A CN115651274 A CN 115651274A CN 202211342135 A CN202211342135 A CN 202211342135A CN 115651274 A CN115651274 A CN 115651274A
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 72
- 239000004927 clay Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000010612 desalination reaction Methods 0.000 title claims abstract description 9
- 239000013535 sea water Substances 0.000 title claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 52
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000661 sodium alginate Substances 0.000 claims abstract description 43
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- 238000000034 method Methods 0.000 claims abstract description 33
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- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims abstract description 17
- 238000001879 gelation Methods 0.000 claims abstract description 13
- 238000010257 thawing Methods 0.000 claims abstract description 13
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 8
- 235000012209 glucono delta-lactone Nutrition 0.000 claims abstract description 8
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- 159000000007 calcium salts Chemical class 0.000 claims abstract description 7
- 230000008014 freezing Effects 0.000 claims description 41
- 238000007710 freezing Methods 0.000 claims description 41
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- 230000032683 aging Effects 0.000 claims description 14
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- 239000000725 suspension Substances 0.000 claims description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
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- -1 mxene Chemical compound 0.000 claims description 2
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 62
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- XXZCIYUJYUESMD-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(morpholin-4-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCOCC1 XXZCIYUJYUESMD-UHFFFAOYSA-N 0.000 description 1
- WWSJZGAPAVMETJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethoxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OCC WWSJZGAPAVMETJ-UHFFFAOYSA-N 0.000 description 1
- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 1
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Images
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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
- Y02A20/124—Water desalination
-
- 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
- Y02A20/124—Water desalination
- Y02A20/138—Water desalination using renewable energy
- Y02A20/142—Solar thermal; Photovoltaics
-
- 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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- Colloid Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the field of hydrogel material preparation, and discloses a preparation method of clay-based solar composite hydrogel for solar seawater desalination, which comprises the following specific steps: dissolving sodium alginate in water solution, adding appropriate amount of clay and carbon-based material to disperse uniformly, slowly adding calcium salt, stirring uniformly, adding gluconolactone water solution or powder, stirring uniformly, pouring into a mold, standing for gelation; and performing directional freeze-thawing on the aged gel for multiple times to obtain the clay-based hydrogel with a vertical pore channel structure. The clay-based composite hydrogel prepared by the invention has the advantages of simple process, green and pollution-free raw materials, low price and contribution to industrial production. The clay-based composite hydrogel has good light absorption efficiency and water evaporation efficiency, rich pore structure and good hydrophilicity, and can be used in the fields of sewage treatment, seawater desalination, brine concentration and the like.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a preparation method of clay-based composite hydrogel for solar seawater desalination.
Background
Fresh water is an essential resource for human beings and all ecosystems to live and plays a vital role. With the growing population, environmental changes and pollution of fresh water resources, how to realize the safety of fresh water supply is a new challenge. The earth's available water only accounts for 3% of the total water volume, and of the very few fresh water resources, more than 70% are frozen in the ice covers of the south and north poles, and less than 1% are available to humans. In addition, the global fresh water resources are not only in short supply but also in unbalanced distribution. By 2025, it is expected that 30 hundred million people in the world face water shortage, and that 40 countries and regions have serious shortage of fresh water.
In order to solve the problem, various seawater and fresh water technologies emerge endlessly. Such as Reverse Osmosis (RO), multi-effect seawater desalination (MED), thermal Vapor Compression (TVC), humidification Dehumidification (HDH), hybrid systems, and multi-level flash Memory (MSF). However, these techniques are expensive to operateIt is difficult to obtain wide popularization and application. Solar energy is an inexhaustible renewable resource in the nature, and the solar energy driving fresh water technology is superior to other technologies in low cost and high photothermal conversion efficiency, and becomes one of effective ways for relieving water resource shortage, such as (CN 112108084A, CN 113735208A) but under natural light (solar intensity is less than or equal to 1 KW.m) -2 The low utilization efficiency of sunlight causes that the existing solar water purification technology cannot achieve the expectation of commercialization. To improve evaporation efficiency, current work focuses mainly on the following three problems: (1) the photo-thermal conversion efficiency is improved; (2) continuously and stably supplying water in the evaporation process; (3) prevent the salting-out from blocking the pore channels. Based on the above requirements, new solar evaporation materials such as plasma nanoparticles, conjugated polymers, carbon-based materials, etc., and solar evaporation devices such as thermal localization films, bionic nanostructures, mushroom bionics, etc., have been highly valued and rapidly developed.
