WO2019015222A1 - 一种基于碳纳米管薄膜的太阳能海水淡化或污水处理方法 - Google Patents

一种基于碳纳米管薄膜的太阳能海水淡化或污水处理方法 Download PDF

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WO2019015222A1
WO2019015222A1 PCT/CN2017/114782 CN2017114782W WO2019015222A1 WO 2019015222 A1 WO2019015222 A1 WO 2019015222A1 CN 2017114782 W CN2017114782 W CN 2017114782W WO 2019015222 A1 WO2019015222 A1 WO 2019015222A1
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carbon nanotube
nanotube film
water
hydrophilic
carbon nanotubes
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PCT/CN2017/114782
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English (en)
French (fr)
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张莹莹
訚哲
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清华大学
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for 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
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the invention relates to the technical field of solar water desalination or sewage treatment, in particular to a solar water desalination or sewage treatment technology based on a carbon nanotube film.
  • a type of solar seawater desalination or sewage treatment method is a photothermal conversion method, mainly including two types: 1.
  • the whole water body is heated by sunlight, water vapor is generated after boiling, and fresh water is obtained by condensing water vapor.
  • This method requires a long time to heat the water to obtain water vapor, and the heat loss due to heat dissipation of the water body is not efficient.
  • the use of a thin film material absorbs solar energy and transfers the generated heat to the surface layer of the seawater, thereby reducing the heat transfer loss to the internal water, thereby evaporating the surface seawater.
  • the structure of the film material can be designed to improve the absorption rate of solar energy and the efficiency of photothermal conversion.
  • the reported film materials are mainly metal nanoparticle-based composite film materials, but such materials are complicated in production process and high in cost.
  • composite materials composed of carbon nanoparticles have attracted attention due to their excellent light absorption and high water vapor generation efficiency.
  • Carbon materials are more environmentally friendly and less expensive than metals.
  • the carbon material contains sp 2 hybridized carbon atoms, and its ⁇ -band structure has excellent optical absorption properties, so it is an ideal light absorbing material.
  • the vertical array of carbon nanotubes is a kind of carbon nanotube film, which is the world's blackest man-made material, which has almost constant (0.98-0.99) light absorption in the ultra-wide spectral range (200nm-200 ⁇ m) from ultraviolet to infrared. rate. Vertical arrays of carbon nanotubes therefore behave most similarly to black bodies and have great potential for solar energy utilization.
  • the use of a vertical array of carbon nanotubes as a photothermal conversion layer can greatly improve the absorption efficiency of sunlight. Experiments have shown that a vertical array of carbon nanotubes can convert most of the absorbed light energy into heat.
  • the zero-friction surface of the tube wall also contributes to the rapid flow of water during evaporation, which can further accelerate the evaporation of water, thereby improving the efficiency of solar desalination or sewage treatment.
  • the carbon nanotube film prepared by the invention has a water purification efficiency of up to 90%.
  • the object of the present invention is to propose a solar seawater desalination or sewage treatment method based on a carbon nanotube film material.
  • the carbon nanotube film (for example, vertical array of carbon nanotubes) directly prepared by chemical vapor deposition is used as a raw material, and processed to obtain a vertical array film of carbon nanotubes having strong absorbance and surface hydrophilicity;
  • the carbon nanotube film is placed on the surface of the water to be treated; since the carbon nanotube film can efficiently absorb light and undergo photothermal conversion, the water body is heated to cause rapid evaporation of water, and the steam is condensed to obtain purified water.
  • the technology has the characteristics of green environmental protection, simple process, high photothermal conversion efficiency, fast water purification speed and good durability, and has broad application prospects.
  • a first aspect of the present invention provides a method for solar water desalination or sewage treatment based on a carbon nanotube film, comprising placing a hydrophilic carbon nanotube film on a surface of a water body for absorbing sunlight, converting light energy into heat energy to cause moisture Evaporation, condensation of steam to obtain purified water.
  • the above method can be carried out under the conditions of sunlight or under illumination conditions such as an artificial light source.
  • hydrophilic carbon nanotube film has a plurality of oxygen-containing functional groups at the carbon tube end.
  • a second aspect of the present invention provides a seawater desalination or sewage treatment device, wherein the device uses a hydrophilic carbon nanotube film as a photothermal conversion layer; specifically, the device comprises a light transmissive cover and a hydrophilicity as a photothermal conversion layer
  • the carbon nanotube film, the water inlet port to be treated, and the fresh water outlet; the hydrophilic carbon nanotube film has more oxygen-containing functional groups at the end of the carbon tube.
  • the device is preferably a sealing device. To reduce the loss of water vapor, only the water inlet and the water outlet can be connected to the outside.
  • the light transmissive cover is made of a transparent material, and may preferably be glass.
  • the device further includes a heat insulating layer; the heat insulating layer may be a double-layer vacuum glass.
  • the method for using the seawater desalination or sewage treatment device comprises: injecting water to be treated into the device, placing the hydrophilic carbon nanotube film on the surface of the water to be treated, or further disposing the heat insulating layer on the hydrophilic carbon.
  • the lower part of the nanotube film is then covered with a translucent cover and placed under light; the generated water vapor condenses on the lower surface of the translucent cover, and is purified or recirculated through the fresh water outlet to obtain purified water or fresh water.
  • a hydrophilic carbon nanotube film having a plurality of oxygen-containing functional groups at a carbon tube terminal.
  • the contact angle of the surface of the hydrophilic carbon nanotube film is from 0 to 90, preferably 50.
  • the longitudinal direction (refer to the direction perpendicular to the substrate) of the carbon nanotube array in the hydrophilic carbon nanotube film is 40-190 nm.
