Industrial production method of nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation coordination tungsten salt

Abstract

The present invention discloses an industrial manufacturing method of nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation coordination tungsten salt, and the application of nano-alkali metal tungsten bronze coating. The method of the present invention applies one-step low-temperature heating hydrolysis to synthesize nano-alkali metal tungsten bronze, without the need for special equipment in the manufacturing process, without the need for high temperature and high pressure, with mild process conditions, low energy consumption, short cycle, high production volume, high yield, and low cost. The synthesized product has good crystallinity, and its components are Cs x WO3, Rb x WO3, K x WO3, Na x WO3, where X = 0.2 - 0.33. The particle length of the synthesized short rod-shaped alkali metal tungsten bronze is 10 - 150 nm, the diameter is 10 - 50 nm, and the size in each direction of the synthesized equiaxed alkali metal tungsten bronze is less than 100 nm. All of the above powders have excellent near-infrared shielding performance, visible light transmission performance, good ultraviolet shielding performance, and certain mid- and far-infrared shielding performance. The nano-alkali metal tungsten bronze coating manufactured by the present invention has a simple and controllable manufacturing process, high near-infrared shielding performance, and excellent ultraviolet shielding performance.

Description

Technical Field

[0001] The present invention relates to an alkali metal tungsten bronze nanomaterial, and particularly to an industrial manufacturing method of nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation coordination tungsten salt, and the use of the manufactured nano-alkali metal tungsten bronze in a building decoration curtain wall to achieve heat insulation and temperature reduction performance.

Background Art

[0002] Alkali metal tungsten bronze is a typical non-stoichiometric compound, and its chemical formula is M x WO3 (0 ≦ X ≦ 0.33). Because it has a one-dimensional tunnel structure marked by a special six-membered ring and mixed-valence W ions, it is given many excellent physicochemical properties such as photothermal conversion, selective light absorption, and near-infrared shielding, and has broad application prospects in fields such as energy, military, architecture, and medicine.

[0003] With the wide application of alkali metal tungsten bronze nanomaterials, their manufacturing technology has become increasingly important. Currently, the manufacturing of alkali metal tungsten bronze powder mainly includes the following methods.

[0004] Solid-phase method: In the solid-phase method, generally, a simple metal, oxide or salt and tungsten and tungsten oxides are mixed, and various types of alkali metal tungsten bronzes are obtained by a solid-phase reaction under conditions such as higher temperature, pressure or ball milling. However, the alkali metal tungsten bronze synthesized by this method is difficult to control in morphology, and the particle size of the product is relatively large.

[0005] Wet chemical method: The wet chemical method mainly includes the solvothermal method and the hydrothermal method. The wet chemical method features mild synthesis conditions, simple operation, and easy control of the size and morphology of the products. The alkali metal tungsten bronze nanopowders produced by the wet chemical method have a narrow particle size distribution, low powder aggregation degree, and do not require high-temperature annealing treatment in a reducing atmosphere. However, due to the low concentration of reactants and the high reaction temperature and pressure, special equipment (reaction kettle) is required in the synthesis process, there is a certain risk in the reaction, the reaction time is long, and the single production volume is extremely low, which is not suitable for industrial production.

[0006] High-temperature reduction method: In the high-temperature reduction method, it is necessary to introduce hydrogen gas during the heating process at a high temperature (800 °C). The manufacturing process is complex, the utilization rate of raw materials is low, and there is a certain risk (H. Takeda, K. Adachi, J. Am. Ceramic Soc., 2007, 90(12), 4059 - 4061). Solvothermal or hydrothermal reactions also require a high reaction temperature (generally above 200 °C), and the manufacturing time is as long as more than ten hours or even several days (C. Guo, S. Yin, M. Yan, T. Sato, J. Mater. Chem., 2011, 21(13), 5099).

[0007] Architectural decorative curtain wall is a lightweight wall material with a decorative effect commonly used in modern large-scale and high-rise buildings. Due to being restricted by materials and processing processes, curtain walls do not meet the requirements of thermal physical elements (thermal radiation, condensation) and sound insulation, fire prevention, etc., and have not achieved good development and popularization. Currently, with the combination of curtain wall processes and science and technology, in response to the global call for energy conservation, smart curtain walls such as glass curtain walls, solar power generation curtain walls, ventilation duct breathing curtain walls, and wind and rain-sensitive smart curtain walls are showing the unique charm of buildings.

