Self-circulating solar interface catalytic concentration evaporator and preparation method and application thereof

Abstract

The application discloses a self-circulation solar interface catalytic concentration evaporator and a preparation method and application thereof. The whole self-circulation reaction system is driven by solar energy, is green and environment-friendly, and has multiple functions such as fresh water resource acquisition and high value-added utilization of water body contained resources; the gravity difference driven one-way fluid transportation can effectively improve the fresh water preparation capacity of the interface water evaporator, the high performance design of the organic supramolecular hybrid array type catalytic evaporation material is combined, the solar light absorption capacity and evaporation performance of the evaporator are improved, and more importantly, the catalytic conversion and concentration treatment of the high value resources in the water body can be realized; further, the sun light is collected by a solar panel to drive a peristaltic pump, the water body resources which are not completely reacted can be recycled again until all the catalytic conversion and continuous concentration are realized, and then a green and sustainable self-circulation system based on solar energy is constructed.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of solar energy utilization and water treatment and resource utilization, and particularly relates to a self-circulating solar interfacial catalytic concentration evaporator and a preparation method and application thereof. BACKGROUND

[0002] Solar thermal technology can directly collect solar energy for heating and energy storage applications, such as solar water evaporation technology, which can use green and environmentally friendly solar energy to produce clean fresh water from seawater / wastewater. This technology is of great significance for alleviating the current world shortage of fresh water resources.

[0003] Traditional solar water heating technology has low light absorption efficiency and serious heat loss, resulting in very low photo-thermal conversion efficiency. In recent years, unlike traditional solar evaporation heating of large amounts of water, a promising water purification technology, solar interfacial water evaporation, has developed rapidly.

[0004] Solar interfacial water evaporation is a technology that realizes water and air interfacial heating through the use of solar photo-thermal conversion, which can evaporate water into the air and collect it through the condensation process, greatly improving the heat utilization efficiency, and the cost and energy input are relatively low. This technology has great research value and application potential.

[0005] So far, most of the designed evaporators are only for seawater desalination and wastewater purification. For example, the patent specification with publication number CN212450720U discloses a self-gravity water inlet heat recovery type liquid film evaporation type solar seawater distillation device, which can use the potential energy of seawater to realize self-gravity water inlet of seawater, saving power consumption. For example, ZL202220478734.0 discloses a light-heat evaporation and photocatalytic degradation of pollutants treatment device, which can realize water evaporation and organic pollutant degradation into carbon dioxide and water. However, directly degrading all organic pollutants in water body causes great resource waste for some polluted water bodies containing high-value resources, and the designed equipment is relatively complex. In addition, the liquid backflow phenomenon in the current conventional interfacial evaporation process does not have effective concentration effect.

[0006] Therefore, how to realize evaporation while catalyzing and concentrating the useful resources contained in the water body has very important practical significance. For example, there is a large amount of lignin in papermaking wastewater. As an important part of biomass resources, lignocellulose has the characteristics of wide distribution, high reserves and renewable, and has great potential for development and utilization. For example, the concentration of lithium and other resources in salt lakes or seawater can greatly improve the economic benefits of lithium extraction technology. Therefore, if lignin can be catalytically decomposed into small molecules while solar energy is used to evaporate water to obtain fresh water resources, or if lithium, magnesium and other valuable substances can be concentrated, it is expected to realize all-round use of non-fresh water bodies containing high-value resources and greatly improve their added value. SUMMARY

[0007] The present application provides a self-circulating solar interface catalytic concentration evaporator and its preparation method and application. The whole self-circulating reaction system is driven by solar energy, which is green and environmentally friendly, and has multiple functions such as obtaining fresh water resources and high-value utilization of resources contained in water body; the one-way fluid transport driven by gravity difference can effectively improve the fresh water preparation capacity of the interface water evaporator and greatly improve its concentration degree, combined with the high-performance design of the array-type catalytic evaporation material of organic supramolecular hybrid, the solar light absorption capacity and evaporation performance of the evaporator are improved, and more importantly, the catalytic conversion and concentration of high-value resources in the water body can be realized. Among them, the array-type catalyst is titanium dioxide material. As an important photocatalyst with low cost, easy availability, no pollution and high practical value, titanium dioxide has been proved to have broad application prospects in the field of photocatalysis, and is one of the important photocatalytic materials that can be put into production in the future. However, its catalytic effect is still limited by limited light absorption and low utilization rate of photo-generated carriers. Organic supramolecular / inorganic hybridization can play a complementary role, and the array-type titanium dioxide material can be enhanced by organic supramolecular hybridization to absorb sunlight, improve the separation and migration of carriers, and significantly improve the utilization rate of carriers. The organic supramolecule selected in the present application is perylene diimide (PDI), which not only has a narrow band gap and can absorb visible light in sunlight, but also can be formed by molecular self-assembly, and the preparation conditions are simple. Further, the sunlight is collected by a solar panel to drive a peristaltic pump, which can recycle the water body resources that have not been completely reacted until all the catalytic conversion and continuous concentration are achieved, thereby building a green and sustainable self-circulating system based on solar energy.