  • the hydrophilic carbon nanotube film can be obtained by plasma oxidation treatment of a carbon nanotube film.
  • the carbon nanotube film is an independently supported film material, wherein the carbon nanotubes may be randomly arranged or arranged in parallel as an array of carbon nanotubes.
  • the carbon nanotube array is a vertical array of carbon nanotubes (also referred to as a carbon nanotube forest), and refers to an assembly of carbon nanotubes and a growth substrate forming a vertically aligned carbon nanotubes, which are oriented uniformly.
  • a macroscopic body composed of carbon nanotubes of highly consistent and ordered arrangement.
  • the carbon nanotube film is a vertical array of carbon nanotubes
  • it is generally required to perform high temperature oxidation treatment on the vertical array of carbon nanotubes, so that the vertical array of carbon nanotubes is separated from the growth substrate to obtain self-supporting carbon nanotubes.
  • the vertical array film is further subjected to plasma oxidation treatment to obtain a hydrophilic carbon nanotube film (having more oxygen-containing functional groups at the carbon tube end).
  • the carbon nanotube film When the carbon nanotube film is a vertical array of carbon nanotubes, the carbon nanotube film may be etched by hydrofluoric acid to obtain a hydrophilic carbon nanotube film (the carbon tube end has more inclusions) Oxygen functional group).
  • the gas atmosphere used in the high temperature oxidation treatment is argon gas and oxygen gas, wherein oxygen The amount of access is less than 2%.
  • the high temperature oxidation treatment temperature is generally 300-1000 ° C, preferably 750 ° C; the treatment time is generally 5-10 min.
  • the high temperature oxidation treatment can be carried out in a tube furnace.
  • the main purpose of the high temperature oxidation treatment is to separate the carbon nanotube array and the growth substrate to obtain a self-supporting carbon nanotube vertical array film.
  • the gas used for plasma oxidation (also called plasma etching) is air, with a power of 50-60 W and an oxidation time of 120-300 s.
  • the main purpose of the plasma oxidation is to bring more oxygen-containing functional groups to the end of the carbon tube to become hydrophilic.
  • the hydrofluoric acid solution used in the hydrofluoric acid etching process has a mass concentration of 5-30%, preferably 10%.
  • the etching time is generally from 1 to 10 min, preferably 2 min.
  • the hydrofluoric acid is etched to separate the vertical array of carbon nanotubes from the substrate, so that the carbon nanotubes end with more oxygen-containing functional groups and become hydrophilic.
  • a fourth aspect of the present invention provides a method for preparing a hydrophilic carbon nanotube film, which comprises preparing a vertical array of carbon nanotubes by high-temperature oxidation treatment and plasma oxidation treatment in sequence; or the preparation method includes The vertical array of carbon nanotubes is prepared by hydrofluoric acid etching; the carbon nanotube end of the prepared hydrophilic carbon nanotube film has more oxygen-containing functional groups.
  • the preparation method of the above hydrophilic carbon nanotube film may be any of the following,
  • Method 1 comprising:
  • the vertical array of carbon nanotubes is placed in a reaction vessel (for example, a tube heating furnace) for high temperature oxidation, and the gas atmosphere used for high temperature oxidation is argon gas and oxygen gas, wherein the oxygen gas input amount is less than 2%;
  • the high temperature oxidation temperature is generally 300-1000 ° C, preferably 750 ° C;
  • high temperature oxidation time is generally 5-10 min;
  • step S2 after the temperature of the reaction vessel in step S1 is lowered to room temperature, the vertical array of carbon nanotubes after high temperature oxidation is removed from the substrate, and plasma oxidation is performed to bring more oxygen-containing functional groups to the end of the carbon tube to become pro- Water;
  • the gas used in the plasma oxidation process is air, the power is 50-60w, and the oxidation time is 120-300s;
  • Method 2 including:
  • the vertical array of carbon nanotubes is placed in hydrofluoric acid for etching to make the vertical array of carbon nanotubes
  • the substrate is separated and simultaneously hydrophilic; the concentration of the hydrofluoric acid solution used for etching is 5-30%, preferably 10%; the etching time is generally 1-10 min, preferably 2 min.
  • the carbon nanotube films (including vertical arrays of carbon nanotubes) used in the present invention are commercially available or can be prepared by conventional methods in the art.
  • the fifth aspect of the invention also provides a vertical array of carbon nanotubes and a preparation method thereof.
  • a method for preparing a vertical array of carbon nanotubes comprising:
  • the method for depositing the catalyst may be a method of magnetron sputtering or electron beam evaporation; preferably, the method of electron beam evaporation includes first depositing a layer of aluminum oxide on the silicon dioxide film, and then performing a layer of aluminum oxide. Evaporating a layer of iron on it;
  • the thickness of the silicon dioxide film is 100-1500 nm, preferably 800 nm;
  • the thickness of the aluminum oxide layer is 5-30 nm, preferably 10 nm;
  • the thickness of the iron layer is 2-5 nm, for example, 2, 3, 4, 5 nm, respectively;
  • the substrate ie, silicon wafer
  • ultrasonically cleaned with acetone, ethanol, water; generally ultrasonic cleaning time is 5-20min, for example 15min;
  • reaction vessel for example, a tubular heating furnace
  • a carbon source gas for example, a carbon source gas
  • the heating rate is 1-200 ° C / min, preferably 73 ° C / min
  • the reaction temperature is 500-850 ° C, preferably 750 ° C
  • the reaction time is 1-240min, preferably 10min;
  • ethylene is preferably introduced into the carbon source gas, and the amount of the gas is 10 to 60 ml per minute (unit: sccm), preferably 30 sccm, and the auxiliary gas is a mixed gas of argon gas and hydrogen gas. They are 140 sccm and 10 sccm, respectively.