[0008] In order to achieve energy conservation of the coating material in the architectural decorative curtain wall, it is urgent to provide an industrial processing method for manufacturing alkali metal tungsten bronze materials on a large scale at low temperature.

Summary of the Invention

[0009] One of the objectives of the present invention is to provide an industrial production method of nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation-coordinated tungsten salt. Since this production method is carried out during the hydrolysis process, the reaction time is short, the reaction temperature is low (40 °C to 95 °C), and industrial production of alkali metal tungsten bronze nano-materials at low cost is realized. The method of the present invention synthesizes nano-alkali metal tungsten bronze by applying one-step low-temperature heating hydrolysis, and its components are Cs x WO3, Rb x WO3, K x WO3, Na x WO3, where X = 0.2 - 0.33. The nano-alkali metal tungsten bronze produced by the method of the present invention has a short rod-like structure and an equiaxial structure. The synthesized alkali metal tungsten bronze nano-particles with a short rod-like structure have a length of 10 to 150 nm and a diameter of 10 to 50 nm. The synthesized alkali metal tungsten bronze nano-particles with an equiaxial structure have a size of less than 100 nm in each direction. The above products have good crystallinity, excellent visible light transmittance, near-infrared shielding performance, and good ultraviolet shielding and certain mid- and far-infrared shielding performance. The present invention precisely controls the coordination between the product of hydrolysis of the tungsten source in the reaction system and the alkali metal element, and reacts in a liquid phase below the boiling point of the solvent, thereby obtaining alkali metal tungsten bronze nano-powder under low-temperature and non-high-pressure conditions. By precisely controlling the stirring speed, reaction time and temperature of the reaction system, the crystallization rate can be controlled and the particle size of alkali metal tungsten bronze can be controlled. The tungsten source, alkali metal source, deionized water and alcohol solution used in the present invention are all environmentally friendly reagents with low cost. The reaction system used in the method of the present invention has a low temperature, is non-high-pressure, has a uniform product morphology, a short production cycle, low energy consumption, does not require special equipment, has a high yield, and a large production volume.

[0010] The second object of the present invention is to provide large-scale and low-cost production for spray-coating an alkali metal tungsten bronze paint onto the glass surface industrially to obtain a glass curtain wall. The coating production proposed in the present invention does not require special equipment, has a simple process, and a short production cycle. The coating produced by the present invention has excellent near-infrared shielding performance, high visible light transmittance, good ultraviolet shielding performance at the same time, and excellent heat insulation performance.

[0011] The industrial production method of nano-alkali metal tungsten bronze by hydrolysis of the low-temperature cation coordination tungsten salt of the present invention includes the following steps: Step 1, preparation of an alkali metal source solution; Step 11, adding deionized water to the first stirring container; Step 12, adding an alkali metal source to the first stirring container; Step 13, setting at normal pressure so that the dissolution temperature is 10°C to 40°C and the stirring speed is 200 r / min to 600 r / min; after stirring for 1 min to 15 min, an alkali metal source solution is prepared; Step 2, preparation of a tungsten source solution; Step 21, adding a tungsten source to the second stirring container; Step 22, adding an alcohol solution to the second stirring container; Step 23, setting at normal pressure so that the dissolution temperature is 10°C to 40°C and the stirring speed is 200 r / min to 600 r / min; after stirring for 10 min to 60 min, a tungsten source solution is prepared; Step 3, heating in a water bath to generate a nano-alkali metal tungsten bronze dispersion by hydrolysis; Dosage: To produce 1 kg of nano-alkali metal tungsten bronze powder, 0.18 kg to 90 kg of alkali metal source solution and 3.68 kg to 184 kg of tungsten source solution are required; Manufacture of an alkali metal tungsten bronze dispersion by low-temperature heating hydrolysis of a process: An alkali metal source solution, a tungsten source solution, and deionized water are added to a water bath heating container (3); the water bath temperature is set to 40~95 °C and the stirring speed is set to 200 r / min~1000 r / min. After stirring for 90 min~2880 min, an alkali metal tungsten bronze dispersion is obtained; Step Four, solid-liquid separation; Step Five, manufacture of nano alkali metal tungsten bronze powder by drying; The alkali metal tungsten bronze solution produced in Step Four is dried by a vacuum resistance furnace, and the vacuum degree is set to 1×10 -2 Pa~1×10 -4 Pa, the drying temperature is 50 °C~100 °C, and the drying time is 180 min~720 min to obtain alkali metal tungsten bronze powder.