The hydrogel is a three-dimensional network structure formed by mutually stacking and polymerizing high-molecular long chains or colloid particles with water as a medium, and can keep a large amount of water without dissolving. Due to their highly tunable physicochemical properties, they have gained widespread attention and development in the fields of inclusion of artificial tissues, hygiene products, contact lenses, drug delivery and agricultural fertilizers. Hydrogels, one of the most important materials in water evaporation and desalination processes, have higher water evaporation rates and efficiencies due to thermal localization at the air-water interface; the weak interaction between water molecules and polymer chains can form intermediate water, thereby reducing the energy requirements for water vaporization. Hu et al prepared an evaporation rate of 1.582 kg-m -2 h -1 Double layer cellulose hydrogel (Carbohydrate Polymer,2020, 243, 116480). Zhao et al prepared a novel hydrogel-based solar evaporator using a one-step crosslinking process. The thermal-optical layer is made of sodium alginate and PEDOT PSS composite hydrogel, and 1.23 kg.m -2 h -1 Evaporation rate (desalinitio, 2020, 482, 114385). Song et al prepared a polycarbonate with a mass of 1.41 kg.m by physical/chemical crosslinking -2 h -1 High content Attapulgite aerogel with evaporation Rate (Journal of Materials Chemistry A,2021,9, 23117)-23126). But in practical application still faces the problem of unstable salt deposition and evaporation performance.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a preparation method of clay-based composite hydrogel for solar seawater desalination, which is characterized in that a super-hydrophilic water delivery channel is constructed based on the characteristics of a clay material, the aperture is adjusted by directional freezing, and the clay-based hydrogel with a vertical micro-pore channel structure is obtained by multiple directional freezing and thawing. The clay-based composite hydrogel prepared by the method has good light absorption efficiency and water evaporation efficiency, rich pore channel structure and good hydrophilicity, and the evaporation rate can reach 3.78 kg.m at most -2 h -1 。
The technical scheme is as follows: the invention provides a preparation method of persulfate activated radiation modified bentonite loaded nZVI, which comprises the following steps:
adding sodium alginate into an aqueous solution to dissolve the sodium alginate to obtain a sodium alginate aqueous solution, and adding clay and a carbon-based material into the sodium alginate aqueous solution to mix;
the adding amount of the sodium alginate in the sodium alginate aqueous solution is 0.5-4 wt%, and the adding amount of the clay in the sodium alginate aqueous solution is 0-15wt%;
step (2), slowly adding calcium salt into the mixed solution obtained in the step (1), and stirring to obtain a mixed suspension;
adding glucolactone into the mixed suspension obtained in the step (2), uniformly stirring, pouring into a mold, and standing for gelation;
and (4) aging the obtained gel, and performing multiple directional freeze thawing to obtain the clay-based composite hydrogel.
Preferably, in the step (1), the clay is one or a combination of more than two of nanoscale attapulgite, bentonite, kaolin, illite, diatomite or sepiolite.
Preferably, in the step (1), the addition amount of the carbon-based material in the sodium alginate aqueous solution is 0.1 to 10wt%.
Preferably, in step (1), the carbon-based material is one or a combination of two or more of graphite, graphene, carbon black, mxene, fullerene, activated carbon, carbon nanotube, or carbon fiber.