  • the sixth aspect of the invention provides the use of the above hydrophilic carbon nanotube film in seawater desalination or sewage treatment; especially in solar water desalination or sewage treatment. Further, the application comprises directly placing the hydrophilic carbon nanotube film on the surface of the water body to be treated, and condensing and recovering the water vapor generated under the light condition to obtain fresh water.
  • the illumination includes sunlight, an artificial light source, and the like.
  • the invention is based on a (solar) seawater desalination or sewage treatment technology of a carbon nanotube film material, and uses a carbon nanotube film to further obtain high absorbance and hydrophilicity by oxidation treatment, as Solar thermal desalination or sewage treatment of photothermal conversion layer materials.
  • the technology has the characteristics of green environmental protection and simple process; the integrated solar water treatment device has the characteristics of high photothermal conversion efficiency, fast water purification speed and good durability, and has broad application prospects.
  • the seawater desalination or sewage treatment method provided by the invention utilizes the light absorption and photothermal conversion effects of the carbon nanotube film material, taking a vertical array of carbon nanotubes as an example, which has good high absorbance (99%) while having good Hydrophilic (contact angle 50°).
  • Figure 1 is a flow diagram of the preparation and hydrophilic treatment of the materials of the present invention.
  • Figure 2 is a scanning electron micrograph of the material of the present invention after the hydrophilic treatment (Figure 2A) ( Figure 2B). Shown in the figure is the surface topography of a thin film material exemplified by a vertical array of carbon nanotubes.
  • Figure 3 is a scanning electron micrograph of an experimental test device and material of the material of the present invention.
  • (ac) is a schematic diagram of a thin film material absorbing heat and heating surrounding water under illumination
  • (d) and (e) are carbon nanotubes in a vertical array and carbon nanotubes.
  • (f) is the transmission electron micrograph of the dispersed carbon nanotubes.
  • Figure 4 is a structural diagram and mechanism diagram of a solar seawater desalination or sewage treatment device used in the material of the present invention.
  • Fig. 5 is a graph showing the ion concentration test of the purified water obtained by seawater desalination or sewage treatment of the material of the present invention.
  • Figure 6 is a graph showing the data of seawater desalination or sewage treatment efficiency of the material of the present invention.
  • the present invention compares the weight change of water under the same conditions of water and pure water (not covered with carbon nanotube film) covered with carbon nanotube film, ( b) for the rate of water vapor generation under different illumination conditions, comparing the water vapor generation rate of water and pure water (not covered with carbon nanotube film) covered with carbon nanotube film under the same conditions, (c) For energy conversion efficiency under different lighting conditions.
  • C opt represents the optical intensity
  • 1C opt is the intensity of a solar light, approximately 1 kW m - 2 .
  • Figure 7 is an infrared image of the material of the present invention under illumination conditions.
  • i) An infrared image taken from the upper part of the water body after the end of the 20 minute test.
  • (j) is an infrared image taken from the upper part of the water body after the end of the 20-minute test.
  • the test environment conditions were 22 ° C and a relative humidity of 36%.
  • Figure 8 is a graphical representation of the optical properties of the materials of the present invention.
  • a catalyst required for growing carbon nanotubes is deposited on a silicon wafer containing a 800 nm thick silicon dioxide film.
  • the catalyst is deposited by electron beam evaporation, which comprises first depositing a layer of 10 nm of aluminum oxide on the silicon dioxide film, and then depositing a layer of 2-5 nm of iron on the aluminum oxide layer. .
  • the substrate ie, the silicon wafer
  • the cleaning process includes ultrasonication with acetone, ethanol, and water for 15 minutes.
  • the carbon source gas is ethylene
  • the amount of introduction is 30 ml per minute (unit: sccm)
  • the auxiliary gas is a mixture of argon and hydrogen
  • the amount of introduction is 140 sccm, 10 sccm .
  • the heating rate of the tube furnace was 73 ° C / min, the reaction temperature was 750 ° C, and the reaction time was 10 min.
  • Fig. 1A from top to bottom, there are iron, aluminum oxide, silicon dioxide, and silicon wafer.
  • the reaction temperature is maintained at 750 ° C, and the high temperature oxidation is performed for 5-10 minutes.
  • the gas atmosphere used for the high temperature oxidation is argon gas and oxygen gas.
  • the oxygen flux is less than 2%.
  • the vertical array of carbon nanotubes after high temperature oxidation is removed from the substrate, and plasma etching is performed to bring more oxygen-containing functional groups to the end of the carbon tube.
  • Hydrophilic The gas used in the plasma etching process is air with a power of 50-60 W and an oxidation time of 120-300 s.
  • Example 1 In the reaction of Example 1, after the completion of the chemical vapor deposition reaction, ethylene was turned off, and after the temperature of the tubular furnace was lowered to room temperature, the sample was taken out. Etching is carried out by placing it in hydrofluoric acid to separate the vertical array of carbon nanotubes from the substrate. The concentration of the hydrofluoric acid solution used for the corrosion was 10%.
  • Both of the above methods can obtain a hydrophilic carbon nanotube film, and the contact angle of the surface of the hydrophilically treated carbon nanotube film is changed from 153° to 50°.
  • Example 3 Water evaporation test using a carbon nanotube film as a photothermal conversion layer
  • the carbon nanotube film obtained in Example 2 was transferred to the surface of a water body (tap water), and water vapor was generated by irradiation with a solar simulator (ceramic light source). Place the beaker containing the water and carbon nanotube film on the electronic balance (see Figure 3c), connect the electronic balance to the computer, and record the change in the balance by the data recording program to calculate the amount of water vapor change.
