The present disclosure relates to a novel energy-saving seawater desalination method, the method is based on highly effective photothermal conversion efficiency and Joule heating effects of carbon-based materials, such as carbon nanotubes or graphene, and the method combines thermal phase change and evaporation mass transmission to achieve seawater desalination.
With population growth and water pollution becoming more and more serious, water shortages have become one of the most severe global challenges for humans and society. At present, seawater desalination technologies that have been developed and have been widely used in large-scale commercial applications comprise reverse osmosis (RO), electrodialysis (ED), multi-stage flash (MSF), low-temperature multi-effect (MED), etc. These technologies are highly effective in desalination. At the same time, the energy consumption caused by equipment operation cannot be ignored, and solar seawater desalination technology is considered to be a promising technology due to its advantages of low energy consumption, low cost, high energy conversion efficiency, and environmental friendliness. At present, the field of solar seawater desalination has achieved interface solar-driven steam generation through photon management, nano-scale thermal control, development of new photothermal conversion materials, and design of high-efficiency light-absorbing solar distillers. This green and sustainable seawater desalination technology has become a research hotspot in recent years. Carbon-based materials such as carbon nanotubes, graphene, carbon black, graphite, etc. have light absorption capabilities covering the entire solar spectrum and are a new type of light-to-heat conversion material.
For embodiment, CN200910169726.7 provides a method of using carbon nanotubes to absorb solar energy and efficiently desalinate seawater using carbon nanotubes to realize the conversion of light energy to heat energy and using circulating carrier gas to take away and transfer the heat energy on the surface of carbon nanotubes to seawater. The carrier gas enters the seawater storage tank to divide the seawater into upper and lower layers with different temperatures and concentrations. The upper and lower layers of seawater and the carrier gas have a continuous heat, mass, and momentum transfer process to realize the separation of fresh water and concentrated seawater. CN201710591777.3 discloses a solar seawater desalination or sewage treatment method based on a carbon nanotube membrane. This disclosure uses a carbon nanotube vertical array directly prepared by a chemical vapor deposition method as a raw material, and obtains a carbon nanotube vertical array membrane with strong light absorption and surface hydrophilicity. This hydrophilic carbon nanotube membrane is placed on a surface of the water to be treated. As the carbon nanotube membrane can efficiently absorb light and perform light-to-heat conversion, heating the water body causes rapid evaporation of water, and the steam is condensed to obtain purified water.
However, the solar desalination process is affected by the intensity of sunlight. The four seasons and geographical limitations related to the intensity of sunlight make traditional solar desalination processes unable to achieve continuous and efficient desalination under natural conditions.
CN201810956984.9 provides a carbon nanotube-cellulose acetate membrane for high-efficiency desalination of seawater and a preparation method thereof. This method introduces magnetized carbon nanotubes into the cellulose acetate reverse osmosis membrane, and aligns the carbon nanotubes through a magnetic field to form a permeation channel. When in use, a high-frequency pulsed magnetic field is applied to make the carbon nanotubes micro-oscillate to weaken the interaction of water molecules and cellulose acetate and promote the passage of water molecules through the membrane. Compared with the traditional method, the carbon nanotube-cellulose acetate membrane prepared by the disclosure can still maintain a higher desalination rate and water flux after long-term use and has high seawater desalination efficiency and long service life.
However, it still has not solved the technical problem of continuous desalination of seawater.