Preferably, in the step (2), the addition amount of the calcium salt in the mixed suspension is 0.1 to 1wt%;
and/or the calcium salt is one or the combination of more than two of calcium carbonate, calcium sulfate, calcium sulfite, hydroxyapatite and calcium phosphate.
Preferably, in the step (3), the gluconolactone is added to the mixed suspension in an amount of 0.1 to 1wt%.
Preferably, the mass ratio of the sodium alginate to the clay in the clay-based composite hydrogel is 1 to 1.
Preferably, the total solid content of the sodium alginate and the clay in the clay-based composite hydrogel is 4% -8%.
Preferably, in the step (4), the thickness of the clay-based composite hydrogel is 0.5 to 1.1cm.
Preferably, in the step (4), the directional freezing and thawing times are 6 to 8;
and/or the directional freezing temperature in the directional freezing and thawing is-20 ℃ to-70 ℃.
Has the advantages that: according to the invention, based on the characteristics of clay materials, a super-hydrophilic water delivery channel is constructed, and the aperture is adjusted by utilizing directional freezing, so that the prepared clay-based composite hydrogel has good light absorption efficiency and water evaporation efficiency, rich pore channel structures and good hydrophilicity, and has the following specific beneficial effects:
1. the invention utilizes the characteristics of clay materials, and has good hydrophilicity and low thermal conductivity;
2. the super-hydrophilic clay material is combined with sodium alginate, the concentration proportion of the super-hydrophilic clay material is adjusted, the thickness of the hydrogel is adjusted, a vertical micron-sized macro pore (the pore diameter range is 50 to 380 mu m) is constructed on a pore channel by multiple times of expansion through the directional freeze-thaw technology, the flux of water vapor can be effectively improved under the combined action of the vertical micron-sized macro pore and a mesoporous structure (2 to 45nm) built by the clay on the wall of the pore, and the evaporation rate can reach 3.78 kg.m at most -2 h -1 ；
3. The invention has simple preparation process, green and pollution-free raw materials and low price, and is beneficial to industrial production.
Drawings
FIG. 1 is an appearance view of the diatomaceous earth-based hydrogel prepared in example 3;
FIG. 2 is an SEM picture of a freeze-dried attapulgite-based aerogel prepared in example 2;
fig. 3 is an SEM picture of the bentonite-based aerogel after freeze-drying prepared in example 5;
FIG. 4 is a mesoporous structure built with attapulgite;
fig. 5 is an adsorption-desorption curve of the clay-based aerogel after freeze-drying;
fig. 6 is a pore size distribution of a clay-based aerogel after freeze-drying;
FIG. 7 is a diagram of an experimental apparatus for water evaporation.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following description is further described with reference to the accompanying drawings and specific examples, which are only used for explaining the present invention and are not used for limiting the present invention.
Example 1
Dissolving 0.5g sodium alginate in 49.5ml deionized water, adding 0.5g activated carbon powder, and dispersing at high speed for 30min until the activated carbon is completely dispersed; slowly adding 0.1g of hydroxyapatite in the stirring process, continuously stirring for 10min, then adding 0.5g of glucolactone, stirring for 2min, pouring into a mould, standing for gelling; and aging the gel overnight, and performing directional freeze-thaw treatment for 6 times to obtain the hydrogel. The directional freezing temperature is-20 ℃, and the specific surface area of the hydrogel reaches 20.72m by measurement 2 The directional freezing aperture range is 320-360 mu m, and the gel thickness is 1cm. The water evaporation efficiency of the hydrogel under the sun illumination intensity is 2.53kg.m by testing through the device shown in figure 7 -2 ·h -1 The photothermal conversion efficiency was 87.3%.