  • the evaporation rate of water can be obtained by calculating the amount of water vapor change over a certain period of time to determine the evaporation efficiency.
  • Example 4 Seawater desalination device using carbon nanotube film as photothermal conversion layer
  • the solar seawater desalination or sewage treatment device used is composed of an upper transparent cover, a carbon nanotube light absorption film on the surface of the water to be treated, a lower heat insulation layer, a water inlet port to be treated, and a fresh water outlet.
  • the device is a sealed device with only water inlets and outlets to reduce water vapor loss.
  • the light transmissive cover above the device is made of a transparent material, which may preferably be glass; the lower heat insulating layer may be a double-layer vacuum glass.
  • the step of solar water desalination or sewage treatment technology is: injecting water to be treated into the device, Transfer the carbon nanotube film to the surface of the water to be treated, then cover the transparent cover, open the solar simulator, generate water vapor under the sunlight, the water vapor condenses on the lower surface of the transparent cover, and condenses and returns to the fresh water. Purified water is obtained at the output.
  • the mechanism of seawater desalination is shown in Figure 4.
  • the sunlight is captured by the carbon nanotube film and transmitted to the water body through the carbon nanotubes to generate water vapor.
  • the special structure of the surface makes it have an ultra-high absorbance.
  • the carbon nanotubes in the photothermal conversion layer used in the present invention are complete single carbon nanotubes from top to bottom, and the carbon nanotubes have good thermal conductivity in the radial direction, and can rapidly transfer heat to the water body.
  • the wall of the carbon nanotubes also has zero friction characteristics, which allows water to flow rapidly between the carbon nanotubes and accelerates the evaporation rate of water.
  • Example 5 Calculation of seawater desalination or sewage treatment efficiency using carbon nanotube film as photothermal conversion layer
  • ⁇ mh LV /q i C opt , where ⁇ is the efficiency of water vapor generation, m is the mass of water vapor, and h LV is the phase change enthalpy of water to water vapor (2.26 MJ kg -1 ),q i is the ratio of the light intensity to the intensity of the sunlight, and C opt is the intensity of a sunlight (1 kW m -2 ).