[0008] The first aspect of the present application provides a preparation method of a self-circulating solar interface catalytic concentration evaporator, comprising the steps of:

[0009] S1, cut the hydrophilic transport material into a long strip, overlap it, seal it with an opaque bag, and only leave two end interfaces to obtain a sealed transport material that can transport liquid;

[0010] S2, the clean carbon is arranged in a hydrothermal kettle containing a solution of tetrabutyl titanate and hydrochloric acid for hydrothermal reaction, and the reaction is cooled to room temperature after completion to obtain an evaporation light heat material loaded with array type titanium dioxide photocatalyst; the evaporation light heat material is placed in sulfuric acid for static treatment, 3, 4, 9, 10-tetraformyl diimide (CAS No.: 81-33-4) is added and ultrasonic treatment is performed, room temperature stirring treatment is performed after ultrasonic treatment, and the evaporation light heat material is taken out after sufficient reaction, washed with deionized water until the pH is neutral, and dried to obtain an organic supramolecular hybrid high-performance evaporation light heat material;

[0011] S3, the two ends of the organic supramolecular hybrid high-performance evaporation light heat material are connected with the sealing transmission material respectively, the connection parts are sealed, the obtained assembly is fixed on a polyurethane foam to obtain a transport and reaction device for solution flow and interfacial evaporation, catalysis and concentration;

[0012] S4, the other ends of the two sealing transmission materials in the transport and reaction device are respectively placed in a container I containing a solution to be reacted and a container II for collecting reaction liquid, the liquid levels in the two containers are kept at a certain height difference to obtain a gravity-driven one-way flow solar evaporation, catalysis and concentration interfacial reaction device; the solution to be reacted is an aqueous solution containing high-value resources;

[0013] S5, a solar panel is connected to a circulating pump to drive the circulating pump to operate, the inlet and outlet of the circulating pump are connected to the container II and the container I respectively; sunlight is irradiated on the organic supramolecular hybrid high-performance evaporation light heat material of the interfacial reaction device and the solar panel to realize completely solar-based self-circulation interfacial evaporation and resource catalysis and concentration contained in water.

[0014] In step S1, the hydrophilic transmission material can be filter paper, carbon paper, hydrophilic non-woven fabric, hydrophilic cotton or carbon felt.

[0015] In a preferred embodiment, in step S2:

[0016] In the solution of tetrabutyl titanate and hydrochloric acid, the volume ratio of hydrochloric acid to water is 1:1, and the mass percentage of HCl in hydrochloric acid is 36% to 38%;

[0017] The amount of the solution of tetrabutyl titanate and hydrochloric acid used is 8 to 32 mL, the amount of tetrabutyl titanate used is 256 to 1024 μL, the amount of sulfuric acid used is 4 to 12 mL, the concentration of sulfuric acid is 1 to 2 mo / L, and the amount of 3, 4, 9, 10-tetraformyl diimide used is 5 to 15 mg, relative to a clean carbon cloth with a single surface area of 2 to 12 cm 2

[0018] ​In a preferred embodiment, in step S2, the hydrothermal reaction is carried out at a temperature of 150-220 DEG C for 6-10 hours.

[0019] In a preferred embodiment, in step S2, the standing treatment is carried out for 6-12 hours.

[0020] In a preferred embodiment, in step S2, the ultrasonic treatment is carried out for 5-10 minutes.

[0021] In a preferred embodiment, in step S2, the room temperature stirring treatment is carried out for 1-3 hours.

[0022] In a preferred embodiment, in step S2, the drying is carried out at a temperature of 50-70 DEG C.

[0023] In step S5, the solar panel can be a silicon solar cell, a dye-sensitized solar cell, a perovskite solar cell, an organic solar cell, etc.