[0012] The advantages of the present invention for industrially manufacturing nano alkali metal tungsten bronze by adopting hydrolysis of a low-temperature cation coordination tungsten salt are as follows.

[0013] 〔1〕Adopting hydrolysis of a low-temperature cation coordination tungsten salt to industrially manufacture nano alkali metal tungsten bronze enables the synthesis of a pure-phase alkali metal tungsten bronze under low-temperature and low-pressure conditions, with mild process conditions, good crystallinity of the product, no need for subsequent firing, and low energy consumption.

[0014] 〔2〕Adopting hydrolysis of a low-temperature cation coordination tungsten salt to industrially manufacture nano alkali metal tungsten bronze does not strictly require the types of raw materials, and there are many types available for the alkali metal source and the solvent.

[0015] 〔3〕Adopting hydrolysis of a low-temperature cation coordination tungsten salt to industrially manufacture nano alkali metal tungsten bronze has a simple industrial process, a short manufacturing cycle, and does not require special equipment for high temperature and high pressure.

[0016] 〔4〕Adopting the hydrolysis of a low-temperature cation-coordinated tungsten salt to industrially produce nano-alkali metal tungsten bronze has a high yield and a large production volume.

[0017] 〔5〕Adopting the hydrolysis of a low-temperature cation-coordinated tungsten salt to industrially produce nano-alkali metal tungsten bronze can control the synthesis cycle of pure-phase alkali metal tungsten bronze according to the stirring time and stirring speed, and does not affect the form of pure-phase cesium tungsten bronze.

[0018] 〔6〕Adopting the hydrolysis of a low-temperature cation-coordinated tungsten salt to industrially produce nano-alkali metal tungsten bronze is not sensitive to the volume, liquid phase volume and material of the reaction vessel, and the production volume can be easily controlled by increasing the volume of the reaction vessel or the liquid phase volume.

[0019] 〔7〕Adopting the hydrolysis of a low-temperature cation-coordinated tungsten salt to industrially produce nano-alkali metal tungsten bronze results in excellent product performance.

[0020] 〔8〕In the spray coating process, the present invention sets the distance between the ultrasonic atomization nozzle array and the upper surface of the pre-coated substrate to 5 - 20 cm, enabling the ultrasonic atomization nozzle array to achieve large-area spray coating in a short time in a spray coating area of 0.8 m × 0.8 m or more, and then curing with hot air to improve the bonding force between the coating and the glass surface.

Brief Description of the Drawings

[0021]

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Mode for Carrying Out the Invention

[0022] Hereinafter, the present invention will be described in more detail with reference to the drawings and examples.

[0023] As shown in FIG. 1, the present invention provides an industrial manufacturing method of nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation coordination tungsten salt, including the following manufacturing steps.

[0024] Step 1, manufacturing an alkali metal source solution; Step 11, adding deionized water to the first stirring container; Step 12, adding an alkali metal source to the first stirring container; In the present invention, the alkali metal source includes a hydroxide corresponding to an alkali metal ion, a chloride salt, and one or a combination of two salts of nitrate, sulfate, and carbonate.

[0025] The hydroxide is cesium hydroxide, potassium hydroxide, or sodium hydroxide.

[0026] The chloride salt is cesium chloride, rubidium chloride, potassium chloride, or sodium chloride.

[0027] The nitrate is cesium nitrate, potassium nitrate, or sodium nitrate.

[0028] The sulfate is cesium sulfate, potassium sulfate, or sodium sulfate.

[0029] The carbonate is cesium carbonate, potassium carbonate, or sodium carbonate.

[0030] Step 13, set at normal pressure so that the dissolution temperature is 10°C to 40°C and the stirring speed is 200 r / min to 600 r / min; after stirring for 1 min to 15 min, an alkali metal source solution is manufactured.

[0031] The concentration of the alkali metal source in the manufactured alkali metal source solution is 0.1 mol / L to 6 mol / L.