The present disclosure provides an electrothermal-photothermal alternative continuous seawater desalination system based on Joule heating effects and photothermal conversion effects of carbon-based materials, such as, carbon nanotubes or graphene. The system can store some solar energy in a form of electric energy during daylight. At the same time, a carbon nanotube composite porous membrane can directly absorb solar energy, and a photothermal conversion is complete. This heat promotes water molecules evaporate and pass through micrometer-nanometer multi-level pores of the carbon nanotube composite porous membrane. Evaporated water molecules are collected, and a first solar seawater desalination is finally achieved. The system can release electric energy when there are insufficient daylight hours or at night, and the carbon nanotube composite porous membrane generate Joule heat due to the electric energy. The Joule heat drives the water molecules evaporate and pass through the micrometer-nanometer multi-level pores. Evaporated water molecules is collected, and a second solar seawater desalination is finally achieved. The system achieves a highly effective and energy-saving seawater desalination process and solves the common technical problems, such as, corrosion resistance and fouling resistance of membrane materials. It utilizes the excellent conductivity, light absorption characteristics, and anti-fouling and salt-resistance effects of carbon-based composite membranes, and, combined with solar cells, the system realizes 24 hour continuous seawater desalination.
1. In this method, carbon nanotubes are used as carbon-based materials, which have light absorption capacity covering entire sunlight spectrum and excellent photothermal conversion characteristics. This type of material shows strong Joule heat effects and electrochemical corrosive resistance under energized conditions. A multi-level and multi-scale pore channel system in this kind of material can continuously and efficiently provide structural support for water transport and salt blocking. It is a new type of photothermal and electrothermal dual-responsive seawater desalination membrane material.
2. This method uses a laser perforating method to construct a micrometer-nanometer multi-level pore structure, which has both high salt rejection rate and quick water transport capabilities.
3. The hydrophobic polymer is used as the structural support when the method is implemented, and the carbon-based composite membrane has good mechanical strength (no deformation happens after immersing in salt water for 30 minutes).
4. When this method is implemented, the carbon nanotubes, graphene, or other carbon-based materials can still maintain good hydrophobicity under long-term energized conditions (after 1.5 hours of electrification, a contact angle of 100 g/L NaCl solution on the membrane surface can still be maintained above 120° C.), which breaks through membrane wetting barriers of the traditional commercial separation membranes in practical applications.
5. When this method is implemented, an interdigital electrode is connected to the carbon nanotube composite porous membrane used in parallel to ensure that each membrane can reach a highest temperature under the same voltage.
6. When this method is implemented, a sandwich structure (i.e., a sandwich package structure) is used to package the carbon nanotube composite porous membrane and the electrode. That is, a first polymethyl methacrylate (PMMA) plate, a first silica gel, the carbon nanotube composite porous membrane and the electrode, a second silica gel, a second PMMA plate are superimposed in sequence, and the sandwich structure can effectively reduce the electrochemical corrosion of materials of the carbon nanotube composite porous membrane and the electrode and avoid circuit aging.
7. When this method is implemented, compared with the traditional commercial separation membranes, the carbon nanotube composite porous membrane can generate heat, and a heating temperature is controllable (a temperature of the membrane surface can be adjusted by adjusting the voltage, and the temperature of the membrane surface can be up to 113.2° C. at 20 V).
8. When this method is implemented, an electrical responsive polymer can be coated on a surface of the carbon nanotube composite porous membrane to reduce an operation voltage of the system and reduce electrochemical reactions on a surface of the electrode. After a carbolong complex 1# is coated, the surface of the membrane can be up to 150° C. under 4 V voltage.
9. When this method is implemented, higher evaporation rate is achieved than the traditional solar seawater desalination process (electrothermal evaporation rate: 12.51 kg/m2·h, photothermal evaporation rate: 15.80 kg/m2·h).
10. The method has a better salt rejection rate (up to 99.959%) than the traditional seawater desalination process.
11. When this method is implemented, the energy utilization efficiency is high. When the voltage is 10 V, the energy utilization efficiency of the electric joule heat is the highest under a condition that four membranes are integrated, and its value is 92.70%. When the light concentration Copt=4, the energy utilization efficiency of light heat is the highest under the condition that four membranes are integrated, and its value is 93.64%.