  • the present invention compares the water body weight change under the same conditions of water and pure water (not covered with carbon nanotube film) covered with a carbon nanotube film.
  • the figure shows the weight loss curve for 15kW m -2 and 1kW m -2 respectively.
  • (c) is the energy conversion efficiency under different lighting conditions.
  • the points in the figure are the water evaporation production efficiency in the case of 1, 5, 10, 15 kW m -2 illumination, respectively.
  • the energy conversion efficiencies are 30, 60, 78, and 90%, respectively. That is, the carbon nanotube film prepared by the invention has a water purification efficiency of up to 90%.
  • the carbon nanotube film can be used to limit the heat to the surface of the water body.
  • the maximum surface temperature of the surface of the water covered with the carbon nanotube film is between 130-150 ° C (the temperature scale can only display up to 60 ° C due to the limitation of the imaging range of the infrared camera). The results are shown in Figure 7.
  • the carbon nanotube film was placed on the support of the spectrometer, and the optical properties of the carbon nanotube film before and after the hydrophilic treatment were tested. The results are shown in Fig. 8; "front” in Fig. 8 indicates the material of the example, and “back” indicates the material of the example 2.

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Abstract

一种基于碳纳米管薄膜的太阳能海水淡化或污水处理方法，将亲水性碳纳米管薄膜置于待处理水表面用于吸收太阳光，并进行光热转化，从而加热水体引起水的快速蒸发，将该蒸汽冷凝即得到纯化的水，亲水性碳纳米管薄膜的碳管末端带有含氧官能团。还包括一种海水淡化或污水处理装置，一种亲水性碳纳米管薄膜，以及一种亲水性碳纳米管薄膜的制备方法。

Description

一种基于碳纳米管薄膜的太阳能海水淡化或污水处理方法
交叉引用
本申请引用于2017年07月19日提交的专利名称为“一种基于碳纳米管薄膜的太阳能海水淡化或污水处理方法”的第2017105917773号中国专利申请，其通过引用被全部并入本申请。
技术领域
本发明涉及太阳能海水淡化或污水处理技术领域，具体涉及一种基于碳纳米管薄膜的太阳能海水淡化或污水处理技术。
背景技术
近年来，随着人类对水资源的需求不断增加，很多国家和地区出现不同程度的缺水问题，目前看来最有前景的解决办法是开发利用某些不可用水。太阳能海水淡化或污水处理就是其中最重要的方法之一。作为太阳能海水淡化或污水处理方法的重要分支，蒸馏法具有对原料海水水质要求低、装置的生产能力大、产水纯度高等特点。而传统的水蒸馏法多采用多效蒸发和多级闪蒸技术，需要庞大的装置且海水蒸发效率低，无法满足日益增长的水资源需求。
还有一类太阳能海水淡化或污水处理的方法是光热转换方法，主要包括两类：1.利用太阳光对整个水体进行加热，水沸腾后产生水蒸气，通过冷凝水蒸气得到淡水。此方法需要较长时间的光照来加热水体才能得到水蒸气，且由于水体散热会有热损失，因此效率不高。2.使用薄膜材料吸收太阳能并将产生的热传给海水表层，因此减少向内部水的传热损失，从而将表层海水蒸发。进一步的，可以通过设计薄膜材料的结构以提高对太阳能的吸收率和光热转化效率。已报道的薄膜材料主要是金属纳米颗粒为主的复合薄膜材料，但此类材料制作流程复杂、成本高。近年来，碳纳米颗粒构成的复合材料因其优异的吸光性和较高的水蒸气产生效率而得到关注。与金属相比，碳材料更环保且成本更低。碳材料中含有sp2杂化的碳原子，其含有的π-带结构有着优异的光学吸收特性，所以是一种理想的光 吸收材料。
碳纳米管垂直阵列是碳纳米管薄膜的一种，是世界上最黑的人造材料，其拥有从紫外到红外的超宽光谱范围内(200nm-200μm)几乎恒定(0.98-0.99)的光吸收率。碳纳米管垂直阵列也因此表现得最类似于黑体而在太阳能利用方面具有巨大潜力。利用碳纳米管垂直阵列作为光热转换层可以极大的提高对太阳光的吸收效率。实验表明，碳纳米管垂直阵列可以将吸收的光能大部分转化为热。此外，碳纳米管的另外一个特性——管壁的零摩擦表面，也有助于水在蒸发过程中的快速流动，这可以进一步加快水的蒸发，从而提高太阳能海水淡化或污水处理效率。本发明所制备的碳纳米管薄膜的净水效率最高可达90％。
发明内容
针对现有技术的不足之处，本发明的目的是提出一种基于碳纳米管薄膜材料的太阳能海水淡化或污水处理方法。