[0032] As shown in FIG. 3, in the present invention, the first stirring container 1 is a double-layer stainless steel round barrel. Inside the first stirring container 1, a stirrer 1E is installed, and the stirrer 1E provides a stirring speed in the process of manufacturing the first solution, and the stirring speed is 200 r / min to 600 r / min.

[0033] Above the cylinder 1A of the first stirring container 1, an alkali metal source supply port 1A1, a deionized water supply port 1A2, and an exhaust port 1A3 are installed; the exhaust port 1A3 discharges the gas generated in the process of manufacturing the alkali metal source solution so as to ensure the safety in the process of manufacturing the alkali metal source solution; below the cylinder 1A, an alkali metal source solution discharge port 1A4 is installed. The discharge port 1A4 can communicate with the water bath heating container 3 through a connected pipe, and as shown in FIG. 2, a pressure gauge, a flow meter, a valve, etc. can be installed on this pipe.

[0034] A base 1B is installed at the bottom of the first stirring container 1. The base 1B supports the stirring container and stabilizes the first stirring container 1 in an operating state.

[0035] In the present invention, in order to monitor the temperature in the process of manufacturing the alkali metal source solution, a temperature sensor is installed in the first stirring container 1 to measure the dissolution temperature in the process of manufacturing the alkali metal source solution. When the current dissolution temperature is higher than the set dissolution temperature (10°C to 40°C), the stirring speed is reduced.

[0036] Step two, manufacturing of tungsten source solution; Step 21, adding a tungsten source to the second stirring container; In the present invention, the tungsten source is tungsten hexachloride (WCl6) or tungsten tetrachloride (WCl4).

[0037] Step 22, adding an alcohol solution to the second stirring container; In the present invention, the alcohol solution is one, two, or a combination of two or more of methanol (CH3OH), ethanol (CH3CH2OH), n-propanol (CH3(CH2)2OH), isopropanol (CH(CH3)2OH), and n-butanol (CH3(CH2)3OH).

[0038] In Step 23, at normal pressure, the dissolution temperature is set to be 15°C to 40°C and the stirring speed is set to be 200 r / min to 600 r / min; after stirring for 10 min to 60 min, a tungsten source solution is produced.

[0039] The tungsten source concentration of the produced tungsten source solution is 0.04 mol / L to 1 mol / L.

[0040] As shown in FIG. 4, in the present invention, the second stirring container 2 is a double-layer stainless steel round barrel. Inside the second stirring container 2, a stirrer 2E is installed, and the stirrer 2E provides the stirring speed in the process of producing the tungsten source solution, and the stirring speed is 200 r / min to 600 r / min.

[0041] Above the cylinder 2A of the second stirring container 2, a tungsten source supply port 2A1, an alcohol source supply port 2A2, and an exhaust port 2A3 are installed. The exhaust port 2A3 discharges the gas generated in the process of producing the tungsten source solution so as to ensure the safety in the process of producing the tungsten source solution; below the cylinder 2A, a discharge port 2A4 for the tungsten source mixed solution is installed. The discharge port 2A4 can communicate with a water bath heating container 3 through a connected pipe. As shown in FIG. 2, a pressure gauge, a flow meter, a valve, etc. can be installed in this pipe.

[0042] A base 2B is installed at the bottom of the second stirring container 2. The base 2B supports the stirring container and stabilizes the stirring container 1 in an operating state. On the outer wall of the inner housing 2C of the second stirring container 2, a resistance wire 2D is wound, that is, the resistance wire 2D is installed between the outer wall of the inner housing 2C and the inner wall of the cylinder 2A, and a heat insulating material is filled. During the production of the tungsten source solution, if the measured temperature of the second stirring container 2 is lower than the set dissolution temperature as measured by a thermometer, it is necessary to provide a heat source by the resistance wire 2D and heat the tungsten source solution in the production process.

[0043] In the present invention, in order to monitor the temperature in the production process of the tungsten source solution, a temperature sensor is installed in the second stirring container 2 to measure the dissolution temperature in the production process of the second solution. If the current dissolution temperature is lower than the set dissolution temperature (10 °C to 40 °C), the resistance wire 2D is activated to heat the tungsten source solution in the production process.

[0044] In the present invention, the second stirring container 2 can also be employed for the production of the alkali metal source mixed solution.

[0045] In the present invention, the first stirring container 1 can also be employed for the production of the tungsten source mixed solution.