12. This method can be alternately operated for 24 hours uninterruptedly. The carbon nanotube composite porous membrane is converted from light to heat to provide heat and a driving force for mass transmission to carry out the seawater desalination process under daylight conditions, and a solar panel is used to convert light energy into a form of electric energy. The energy stored in the solar panel is used to energize the carbon nanotube composite porous membrane to generate Joule heat to provide heat and a driving force of mass transmission to carry out the seawater desalination process under insufficient daylight conditions or at night. This cycle realizes 24 hour continuous seawater desalination by alternating a photothermal process and an electrothermal process.
13. All energy used in this method is directly or indirectly provided by the sunlight without external energy input systems. It is a new energy-saving seawater desalination method.
14. A hydrophobic carbon nanotube composite membrane is made of a hydrophobic polymer and carbon-based materials, and the carbon-based materials are, such as, carbon nanotubes or graphene. The hydrophobic carbon nanotube composite membrane is perforated to obtain the hydrophobic carbon nanotube composite membrane having micrometer-nanometer multi-level pore structure using laser light. Further, a surface is coated with a photothermal-electrothermal responsive polymer to increase electric joule heat and photothermal effects to increase energy utilization efficiencies, and the hydrophobic carbon nanotube composite membrane having multi-level pore structure and electrothermal effects and photothermal effects is finally obtained. A corresponding device is designed, a hydrophobic carbon nanotube composite porous membrane is applied to electro-induced seawater desalination and light-induced seawater desalination, conditions are controlled to enable the hydrophobic carbon nanotube composite porous membrane to generate heat, the heat functions a heat source to provide the driving force for the mass transmission of the water phase change. The present disclosure combines a thermal phase change process and a method using the membrane, and the 24 hour continuous seawater desalination by alternating a photothermal process and an electrothermal process is complete.
The present disclosure will be further described below in combination with the accompanying drawings and embodiments.
1. Preparation of a Hydrophobic Carbon Nanotube Composite Membrane (e.g., a Base Using a Carbon Nanotube Array):
Toluene is used as carbon source, ferrocene is used as a catalyst, and 4 wt % solution of ferrocene and toluene is prepared. A carbon nanotube array with a wide tube diameter (about 80 nm), a high crystallinity degree (IG/D=≠2.51), a high density (0.17 g/cm3), and a controllable height (20-1000 μm) is prepared at 740° C. using floating catalyst chemical vapor deposition (FCCVD) method. Polydimethylsiloxane (PDMS) components A and B are uniformly mixed at a weight ratio of 10:1 to obtain a mixture, air bubbles of the mixture are removed for 30 minutes, and the mixture is dripped onto a surface of the carbon nanotube array by a pipette. After the carbon nanotube array is completely infiltrated, the carbon nanotube array is left to stand for 30 minutes, excessive resin of the PDMS components A and B is removed by setting a spin coating procedure as follows: 1) 500 revolutions for 20 seconds, 2) 3000 revolutions for 40 seconds, and 3) the carbon nanotube array is solidified at 70° C. for 3 hours to obtain a membrane. After a complete solidification, a substrate is peeled off, a surface is polished to expose a carbon nanotube end of the membrane, and the membrane is sliced with an ultra-thin microtome to obtain a hydrophobic carbon nanotube composite membrane, as illustrated in
PDMS components A and B comprise two components: a prepolymer A and a crosslinking agent B. A component of the prepolymer A is mainly poly(dimethyl-methylvinylsiloxane) prepolymer and a trace amount of platinum catalyst. The crosslinking agent B is a prepolymer and a crosslinking agent with a side chain of a vinyl group, for example, poly(dimethyl-methylhydrogensiloxane). The vinyl group is configured to react with a silicon-hydrogen bond to achieve a hydrosilylation reaction to form a three-dimensional net structure by mixing the prepolymer A and the crosslinking agent B. A component ratio of the prepolymer A and the crosslinking agent B is selected to control mechanical properties of PDMS.
2. Perforation of the Hydrophobic Carbon Nanotube Composite Membrane:
A laser cutting machine is used, a cutting power is 25 W, and a cutting speed is 2 m/s. After the laser cutting machine is focused, carbon nanotube composite porous membranes 5 with a pore size of 50 μm are obtained, as illustrated in
3. A package clip (i.e., a package structure) of the one or more carbon nanotube composite porous membranes and an electrode comprises connection structures of the electrode and package clips.