Example 2
Dissolving 1g of sodium alginate in 39.48ml of deionized water, adding 1g of carbon black powder and 9.52g of dispersed 10.5wt% of sodium alginateThe attapulgite slurry is stirred for 30min until being dispersed; slowly adding 0.15g of calcium carbonate while stirring, continuously stirring for 10min, then adding 1g of gluconolactone, stirring for 2min, pouring into a mold, and standing for gelation; and aging the gel overnight, and performing directional freeze-thaw treatment for 6 times to obtain the clay-based composite hydrogel. Fig. 2 is an SEM picture under this condition. The directional freezing temperature is-30 ℃, and the specific surface area of the hydrogel reaches 35.14m by measurement 2 The water evaporation efficiency of the hydrogel under the sun illumination intensity is 2.76kg.m when the water evaporation efficiency is tested by a device shown in figure 7, wherein the directional freezing aperture range is 260-300 mu m, the gel thickness is 0.8cm -2 ·h -1 The photothermal conversion efficiency was 86.2%.
Example 3
Dissolving 0.75g of sodium alginate in 30.5ml of deionized water, adding 2g of graphene and 18.75g of dispersed diatomite slurry with the mass fraction of 8wt%, and stirring for 30min until the mixture is dispersed; slowly adding 0.3g of calcium phosphate while stirring, continuously stirring for 10min, then adding 1.5g of gluconolactone, stirring for 2min, pouring into a mold, and standing for gelation; and performing directional freeze-thaw treatment on the gel for 8 times after aging overnight to obtain the clay-based composite hydrogel, as shown in figure 1. The directional freezing temperature is-40 ℃, and the specific surface area of the hydrogel reaches 38.62m by measurement 2 The volume ratio of the directional freezing aperture is 210 to 250 mu m, and the gel thickness is 1.1cm. The water evaporation efficiency of the hydrogel under the sunlight intensity is 3.11kg.m through the test of the device shown in figure 7 -2 ·h -1 The photothermal conversion efficiency was 89.6%.
Example 4
Dissolving 1g of sodium alginate in 19.37ml of deionized water, adding 3g of carbon black powder and 29.63g of dispersed kaolin slurry with the mass fraction of 13.5wt%, and stirring for 30min until dispersion is achieved; slowly adding 0.45g of hydroxyapatite in the stirring process, continuously stirring for 10min, then adding 2g of glucolactone, stirring for 2min, pouring into a mould, standing for gelling; and aging the gel overnight, and performing directional freeze-thaw treatment for 7 times to obtain the clay-based composite hydrogel. The directional freezing temperature is-55 ℃, and the specific surface area of the hydrogel reaches 50.54m by measurement 2 The directional freezing aperture range is between 60 and 80 mu m, and the gel is thickThe degree was 0.9cm. The hydrogel has a water evaporation efficiency of 3.66kg.m under one sun illumination intensity tested by the device shown in FIG. 7 -2 ·h -1 The photothermal conversion efficiency was 90.4%.
Example 5
Dissolving 1g of sodium alginate in 49ml of deionized water, adding 3g of carbon nano tube and 29.63g of dispersed bentonite slurry with the mass fraction of 13.5wt%, and stirring for 30min until dispersion; slowly adding 0.12g of hydroxyapatite in the stirring process, continuously stirring for 10min, then adding 1.6g of glucolactone, stirring for 2min, pouring into a mold, and standing for gelation; and aging the gel overnight, and performing directional freeze-thaw treatment for 7 times to obtain the clay-based composite hydrogel. Fig. 3 is an SEM picture under this condition. The directional freezing temperature is-70 ℃, and the specific surface area of the hydrogel reaches 52.28m through measurement 2 The volume/g of the directional freezing aperture is between 30 and 50 mu m, and the thickness of the gel is 0.6cm. The water evaporation efficiency of the hydrogel under the illumination intensity of one sun is 3.78 kg.m through the test of the device shown in figure 7 -2 ·h -1 The photothermal conversion efficiency was 92.7%.