[0024] The second aspect of the present application provides a self-circulating solar interface catalytic concentration evaporator prepared by the preparation method.

[0025] The third aspect of the present application provides an application of the self-circulating solar interface catalytic concentration evaporator in catalysis of a lignin solution.

[0026] The fourth aspect of the present application provides an application of the self-circulating solar interface catalytic concentration evaporator in concentration of a valuable substance solution containing lithium and / or magnesium ions.

[0027] As a general inventive concept, the present application also provides a method for catalytic concentration of an aqueous solution containing high-value resources, which uses the self-circulating solar interface catalytic concentration evaporator, and the aqueous solution containing high-value resources is at least one of a lignin solution and a solution containing lithium and / or magnesium ions.

[0028] In a preferred embodiment, the method for catalytic concentration of the aqueous solution containing high-value resources is a lignin solution, and the catalytic product is a lignin-derived phenolic monomer including vanillin and syringaldehyde.

[0029] Compared with the prior art, the present application has the following beneficial effects:

[0030] The application provides a self-circulation solar interface catalytic concentration evaporator and a preparation method and application thereof. The entire self-circulation reaction system is driven by solar energy, is green and environmentally friendly, and has multiple functions such as fresh water resource acquisition and high value-added utilization of water body resources; the one-way fluid transportation driven by gravity difference can effectively improve the fresh water preparation capacity of the interface water evaporator, the high-performance design of the array type catalytic evaporation material combined with organic supramolecular hybridization realizes the improvement of the solar light absorption capacity and evaporation performance of the evaporator, and more importantly, the catalytic conversion and concentration treatment of high value resources in the water body can be realized; further, the unreacted water body resources can be recycled again by the solar panel to drive the peristaltic pump until all the catalytic conversion and continuous concentration are realized, and then a green and sustainable self-circulation system based on solar energy is constructed. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 It is a schematic diagram of the solar-driven evaporation + catalysis + concentration system and self-circulation system.

[0032] Figure 2 It is a scanning electron microscope (SEM) photo and Raman spectrum of the single array type and organic supramolecular hybrid array type catalytic evaporation material in Example 1. DETAILED DESCRIPTION

[0033] The application will be further described below in combination with the drawings and specific examples. It should be understood that these examples are only used to illustrate the application and are not used to limit the scope of the application. The operation methods not specified in the following examples are usually carried out according to the conventional conditions or the conditions recommended by the manufacturers.

[0034] Example 1

[0035] The filter paper is cut into a long strip, overlapped and sealed with an opaque bag, and only two end interfaces are left to obtain a sealed filter paper capable of transporting liquid.

[0036] A clean carbon cloth with a size of 3cm*2cm is arranged in a hydrothermal kettle containing 16mL of a mixed solution of hydrochloric acid (36wt%-38wt%) and pure water with a volume ratio of 1:1 containing 512μL of tetrabutyl titanate, and a hydrothermal reaction is carried out at a reaction temperature of 200℃ and a reaction time of 8h. After the reaction is completed and cooled to room temperature, an evaporation photo-thermal material loaded with an array type titanium dioxide photocatalyst is obtained, and the morphology thereof is shown in Figure 2; the evaporation light heat material is placed in 8 mL of 1 mol / L sulfuric acid for 8 hours, 10 mg of 3, 4, 9, 10-tetraformyl diimide is added and ultrasonic treatment is performed for 5 min, after the ultrasonic treatment, room temperature stirring is performed for 2 h, finally, the evaporation light heat material is taken out, washed with deionized water until the pH is neutral, and dried at a temperature of 60°C to obtain an organic supramolecular hybrid high-performance evaporation light heat material, and the morphology is shown in Figure 2 It can be seen that the array titanium dioxide material surface is successfully loaded with the organic supramolecular material. Meanwhile, compared with the array titanium dioxide material alone, the characteristic peak of the organic supramolecular material is also detected in the Raman spectrum of the organic supramolecular hybrid material.

[0037] Both ends of the obtained organic supramolecular hybrid high-performance evaporation light heat material are connected with sealed filter paper, the two connection positions are sealed with glass slides and adhesive tapes, and the above-mentioned assembled evaporation light heat material and sealed transport material are fixed on a polyurethane foam to obtain a transport and reaction device for solution flow and interfacial evaporation, catalysis and concentration.