(1) The connection structures of the electrode: a device by which an interdigital electrode is connected to the carbon nanotube composite porous membrane in parallel is illustrated in
(2) One of polymethyl methacrylate (PMMA) package clips 12 is illustrated in
(3) One of silica gel pad package clips 10 is illustrated in
(4) A sandwich package structure is illustrated in
{circle around (1)} First, referring to the connection parts 13 of the titanium electrode, four of the carbon nanotube composite porous membranes 5 are bond with the positive pole 1 of titanium electrode or the negative pole 2 of titanium electrode by using conductive silver glue and the method described in step (1) to define the connection parts 13 of the titanium electrode in this step, as illustrated in
{circle around (2)} Second, referring to
{circle around (3)} Finally, the PMMA package clips 12 in step (2) are used. Referring to
{circle around (4)} A 5-layer sandwich package structure comprising a first PMMA package clip, a first silica gel pad package clip, the carbon nanotube composite porous membranes 5 and the connection parts of the titanium electrode, a second silica gel pad package clip, and a second PMMA package clip superimposed in sequence is finally obtained. A screw is inserted into corresponding screw grooves, and the connection parts of the titanium electrode are packaged by stress after the screw is tightened.
4. Referring to
5. Referring to
Step (1), toluene is used as a carbon source, ferrocene is used as a catalyst, and a 4 wt % solution of the ferrocene and the toluene is prepared. Referring to
Step (2), a laser cutting machine is used, a cutting power is 25 W, and a cutting speed is 2 m/s. After the laser cutting machine is focused, carbon nanotube composite porous membranes with a pore size of 50 μm are obtained. A top surface and a side surface of an actual product is illustrated in
Step (3), the carbon nanotube composite porous membranes prepared in step (2) are used. Two sides of the carbon nanotube composite porous membranes are bonded with titanium foils to define titanium electrodes for an external power supply by using conductive silver glue. Parameters of a direct current power are adjusted to enable the carbon nanotube composite porous membranes to generate Joule heat. A surface temperature of the carbon nanotube composite porous membranes are controlled to be highest under a corresponding voltage and are stabilized, and a voltage of the direct current power is adjusted to be, for example, 10V, 11V, 12V, 13V, 14V, or 15V. When the voltage is 15V, the surface temperature of the carbon nanotube composite porous membranes is highest. Referring to
Step (4), corresponding parameters of the direct current power are set according to data adjusted in step (3). Only one of the carbon nanotube composite porous membranes is clamped in the package structure, and a desalination of heavy brine (100 g/L NaCl) is achieved. The desalination device and desalination effects are illustrated in
Step (1), the carbon nanotube composite porous membranes prepared in Embodiment 1 are used, and two sides of the carbon nanotube composite porous membranes are bonded with titanium foils to define titanium electrodes for an external power supply by using conductive silver glue.
Step (2), a voltage of the direct current power is fixed at 15 V, a time for the voltage of the direct current power applied to the carbon nanotube composite porous membranes is adjusted to be, for example, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, or 35 minutes. When the voltage is 15V, a surface temperature of the carbon nanotube composite porous membranes is controlled to be highest within a corresponding time and to be stabilized.