Example 6
Dissolving 2g of sodium alginate in 34.67ml of deionized water, adding 2.25g of carbon black powder and 13.33g of well-dispersed attapulgite slurry with the mass fraction of 7.5wt%, and stirring for 30min until the mixture is dispersed; slowly adding 0.3g of hydroxyapatite in the stirring process, continuously stirring for 10min, then adding 1.5g of glucolactone, stirring for 2min, pouring into a mold, and standing for gelation; and aging the gel overnight, and performing directional freeze-thaw treatment for 8 times to obtain the clay-based composite hydrogel. The directional freezing temperature is-70 ℃, and the specific surface area of the hydrogel reaches 36.49m by measurement 2 The directional freezing aperture range is 50 to 80 mu m, and the gel thickness is 0.5cm. The hydrogel has a water evaporation efficiency of 3.06kg.m under one sun illumination intensity tested by the device shown in FIG. 7 -2 ·h -1 The photothermal conversion efficiency was 89.1%.
Example 7
Dissolving 0.75g of sodium alginate in 49.25ml of deionized water, adding 2.4g of graphite, and stirring for 30min until the graphite is dispersed; adding 0.15g calcium carbonate slowly while stirring, stirring for 10min, and addingAdding 1g of gluconolactone, stirring for 2min, pouring into a mold, and standing for gelation; and aging the gel overnight, and performing directional freeze-thaw treatment for 8 times to obtain the hydrogel. The directional freezing temperature is-40 ℃, and the specific surface area of the hydrogel reaches 21.56m by measurement 2 The directional freezing aperture range is 220 to 250 mu m, and the gel thickness is 1cm. The hydrogel has a water evaporation efficiency of 2.59kg.m under one solar illumination intensity tested by the device shown in FIG. 7 -2 ·h -1 The photothermal conversion efficiency was 88.6%.
Example 8
Dissolving 2g of sodium alginate in 96.4ml of deionized water, adding 1g of carbon black and 1.6g of attapulgite powder, and continuously stirring for 30min until dispersion; slowly adding 0.3g of hydroxyapatite in the stirring process, continuously stirring for 10min, then adding 1g of glucolactone, stirring for 2min, pouring into a mould, and standing for gelation; and aging the gel overnight, and performing directional freeze-thaw treatment for 6 times to obtain the clay-based composite hydrogel. According to measurement, when the ratio of the clay to the sodium alginate is 5 2 The directional freezing aperture range is 240 to 280 mu m, and the gel thickness is 1.5cm. The hydrogel has a water evaporation efficiency of 1.74 kg.m under one sun illumination intensity tested by the device shown in FIG. 7 -2 ·h -1 The photothermal conversion efficiency was 83.2%.
Example 9
Dissolving 2g of sodium alginate in 88ml of deionized water, adding 1g of carbon black and 10g of attapulgite powder, and continuously stirring for 30min until the mixture is dispersed; slowly adding 0.3g of hydroxyapatite in the stirring process, continuously stirring for 10min, then adding 1g of glucolactone, stirring for 2min, pouring into a mould, and standing for gelation; and aging the gel overnight, and performing directional freeze-thaw treatment for 6 times to obtain the clay-based composite hydrogel. According to the determination, when the ratio of the clay to the sodium alginate is 5 and the directional freezing temperature is-30 ℃, the specific surface area of the hydrogel reaches 33.19m 2 The directional freezing aperture range is between 100 and 120 mu m, and the gel thickness is 1.5cm. The water evaporation efficiency of the hydrogel under the sunlight intensity is 1.86 kg.m through the test of the device shown in figure 7 -2 ·h -1 The photo-thermal conversion efficiency is84.9%。
Example 10
Dissolving 2g of sodium alginate in 94ml of deionized water, adding 1g of carbon black and 4g of attapulgite powder, and continuously stirring for 30min until dispersion; slowly adding 0.3g of hydroxyapatite in the stirring process, continuously stirring for 10min, then adding 1g of glucolactone, stirring for 2min, pouring into a mould, and standing for gelation; and aging the gel overnight, and performing directional freeze-thaw treatment for 6 times to obtain the clay-based composite hydrogel. According to the determination, when the ratio of the clay to the sodium alginate is 2 and the directional freezing temperature is-30 ℃, the specific surface area of the hydrogel reaches 35.76m 2 The volume/g of the directional freezing aperture is within 120 to 180 mu m, and the thickness of the gel is 0.3cm. The hydrogel has a water evaporation efficiency of 1.51 kg.m under one sun illumination intensity, as measured by the device shown in FIG. 7 -2 ·h -1 The photothermal conversion efficiency was 82.7%.