本发明以化学气相沉积法直接制备的碳纳米管薄膜(例如碳纳米管垂直阵列)为原料，经处理得到具有强吸光性和表面亲水性的碳纳米管垂直阵列薄膜；将这种亲水性碳纳米管薄膜置于待处理水表面；由于该碳纳米管薄膜可高效吸光并进行光热转化，从而加热水体引起水的快速蒸发，将该蒸汽冷凝即得到纯化的水。该技术具备绿色环保、过程简便、光热转化效率高、净水速度快、耐久性好等特点，具有广阔的应用前景。
本发明第一方面提供一种基于碳纳米管薄膜的太阳能海水淡化或污水处理方法，包括将亲水性碳纳米管薄膜置于水体表面用于吸收太阳光，将光能转化为热能从而引起水分蒸发，将蒸汽冷凝即得到纯净水。
进一步地，上述方法既可在太阳光光照条件下进行，也可在人工光源等光照条件下进行。
进一步地，所述亲水性碳纳米管薄膜的碳管末端带有较多的含氧官能团。
本发明第二方面提供一种海水淡化或污水处理装置，该装置以亲水性碳纳米管薄膜为光热转换层；具体地，所述装置包括透光罩、作为光热转换层的亲水性碳纳米管薄膜、待处理水进入口、淡水输出口；所述亲水性碳纳米管薄膜的碳管末端带有较多的含氧官能团。
该装置优选为密封装置，为减少水蒸汽的损失，可仅设有进水口和出水口与外界相通。
进一步地，所述透光罩为透明材料制作成，可以优选为玻璃。
进一步地，所述装置还包括绝热层；所述绝热层可为双层真空玻璃。
上述海水淡化或污水处理装置使用方法包括：将待处理水注入该装置中，将所述亲水性碳纳米管薄膜设置于待处理水体表面，或进一步将绝热层设置于所述亲水性碳纳米管薄膜下部，然后盖上透光罩，置于光照条件下；所产生的水蒸气凝结在透光罩下表面，通过冷凝回流经淡水输出口得到纯净水或淡水。
本发明第三方面提供一种亲水性碳纳米管薄膜，其碳管末端带有较多的含氧官能团。
进一步地，所述亲水性碳纳米管薄膜表面的接触角为0°-90°，优选为50°。
进一步地，所述亲水性碳纳米管薄膜中碳纳米管阵列的纵向(指垂直于基底方向)间距为40-190nm。
所述亲水性碳纳米管薄膜可由碳纳米管薄膜经等离子体氧化处理而制得。
进一步地，所述碳纳米管薄膜为可独立支撑的薄膜材料，其中的碳纳米管可以无规则排列或者平行排列为碳纳米管阵列。
更进一步地，所述碳纳米管阵列为碳纳米管垂直阵列(又称为碳纳米管森林)，是指碳纳米管与生长基板形成垂直取向排列的碳纳米管的集合体，是由取向一致、高度一致、有序排列的碳纳米管组成的宏观体。
当所述碳纳米管薄膜为碳纳米管垂直阵列时，一般需要先将碳纳米管垂直阵列进行高温氧化处理，使得碳纳米管垂直阵列从生长基底上分离出来，得到可自支撑的碳纳米管垂直阵列薄膜；再进行等离子体氧化处理，制得亲水性碳纳米管薄膜(其碳管末端带有较多的含氧官能团)。
当所述碳纳米管薄膜为碳纳米管垂直阵列时，也可以将碳纳米管薄膜经氢氟酸刻蚀处理，制得亲水性碳纳米管薄膜(其碳管末端带有较多的含氧官能团)。
进一步地，高温氧化处理所使用的气体氛围为氩气和氧气，其中氧气 通入量小于2％。
进一步地，所述高温氧化处理温度一般为300-1000℃，优选为750℃；处理时间一般为5-10min。
所述高温氧化处理可在管式加热炉中进行。
高温氧化处理的主要目的是分离碳纳米管阵列和生长基底，得到可自支撑的碳纳米管垂直阵列薄膜。
所述等离子体氧化(也称等离子体刻蚀)所使用的气体是空气，功率在50-60w，氧化时间为120-300s。
所述等离子体氧化的主要目的是使碳管末端带上较多的含氧官能团而变得亲水。
进一步地，所述氢氟酸刻蚀过程中所用所用的氢氟酸溶液的质量浓度为5-30％，优选为10％。刻蚀时间一般为1-10min，优选为2min。
经氢氟酸刻蚀，使碳纳米管垂直阵列与基底分离，使得碳管末端带上较多的含氧官能团而变得亲水。
本发明第四方面提供一种亲水性碳纳米管薄膜的制备方法，该制备方法包括将碳纳米管垂直阵列依次进行高温氧化处理和等离子体氧化处理而制得；或者所述制备方法包括将碳纳米管垂直阵列进行氢氟酸刻蚀而制得；使所制得的亲水性碳纳米管薄膜的碳管末端带有较多的含氧官能团。
具体地，上述亲水性碳纳米管薄膜的制备方法可选以下任一种，
方法1，包括：
S1、将碳纳米管垂直阵列置于反应容器(例如管式加热炉)中进行高温氧化，高温氧化所使用的气体氛围为氩气和氧气，其中氧气通入量小于2％；高温氧化温度一般为300-1000℃，优选为750℃；高温氧化时间一般为5-10min；
S2、待步骤S1反应容器温度降至室温后，将高温氧化后的碳纳米管垂直阵列从基底上取下，进行等离子体氧化，使碳管末端带上较多的含氧官能团而变得亲水；等离子体氧化过程使用的气体是空气，功率在50-60w，氧化时间为120-300s；
方法2，包括：
将碳纳米管垂直阵列放入氢氟酸中进行刻蚀，使碳纳米管垂直阵列与 基底分离并同时获得亲水性；刻蚀所用的氢氟酸溶液的浓度为5-30％，优选为10％；刻蚀时间一般为1-10min，优选为2min。
本发明所用碳纳米管薄膜(包括碳纳米管垂直阵列)可市售获得，或按本领域常规方法制备。
为获得更好的亲水性能及更好的光热转换性能，本发明第五方面还提供一种碳纳米管垂直阵列及其制备方法。
一种碳纳米管垂直阵列的制备方法，包括：
S1、在含有二氧化硅膜的硅片上沉积生长碳纳米管所需的催化剂；所述催化剂包括三氧化二铝、铁；
沉积催化剂的方法可以是磁控溅射或者电子束蒸镀的方法；优选电子束蒸镀的方法，包括先在二氧化硅膜上蒸镀一层三氧化二铝，再在三氧化二铝层上蒸镀一层铁；
进一步地，所述二氧化硅膜的厚度为100-1500nm，优选为800nm；
进一步地，所述三氧化二铝层的厚度为5-30nm，优选为10nm；
进一步地，所述铁层的厚度为2-5nm，例如分别为2、3、4、5nm；
S2、蒸镀后将基底(即硅片)分别用丙酮、乙醇、水进行超声清洗；一般超声清洗时间为5-20min，例如15min；
S3、将基底放入反应容器(例如管式加热炉)，通入碳源气体并升温；升温速率为1-200℃/min，优选为73℃/min；反应温度为500-850℃，优选为750℃，反应时间为1-240min，优选为10min；
其中，所通入的碳源气体中优选为乙烯，通入量为10-60毫升每分钟(单位：sccm)，优选为30sccm，辅助气体使用的是氩气和氢气的混合气体，通入量分别为140sccm、10sccm。