Step (3), a voltage value and an energized time of the direct current power are set according to data adjusted in step (2). Only one of the carbon nanotube composite porous membranes is clamped in the package structure, and a desalination of heavy brine (100 g/L NaCl) is achieved. The desalination unit and desalination effects are illustrated in
Step (1), 4 mg of powders of photothermal and electrothermal responsive carbolong complexes 1#, 2#, 3#, and 4#, are respectively weighed. The photothermal and electrothermal responsive carbolong complexes 1#, 2#, 3#, and b4# are all osmium-based complexes, and molecular formulas are illustrated in
Step (2), the titanium electrode is connected to the carbon nanotube composite porous membranes respectively modified with the photothermal and electrothermal responsive carbolong complexes 1#, 2#, 3#, and 4# in step (1). The direct current voltage is continuously incremented at 1V until the direct current voltage reaches 15 V, that is, 1 V, 2 V, 3 V, 4 V, 5 V, 6 V, 7 V, 8 V, 9 V, 10 V, 11 V, 12 V, 13 V, 14 V, and 15 V. When a surface of the carbon nanotube composite porous membranes is stable after being energized, a thermal imaging device is used to characterize a working temperature.
Step (3), a required voltage is tested when the surface of the carbon nanotube composite porous membranes respectively modified with the photothermal and electrothermal responsive carbolong complexes 1#, 2#, 3#, and 4# reaches 150° C. When the surface of the carbon nanotube composite porous membranes modified with the photothermal and electrothermal responsive carbolong complex 1# reaches 150° C., the required voltage is 8V. When the surface of the carbon nanotube composite porous membranes modified with the photothermal and electrothermal responsive carbolong complex 2# reaches 150° C., the required voltage is 12V. When the surface of the carbon nanotube composite porous membranes modified with the photothermal and electrothermal responsive carbolong complex 3# reaches 150° C., the required voltage is more than 15 V. When the surface of the carbon nanotube composite porous membrane modified with the photothermal and electrothermal responsive carbolong complex 4# reaches 150° C., the required voltage is 11V.
Step (1), 4 mg of a powder of the photothermal and electrothermal responsive carbolong complex 1# is weighed. The photothermal and electrothermal responsive carbolong complex 1# is an osmium-based complex, and a molecular formula of the photothermal and electrothermal responsive carbolong complex 1# is illustrated in
Step (2), the carbon nanotube composite porous membrane modified with the photothermal and electrothermal responsive carbolong complex 1# prepared in step (1) is connected to the titanium electrode, and the direct current voltage is continuously incremented at 1V until the direct current voltage reaches 15 V. Four of the carbon nanotube composite porous membranes in which a surface can reach 150° C. under the voltage of 8 V is selected, as illustrated in
Step (3), referring to
Step (4), two ends of the interdigital electrode are respectively input with 7.5 V, 10 V, 12.5 V, and 15 V of the direct current voltage, energized for 20 minutes, and tested. Desalination rates of the seawater desalination device are respectively 3.33 kg/m2·h, 10.68 kg/m2·H, 11.36 kg/m2·h, and 12.51 kg/m2·h, mass flow rates of the system are respectively 0.33 g/h, 1.07 g/h, 1.14 g/h, or 1.25 g/h, energy utilization efficiencies of the system are respectively 24.14%, 92.70%, 31.22%, or 18.42%. A temperature of a top of the seawater desalination device is the highest when the direct current voltage is 15 V. Referring to
Step (1), 4 mg of powders of the photothermal and electrothermal responsive carbolong complexes 1#, 2#, and 3# are respectively weighed. The photothermal and electrothermal responsive carbolong complexes 1#, 2#, and 3# are all osmium-based complexes, and molecular formulas of the photothermal and electrothermal responsive carbolong complexes 1#, 2#, and 3# are shown in
Step (2), the carbon nanotube composite porous membranes coated with the different carbolong complexes are placed in the seawater desalination device. Referring to
Step (1), the hydrophobic carbon nanotube composite membrane prepared in step (1) in Embodiment 1 is used. A top surface and a side surface of an actual product are illustrated in