Example 11
Dissolving 2g of sodium alginate in 94ml of deionized water, adding 1g of carbon black and 4g of attapulgite powder, and continuously stirring for 30min until dispersion; slowly adding 0.3g of hydroxyapatite in the stirring process, continuously stirring for 10min, then adding 1g of gluconolactone, stirring for 2min, pouring into a mold, and standing for gelation; and aging the gel overnight, and performing directional freeze-thaw treatment for 10 times to obtain the clay-based composite hydrogel. According to the determination, when the ratio of the clay to the sodium alginate is 2 and the directional freezing temperature is-30 ℃, the specific surface area of the hydrogel reaches 36.73m 2 The volume/g of the directional freezing aperture is between 80 and 120 mu m, and the thickness of the gel is 0.3cm. The water evaporation efficiency of the hydrogel under one solar illumination intensity is 1.65kg.m by testing through a device shown in figure 7 -2 ·h -1 The photothermal conversion efficiency was 84.5%.
Example 12
Dissolving 2g of sodium alginate in 96.4ml of deionized water, adding 1g of carbon black and 1.6g of attapulgite powder, and continuously stirring for 30min until dispersion; slowly adding 0.3g of hydroxyapatite in the stirring process, continuously stirring for 10min, then adding 1g of gluconolactone, stirring for 2min, pouring into a mold, and standing for gelation; and aging the gel overnight, and performing directional freeze-thaw treatment for 6 times to obtain the clay-based composite hydrogel. By measuring in clay and sea
The ratio of the sodium alginate is 1 2 The directional freezing aperture range is 130 to 160 mu m, and the gel thickness is 1.5cm. The water evaporation efficiency of the hydrogel under the sunlight intensity is 1.44kg.m through the test of the device shown in figure 7 -2 ·h -1 The photothermal conversion efficiency was 83.8%.
The following examples 8 to 12 were compared to investigate the influence of freezing temperature, freezing and thawing times and the ratio of clay to sodium alginate on the water evaporation efficiency of the clay-based composite hydrogel prepared by the present invention, and the results are shown in table 1:
TABLE 1
| Sample(s) | Illumination time/h | Ratio of attapulgite to sodium alginate | Freezing temperature/. Degree.C | Number of freeze thawing | Water evaporation rate/kg/(m) 2 ·h) | Photothermal conversion efficiency/%) |
| Example 8 | 1 | 1：0.8 | -30 | 6 | 1.74 | 83.2 |
| Example 9 | 1 | 5：1 | -30 | 6 | 1.86 | 84.9 |
| Example 10 | 1 | 2：1 | -30 | 6 | 1.51 | 82.7 |
| Example 11 | 1 | 2：1 | -30 | 10 | 1.65 | 84.5 |
| Example 12 | 1 | 1：0.8 | -90 | 6 | 1.44 | 83.8 |
Analysis examples 8-12 show that the aperture of the porous material in the range of 80 to 380 μm and the mesoporous structure formed on the hole wall by the attapulgite can be obtained by adjusting the directional freezing temperature, the freezing and thawing times and the ratio of the attapulgite to the sodium alginate, and the pore diameter is mainly distributed in the range of 2 to 50nm. The attapulgite on the pore wall and the formed mesoporous structure can greatly improve the hydrophilicity of the hydrogel and realize rapid water absorption, as shown in figure 4. When the content of the attapulgite is too high, the growth speed of ice crystals is hindered, the aperture size is gradually reduced, the structure becomes compact, and water vapor cannot smoothly pass through a steam channel of a directional freezing structure. When the content of the attapulgite is too low, the mesoporous structure built by the attapulgite on the hole wall is reduced, and the water absorption capacity is reduced, so that the water evaporation rate is influenced; with the reduction of the directional freezing temperature, although the ice crystal grows fast and the aperture range is gradually reduced, the whole water delivery effect is still poor and a lower water evaporation rate is shown. And due to the increase of the freezing and thawing times, a larger pore channel structure can be constructed to enhance the water transportation, but the water evaporation rate is still not high due to the capillary action. Therefore, the selection of proper freezing temperature, freezing and thawing times and the proportion of the clay and the sodium alginate have important significance on the water evaporation efficiency.