[0038] The other end of the two sections of the sealed transport material in the transport and reaction device is respectively placed in a container I containing a solution to be reacted and a container II for collecting the reaction liquid, and the solution to be reacted is an aqueous solution containing 300 mg / L lignin, wherein the two containers maintain a certain height difference to obtain a gravity-driven one-way flow solar evaporation, catalysis and concentration interfacial reaction device.

[0039] A silicon solar panel is placed below the organic supramolecular hybrid high-performance evaporation light heat material of the interfacial reaction device, and the silicon solar panel is connected to a suitable electric peristaltic pump to drive its operation, wherein the inlet and outlet of the peristaltic pump are connected to the container II and the container I respectively; 1 intensity of simulated sunlight is irradiated on the organic supramolecular hybrid high-performance evaporation light heat material of the interfacial reaction device and the silicon solar panel to realize completely solar-based self-circulation interfacial evaporation and water body resource catalysis and concentration. The overall evaporation + catalysis + concentration system and the self-circulation system are shown in Figure 1 .

[0040] In this embodiment, the evaporation, catalysis and concentration of the lignin aqueous solution are carried out, the evaporation rate of the organic supramolecular hybrid high-performance evaporation light heat material is 4.4 kg m –2 h –1 , part of the lignin can be converted into aromatic compounds such as vanillin and eugenol, and the lignin catalytic conversion rate is about 34.8%.

[0041] Example 2

[0042] The hydrophilic non-woven fabric is arranged in a strip shape, and after being overlapped and treated, the sealed filter paper capable of conveying liquid is obtained by sealing treatment with an opaque bag, leaving only two end interfaces;

[0043] A clean carbon cloth with a size of 3 cm x 2 cm is placed in a hydrothermal kettle containing 16 mL of a mixed solution of hydrochloric acid (36% to 38% by mass) and pure water in a volume ratio of 1:1, and 512 μL of tetrabutyl titanate is added to the hydrothermal kettle for hydrothermal reaction, wherein the reaction temperature and time are 220°C and 6 h, respectively. After the reaction is completed and the temperature is cooled to room temperature, an evaporation light-heat material loaded with an array type photocatalyst is obtained. The evaporation light-heat material is placed in 8 mL of 2 mol / L sulfuric acid for 10 hours of standing treatment, and then 10 mg of 3,4,9,10-tetraformyl diimide is added and ultrasonicated for 5 min. After ultrasonic treatment, the evaporation light-heat material is stirred at room temperature for 2 h. Finally, the evaporation light-heat material is taken out, washed with deionized water until the pH is neutral, and dried at a temperature of 60°C to obtain an organic supermolecular hybrid high-performance evaporation light-heat material.

[0044] The two ends of the obtained organic supermolecular hybrid high-performance evaporation light-heat material are connected to sealed filter papers, and the two connection parts are sealed with glass slides and adhesive tapes. The assembled evaporation light-heat material and sealed transport material are fixed on a polyurethane foam to obtain a transport and reaction device for solution flow and interfacial evaporation, catalysis and concentration.

[0045] The other ends of the two sections of the sealed transport material in the transport and reaction device are placed in a container I containing a reaction solution and a container II for collecting the reaction liquid, respectively. The reaction solution is an aqueous solution containing 20 mmol / L lithium ions. The two containers maintain a certain height difference to obtain a gravity-driven one-way flow solar evaporation and concentration interfacial reaction device.

[0046] A dye-sensitized solar panel is placed below the organic supermolecular hybrid high-performance evaporation light-heat material of the interfacial reaction device, and the dye-sensitized solar panel is connected to a suitable motorized peristaltic pump to drive its operation. The inlet and outlet of the peristaltic pump are connected to the container II and the container I, respectively. Sunlight is irradiated on the organic supermolecular hybrid high-performance evaporation light-heat material and the dye-sensitized solar panel of the interfacial reaction device to realize completely solar-based self-circulating interfacial evaporation and water body resource catalysis and concentration.

[0047] In this embodiment, the evaporation and concentration of lithium ion aqueous solution are carried out. The evaporation rate of the organic supermolecular hybrid high-performance evaporation light-heat material is 4.3 kg m –2 h –1 The molar concentration of lithium ions in the reaction liquid collected by the container II is increased to 38 mmol / L, and the concentration effect is 190%.