Step (2), a laser cutting machine is used to design different pore diameters. A cutting power is set to 25 W, and a cutting speed is set to 2 m/s. After the laser cutting machine is focused, carbon nanotube composite porous membranes with different pore diameters of 50 μm, 75 μm, 100 μm, and 125 μm are respectively obtained. A density is 64 pores per 5 mm×5 mm A preparation process and related pore sizes are illustrated in
Step (3), the carbon nanotube composite porous membranes with different pore diameters of 50 μm, 75 μm, 100 μm, and 125 μm are respectively placed in the seawater desalination device, and a heavy brine (100 g/L of NaCl) is used in the seawater desalination device. Referring to
Step (1), 4 mg of a powder of photothermal and electrothermal responsive carbolong complex 3# is weighed. The photothermal and electrothermal responsive carbolong complex 3# is an osmium-based complex, and a molecular formula of the photothermal and electrothermal responsive carbolong complex 3# is illustrated in
Step (2), the carbon nanotube composite porous membranes modified with the photothermal and electrothermal responsive carbolong complex 3# prepared in step (1) is used, and the interdigital electrode in
Step (3), a solar simulator is used, power densities of the solar simulator are respectively set to 2 kW/m2, 4 kW/m2, 6 kW/m2, and 8 kW/m2. That is, simulated optical concentration Copt corresponds to 2, 4, 6, and 8 times the sunlight intensity. After a light radiation test for 30 minutes, desalination rates of the seawater desalination device are respectively 1.54 kg/m2·h, 10.43 kg/m2·h, 12.73 kg/m2·h, and 15.80 kg/m2·h, mass flow rates of the system are respectively 0.15 g/h, 1.04 g/h, 1.27 g/h, and 1.38 g/h, and energy utilization efficiencies of the system are respectively 27.61%, 93.64%, 76.15%, and 70.91%. When the simulated optical concentration Copt=8, a temperature of a top of the seawater desalination device is highest, and a highest temperature is 65.7° C. Referring to
Step (1), 4 mg of a powder of photothermal and electrothermal responsive carbolong complex 1# is weighed. The photothermal and electrothermal responsive carbolong complex 1# is an osmium-based complex, and a molecular formula of the photothermal and electrothermal responsive carbolong complex 1# is illustrated in
Step (2), the carbon nanotube composite porous membranes modified with the photothermal and electrothermal responsive carbolong complex 1# prepared in step (1) are used. Referring to
Step (3), referring to an electrothermal-photothermal 24 hour continuous seawater desalination device in
60. A surface of the carbon nanotube composite porous membranes generates Joule heat under an action of electric current. The carbon nanotube composite porous membranes can also achieve electro-induced seawater desalination due to the Joule heat. A maximum of an evaporation rate of the seawater desalination device is up to 26.7 kg/m2·h, and a salt rejection rate is >99%. As a result, a 24 hour continuous seawater desalination is achieved. When a voltage is 15 V, an electrochemical corrosion is less. An evaporation rate of the seawater desalination device is 12.51±0.08 kg/m2·h under the action of the electric current. A maximum of a salt rejection rate of the seawater desalination device is up to 10.61±0.17 kg/m2·h under optimal conditions (Copt=4), and an average desalination rate in 24 hours is 11.56±0.13 kg/m2·h under this condition.
Step (1), 4 mg of a powder of a photothermal and electrothermal responsive carbolong complex 5# is weighted. The photothermal and electrothermal responsive carbolong complex 5# is an osmium-based polycarbolong polymer. A molecular formula of the photothermal and electrothermal responsive carbolong complex 5# is illustrated in
Step (2), the carbon nanotube composite porous membranes modified with the photothermal and electrothermal responsive carbolong complex 5# prepared in step (1) are used. Referring to
Step (3), referring to the Joule heat-photothermal 24 hour continuous seawater desalination device in
Number | Date | Country | Kind |
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201910926145.7 | Sep 2019 | CN | national |
This application is a continuation of and claims priority to International patent application number PCT/CN2020/115368, filed Sep. 15, 2020, which claims priority to Chinese patent application number 201910926145.7, filed on Sep. 27, 2019. International patent application number PCT/CN2020/115368 and Chinese patent application number 201910926145.7 are incorporated herein by reference.
Number | Date | Country | |
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Parent | PCT/CN2020/115368 | Sep 2020 | US |
Child | 17706538 | US |