Where mentioned above are merely embodiments of the invention, any feature disclosed in this specification may, unless stated otherwise, be replaced by alternative features serving equivalent or similar purposes; all of the disclosed features, or all of the method or process steps, may be combined in any combination, except mutually exclusive features and/or steps.
Claims (10)
1. A preparation method of clay-based composite hydrogel for solar seawater desalination is characterized by comprising the following steps:
step (1), adding sodium alginate into an aqueous solution to dissolve to obtain a sodium alginate aqueous solution, adding clay and a carbon-based material into the sodium alginate aqueous solution, and mixing;
wherein the addition amount of the sodium alginate in the sodium alginate aqueous solution is 0.5-4 wt%, and the addition amount of the clay in the sodium alginate aqueous solution is 0-15wt%;
step (2), slowly adding calcium salt into the mixed solution obtained in the step (1), and stirring to obtain a mixed suspension;
adding glucolactone into the mixed suspension obtained in the step (2), uniformly stirring, pouring into a mold, and standing for gelation;
and (4) aging the obtained gel, and performing multiple directional freeze thawing to obtain the clay-based composite hydrogel with the preset thickness.
2. The method for preparing a clay-based composite hydrogel according to claim 1, wherein the method comprises the following steps: in the step (1), the clay is one or a combination of more than two of nanoscale attapulgite, bentonite, kaolin, illite, diatomite or sepiolite.
3. The method for preparing a clay-based composite hydrogel according to claim 1, wherein the method comprises the following steps: in the step (1), the addition amount of the carbon-based material in the sodium alginate aqueous solution is 0.1-10wt%.
4. The method for preparing a clay-based composite hydrogel according to claim 1, wherein the method comprises the following steps: in the step (1), the carbon-based material is one or a combination of more than two of graphite, graphene, carbon black, mxene, fullerene, activated carbon, carbon nano-tubes or carbon fibers.
5. The method for preparing a clay-based composite hydrogel according to claim 1, wherein the method comprises the following steps: in the step (2), the addition amount of the calcium salt in the mixed suspension is 0.1 to 1wt%;
and/or the calcium salt is one or the combination of more than two of calcium carbonate, calcium sulfate, calcium sulfite, hydroxyapatite and calcium phosphate.
6. The method for preparing the clay-based composite hydrogel according to claim 1, wherein the method comprises the following steps: in the step (3), the addition amount of the gluconolactone in the mixed suspension is 0.1 to 1wt%.
7. The method for preparing a clay-based composite hydrogel according to claim 1, wherein the method comprises the following steps: the mass ratio of the sodium alginate to the clay in the clay-based composite hydrogel is 1 to 1.
8. The method for preparing a clay-based composite hydrogel according to claims 1 to 7, wherein: the total solid content of the sodium alginate and the clay in the clay-based composite hydrogel is 4-8%.
9. The method for preparing the clay-based composite hydrogel according to claim 1, wherein the method comprises the following steps: in the step (4), the preset thickness is 0.5 to 1.1cm.
10. The method for preparing a clay-based composite hydrogel according to claim 1, wherein the method comprises the following steps: in the step (4), the directional freezing and thawing times are 6 to 8;
and/or the directional freezing temperature in the directional freezing and thawing is-20 ℃ to-70 ℃.
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