[0048] Comparative Example 1

[0049] The difference from Example 1 is only that the vaporization light-thermal material loaded with array type titanium dioxide photocatalyst is used instead of the organic supermolecular hybrid high-performance vaporization light-thermal material, and the rest is the same. It is found that the evaporation rate is 3.4 kg m – 2 h –1 The catalytic conversion rate of lignin is about 25.4%. The evaporation efficiency and lignin catalytic effect of the interface reactor are not as good as those of Example 1.

[0050] Comparative Example 2

[0051] The difference from Example 2 is only that the clean carbon cloth with a size of 3 cm x 2 cm is directly used instead of the organic supermolecular hybrid high-performance vaporization light-thermal material, and the rest is the same. It is found that the evaporation rate is 2.8 kg m –2 h –1 , and the concentration effect is 130%. The evaporation and concentration effect of the interface reactor is not as good as that of Example 2.

[0052] In addition, it should be understood that, after reading the above description of the present application, those skilled in the art can make various modifications or modifications to the present application, and these equivalent forms also fall within the scope defined by the claims attached hereto.

Claims

1. The application of a self-circulating solar-powered interfacial catalytic concentrator in lignin solution catalysis, characterized in that, The preparation method of the self-circulating solar interface catalytic concentrator includes the following steps: S1. Cut the hydrophilic transport material into long strips, overlap them, and then seal them with a light-proof bag, leaving only the two ends open, to obtain a sealed transport material that can transport liquids. S2. Clean carbon is placed in a hydrothermal reactor containing an aqueous solution of tetrabutyl titanate and hydrochloric acid for a hydrothermal reaction. After the reaction is completed, the mixture is cooled to room temperature to obtain an evaporative photothermal material supported on an array-type titanium dioxide photocatalyst. The evaporative photothermal material is then placed in sulfuric acid for static treatment, followed by the addition of 3,4,9,10-tetraformamide and sonication. After sonication, the mixture is stirred at room temperature until fully reacted. The evaporative photothermal material is then removed, rinsed with deionized water until the pH is neutral, and dried to obtain a high-performance organic supramolecular hybrid evaporative photothermal material. In the aqueous solution of tetrabutyl titanate and hydrochloric acid, the volume ratio of hydrochloric acid to water is 1:1, and the mass percentage of HCl in the hydrochloric acid is 36%~38%. The single-sided area is 2~12 cm². 2 The clean carbon cloth, wherein the amount of the aqueous solution of tetrabutyl titanate and hydrochloric acid is 8-32 mL, wherein the amount of tetrabutyl titanate is 256-1024 μL, the amount of sulfuric acid is 4-12 mL, the concentration of sulfuric acid is 1-2 mol / L, and the amount of 3,4,9,10-tetracarboxydiimide is 5-15 mg; S3. The two ends of the organic supramolecular hybrid high-performance evaporative photothermal material are respectively connected to the sealing transport material, and the connection between the two ends is sealed. The resulting component is fixed on polyurethane foam to obtain a transport and reaction device for solution flow and interfacial evaporation, catalysis and concentration. S4. Place the other ends of the two sealed transport materials in the transport and reaction device into container I containing the solution to be reacted and container II for collecting the reaction liquid, respectively. Maintain a certain height difference between the liquid levels in the two containers to obtain a gravity-driven unidirectional flow solar evaporation, catalysis and concentration interface reaction device; the solution to be reacted is an aqueous solution containing high-value resources; the aqueous solution containing high-value resources is a lignin solution, and the catalytic product is a lignin-derived phenolic monomer including vanillin and syringin. S5. Connect the solar panel to the circulation pump to drive the circulation pump to run. The inlet and outlet of the circulation pump are respectively connected to container II and container I. Sunlight is irradiated onto the high-performance evaporative photothermal material of the organic supramolecular hybrid in the interface reaction device and the solar panel to realize self-circulating interface evaporation and catalysis and concentration of water-containing resources based entirely on solar energy.

2. The application according to claim 1, characterized in that, In step S1, the hydrophilic transport material is filter paper, carbon paper, hydrophilic nonwoven fabric, hydrophilic cotton, or carbon felt.

3. The application according to claim 1, characterized in that, In step S2, the hydrothermal reaction temperature is 150~220℃ and the reaction time is 6~10 h.

4. The application according to claim 1, characterized in that, In step S2: The settling time is 6-12 hours; The ultrasound session lasted 5-10 minutes. The room temperature stirring treatment time is 1~3 h; The drying temperature is 50~70℃.

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