本发明第六方面提供上述亲水性碳纳米管薄膜在海水淡化或污水处理方面的应用；尤其是在太阳能海水淡化或污水处理方面的应用。进一步地，所述应用包括将所述亲水性碳纳米管薄膜直接放置在待处理的水体表面上，将在光照条件下产生的水蒸气冷凝回收而得到淡水。
进一步地，所述光照包括太阳光、人工光源等。
本发明基于碳纳米管薄膜材料的(太阳能)海水淡化或污水处理技术，利用碳纳米管薄膜，进一步通过氧化处理获得高吸光率和亲水性，作为太 阳能海水淡化或污水处理的光热转化层材料。该技术具备绿色环保、过程简便的特点；所集成的太阳能水处理装置具有光热转化效率高、净水速度快、耐久性好等特点，具有广阔的应用前景。
本发明提供的海水淡化或污水处理方法，利用碳纳米管薄膜材料的吸光性和光热转化效应，以碳纳米管垂直阵列为例，其在保持高吸光率(99％)的同时具有良好的亲水性(接触角50°)。
附图说明
图1为本发明材料的制备和亲水处理流程图。
图2为本发明材料的在亲水处理前(图2A)后(图2B)的扫描电镜图。图中所示的是以碳纳米管垂直阵列为例的薄膜材料的表面形貌。
图3为本发明材料的实验测试装置和材料的扫描电镜图。
(a-c)是以碳纳米管垂直阵列为例的薄膜材料在光照下吸热并加热周围水的示意图，(d)、(e)图中所示的是碳纳米管垂直阵列中与碳纳米管垂直方向的平行的表面形貌，(f)是分散的碳纳米管的透射电镜图。
图4为本发明材料所用的太阳能海水淡化或污水处理装置结构图和机理图。
图5为本发明材料用于海水淡化或污水处理所得纯化水的离子浓测试图。
图6为本发明材料的海水淡化或污水处理效率数据图。
(a)为在不同光照条件下的水体失重变化曲线，本发明对比了表面覆盖有碳纳米管薄膜的水和纯水(不覆盖有碳纳米管薄膜)在相同条件下的水体重量变化，(b)为在不同光照条件下的水蒸气产生速率，对比了表面覆盖有碳纳米管薄膜的水和纯水(不覆盖有碳纳米管薄膜)在相同条件下的水蒸气产生速率，(c)为在不同光照条件下的能量转换效率。其中Copt表示光学强度，1Copt为一个太阳光的强度，约为1kW m-2。
图7为本发明材料在光照条件下的红外成像。
(a-e)为在Copt＝15的光强照射下的表面覆盖有碳纳米管薄膜的水体在不同时间的红外照片。(f-j)为在Copt＝15的光强照射下的纯水(不覆盖有碳纳米管薄膜)在不同时间的红外照片。i)为在20分钟测试结束后从水体上部拍摄的红外图像。(j)为在20分钟测试结束后从水体上部拍 摄的红外图像。测试环境条件为22℃，相对湿度36％。
图8为本发明材料的光学性能表征图。
(a)以碳纳米管垂直阵列为例，薄膜材料在亲水处理前后的吸光率图，(b)亲水处理前的反射率和透射率图，(c)亲水处理后的反射率和透射率图，(d)实物照片：(i)为在光照条件下表面覆盖有碳纳米管薄膜的水体产生水蒸气的照片，(ii)为不同角度的碳纳米管薄膜材料的实物图。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件，或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可通过正规渠道商购买得到的常规产品。
下面将结合本发明实施例中的附图，对本发明实施例中的技术方
案进行清楚、完整地描述。
实施例1：碳纳米管垂直阵列的制备
S1、在含有800nm厚的二氧化硅膜的硅片上沉积生长碳纳米管所需的催化剂。本实施例采用电子束蒸镀的方法沉积催化剂，具体包括先在二氧化硅膜上蒸镀一层10nm的三氧化二铝，再在三氧化二铝层上蒸镀一层2-5nm的铁。
S2、蒸镀后将基底(即硅片)进行超声清洗，清洗过程包括用丙酮、乙醇、水各超声15分钟。
S3、将基底放入管式加热炉内，通入碳源反应气体并升温：
S3.1、所通入的碳源气体中为乙烯，通入量为30毫升每分钟(单位：sccm)，辅助气体使用的是氩气和氢气的混合气体，通入量分别为140sccm、10sccm。
S3.2、管式加热炉的升温速率为73℃/min，反应温度为750℃，反应时间为10min。
以上制备过程参见图1中的A和B。
图1A中，从上到下依次为铁、三氧化二铝、二氧化硅、硅片。
实施例2：亲水性碳纳米管薄膜的制备方法
方法1：
S1、在实施例1的反应中，化学气相沉积反应完毕后关闭乙烯和氢气，保持反应温度750℃，进行高温氧化，时间为5-10min，高温氧化所使用的气体氛围为氩气和氧气，其中氧气通入量小于2％。
S2、待管式加热炉温度降至室温后，将高温氧化后的碳纳米管垂直阵列从基底上取下，进行等离子体刻蚀，使碳管末端带上较多的含氧官能团而变得亲水。等离子体刻蚀过程使用的气体是空气，功率在50-60w，氧化时间为120-300s。
方法2：
在实施例1的反应中，化学气相沉积反应完毕后关闭乙烯，待管式加热炉温度降至室温后，取出样品。放入氢氟酸中进行刻蚀，使碳纳米管垂直阵列与基底分离。腐蚀所用的氢氟酸溶液的浓度为10％。
以上两种方法均可得到亲水的碳纳米管薄膜，经过亲水处理的碳纳米管薄膜表面的接触角由153°变为50°。
以上制备过程参见图1中的C和D。
亲水性处理前后材料的扫描电镜图见图2。
实施例3：以碳纳米管薄膜为光热转换层的水蒸发测试
如图3所示，将实施例2中得到的碳纳米管薄膜转移至水体(自来水)表面，在太阳光模拟器(氙灯光源)的照射下，可以产生水蒸气。将装有水和碳纳米管薄膜的烧杯放到电子天平上(见图3c)，将电子天平连接电脑，通过数据记录程序可以记录天平的示数变化，从而计算出水蒸气变化量。通过计算一定时间内的水蒸气变化量可以得出水的蒸发速率进而求出蒸发效率。
实施例4：以碳纳米管薄膜为光热转换层的海水淡化装置
所用的太阳能海水淡化或污水处理装置由上部透光罩、位于待处理水表面的碳纳米管吸光薄膜、下方绝热层、待处理水进入口、淡水输出口所组成。该装置是一个密封装置，只留有进水口和出水口，以减少水蒸汽的损失。该装置上方的透光罩为透明材料制作成，可以优选为玻璃；下方的绝热层可为双层真空玻璃。
太阳能海水淡化或污水处理技术的步骤是：将待处理水注入装置中， 将碳纳米管薄膜转移至待处理水表面，然后盖上透光罩，打开太阳光模拟器，在太阳光的照射下产生水蒸气，水蒸气凝结在透光罩下表面，通过冷凝回流在淡水输出口得到纯化水。
海水淡化机理见图4。太阳光被碳纳米管薄膜捕获，通过碳纳米管传输给水体，产生水蒸气。以碳纳米管垂直阵列为例，其表面的特殊结构使其具有超高的吸光率。本发明所用的光热转换层中的碳纳米管是自上而下的完整单根碳纳米管，碳纳米管在径向上具有良好的导热性，可以将热量快速的传给水体。碳纳米管的管壁也具有零摩擦的特性，可以使水在碳纳米管间快速流动而加快水的蒸发速率。
以世界卫生组织出版的《饮用水是指标准》为检测标准，利用电感耦合等离子体发射光谱仪，对海水和淡水进行离子浓度测定。测定结果显示，得到的淡水中的离子浓度符合饮用水标准(见图5)。
实施例5：以碳纳米管薄膜为光热转换层的海水淡化或污水处理效率计算
计算公式为η＝mhLV/qiCopt，其中η为水蒸气产生的效率，m是水蒸气的质量，hLV是水变为水蒸气的相变焓(2.26MJ kg-1)，qi是光照强度与太阳光强度的比值，Copt是一个太阳光的强度(1kW m-2)。
结果见图6：
(a)为在不同光照条件下的水体失重变化曲线，本发明对比了表面覆盖有碳纳米管薄膜的水和纯水(不覆盖有碳纳米管薄膜)在相同条件下的水体重量变化。图中分别是15kW m-2和1kW m-2情况下的失重曲线。
(b)为在不同光照条件下的水蒸气产生速率，对比了表面覆盖有碳纳米管薄膜的水和纯水(不覆盖有碳纳米管薄膜)在相同条件下的水蒸气产生速率。图中的点分别是1、5、10、15kW m-2光照情况下的水蒸发速率，表面覆盖有碳纳米管薄膜的水的蒸发速率最高为21.47kg m-2h-1(15kW m-2)。
(c)为在不同光照条件下的能量转换效率。图中的点分别是1、5、10、15kW m-2光照情况下的水蒸发产生效率。能量转换效率分别为30、60、78、90％。即本发明所制备的碳纳米管薄膜的净水效率最高可达90％。
值得注意的是，为了除去实验设备的影响，本发明中做了对比实验。 以纯水为对照组，对比了20分钟内表面覆盖有碳纳米管薄膜的水和纯水的蒸发速率比值，分别为1.89倍(Copt＝1),5.2倍(Copt＝5),9.6倍(Copt＝10),10倍(Copt＝15)。这表明本发明的材料具有良好的光热效率。
另外利用碳纳米管薄膜可以将热量限制在水体的表面。对比了在Copt＝15的光强照射下的表面覆盖有碳纳米管薄膜的水体在不同时间的红外照片。其中，表面覆盖有碳纳米管薄膜的水体表面的最高温度在130-150℃之间(由于红外相机的成像范围限制，温度标尺最高只能显示到60℃)。结果见图7。
实施例6：碳纳米管薄膜的吸光率测量
利用光谱仪(UV-2600,SHIMADZU)对实施例1制备的碳纳米管垂直阵列、实施例2(氢氟酸刻蚀法)制备的碳纳米管薄膜进行吸光率测量。吸光率＝1-反射率-投射率。将碳纳米管薄膜放置于光谱仪配套的支架上，分别测试了其在亲水处理前、后的光学性能变化。结果见图8；图8中“前”表示实施例材料，“后”表示实施例2材料。
虽然，上文中已经用一般性说明、具体实施方式及试验，对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。

Claims (10)

  1. 一种基于碳纳米管薄膜的太阳能海水淡化或污水处理方法，其特征在于，包括将亲水性碳纳米管薄膜置于水体表面用于吸收太阳光，将光能转化为热能从而引起水分蒸发，将蒸汽冷凝即得到纯净水；所述亲水性碳纳米管薄膜的碳管末端带有含氧官能团。
  2. 一种海水淡化或污水处理装置，其特征在于，包括透光罩、作为光热转换层的亲水性碳纳米管薄膜、待处理水进入口、淡水输出口；所述亲水性碳纳米管薄膜的碳管末端带有含氧官能团。
  3. 根据权利要求2所述的海水淡化或污水处理装置，其特征在于，所述装置还包括绝热层；优选地，所述绝热层可为双层真空玻璃。
  4. 一种亲水性碳纳米管薄膜，其碳管末端带有含氧官能团。
  5. 根据权利要求4所述的亲水性碳纳米管薄膜，其表面的接触角为0°-90°，优选为50°；和/或，
    所述亲水性碳纳米管薄膜中碳纳米管阵列的纵向间距为40-190nm。
  6. 根据权利要求4或5所述的亲水性碳纳米管薄膜，其特征在于，所述碳纳米管薄膜为可独立支撑的薄膜材料，其中的碳纳米管以无规则排列或者平行排列为碳纳米管阵列；
    优选地，所述碳纳米管阵列为碳纳米管垂直阵列。
  7. 权利要求4-6任一项所述亲水性碳纳米管薄膜的制备方法，其特征在于，所述亲水性碳纳米管薄膜由碳纳米管薄膜经等离子体氧化处理而制得；
    优选地，所述等离子体氧化所使用的气体是空气，功率在50-60w，氧化时间为120-300s。
  8. 根据权利要求7所述亲水性碳纳米管薄膜的制备方法，其特征在于，所述碳纳米管薄膜为碳纳米管垂直阵列，所述制备方法包括：先将碳纳米管垂直阵列进行高温氧化处理，使得碳纳米管垂直阵列从生长基底上分离出来，得到可自支撑的碳纳米管垂直阵列薄膜；再进行等离子体氧化处理，制得亲水性碳纳米管薄膜；
    优选地，所述高温氧化处理所使用的气体氛围为氩气和氧气，其中氧气通入量小于2％；和/或，
    所述高温氧化处理温度为300-1000℃，优选为750℃；处理时间为5-10min。
  9. 权利要求4-6任一项所述亲水性碳纳米管薄膜的制备方法，其特征在于，所述碳纳米管薄膜为碳纳米管垂直阵列，所述制备方法包括：将碳纳米管垂直阵列经氢氟酸刻蚀处理，制得亲水性碳纳米管薄膜；
    优选地，所述氢氟酸刻蚀过程中所用所用的氢氟酸溶液的质量浓度为5-30％，优选为10％；刻蚀时间为1-10min，优选为2min。
  10. 权利要求4-6任一项所述亲水性碳纳米管薄膜或权利要求7-9任一项所述方法制备的亲水性碳纳米管薄膜在海水淡化或污水处理方面的应用；
    优选地，所述应用包括将所述亲水性碳纳米管薄膜直接放置在待处理的水体表面上，将在光照条件下产生的水蒸气冷凝回收而得到淡水。
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