[0046] Step 3: Heating in a water bath and generating a nano-alkali metal tungsten bronze dispersion by hydrolysis; As shown in FIGS. 1, 2, and 5, in the present invention, an alkali metal cation (M + ) and a tungsten salt are coordinated, and then deionized water is added to complete the stepwise hydrolysis of the tungsten salt coordinated with the alkali metal cation. Finally, in order to obtain a nano-alkali metal tungsten bronze dispersion, the alkali metal source solution is mixed with the tungsten source solution using a water bath heating container. In the present invention, the means of performing hydrolysis after coordination is adopted to quickly limit the desired alkali metal element (M) into the product M x WO3, and M +It avoids the drawback that it is not involved in the hydrolysis reaction later and greatly improves the utilization rate of element M. The change in the electronic structure due to coordination reduces hexavalent tungsten in the mixed solution of the alkali metal source solution and the tungsten source solution, thereby rapidly forming crystal formation particles necessary for nano-alkali metal tungsten bronze in the mixed solution and accelerating the industrial hydrolysis reaction rate.

[0047] Dosage: To produce 1 kg of alkali metal tungsten bronze powder, 0.31 kg to 18 kg of alkali metal source solution and 3.68 kg to 92 kg of tungsten source solution are required.

[0048] Production of alkali metal tungsten bronze dispersion by low-temperature heating hydrolysis in one step: Add the alkali metal source solution, tungsten source solution and deionized water to a water bath heating container; set the water bath temperature to 40°C to 90°C and the stirring speed of the water bath heating container to 200 r / min to 1000 r / min, and stir for 90 min to 2880 min to obtain an alkali metal tungsten bronze dispersion.

[0049] In the present invention, using the low-temperature environment of 40°C to 95°C provided by the water bath heating container 3 to produce the alkali metal tungsten bronze dispersion achieves the synthesis of alkali metal tungsten bronze under extremely mild process conditions and avoids the extreme conditions (high temperature, high pressure) required by the two conventional traditional methods, namely the solvothermal method and the hydrothermal method. Using a water bath heating container instead of special equipment for high temperature and high pressure realizes the use of medium and low complexity equipment instead of high complexity equipment.

[0050] Manufacturing the nano-alkali metal tungsten bronze dispersion using the water bath heating container 3 avoids the use of special equipment under high temperature and high pressure in the large-scale production process. On the one hand, instead of special equipment under high temperature and high pressure, a water bath heater is used, significantly reducing the equipment purchase cost; on the other hand, the water bath heater has good operability, is easy to operate, and does not increase a large amount of time cost (such as the training of experimenters) during the change of process equipment, nor does it introduce the factory / laboratory design cost (such as issues of heating, electrical wiring, etc.) required for excessive equipment replacement.

[0051] Manufacturing the alkali metal tungsten bronze dispersion using a water bath heater under a low-temperature environment (40 °C to 95 °C) realizes the use of medium- and low-complexity equipment instead of high-complexity equipment and the use of a low-risk process flow instead of a high-risk process flow: while enabling temperature control, by introducing a stirring operation, it expands the selectivity of the process, improves the controllability of the reaction progress, significantly improves the process safety, reduces the time cost required for the same production volume, and reduces the production energy consumption.

[0052] Refer to the water bath heating container 3 designed according to the present invention shown in FIG. 5. The water bath heating container 3 is divided into a heating cylinder 3C and a water bath cylinder 3A, and is made of stainless steel. A heating coil 3D is installed between the heating cylinder 3C and the water bath cylinder 3A, and tap water is injected into the water bath cylinder 3A. A stirrer 3E is installed inside the heating cylinder 3C, and the stirrer 3E provides the stirring speed during the manufacturing process of the dispersion, and the stirring speed is 200 r / min to 1000 r / min.

[0053] Above the water bath heating container 3, there are a CA supply port 3A1 (for injecting an alkali metal source solution), a CB supply port 3A2 (for injecting a tungsten source solution), a CC supply port 3A3 (for injecting deionized water), and an exhaust port 3A4. The exhaust port 3A4 discharges the gas generated during the production process of the dispersion; below the cylinder 3A, a dispersion discharge port 3A5 is installed. The dispersion discharge port 3A5 can communicate with the solid-liquid separator 4 through a connected pipe, and a pressure gauge, a flow meter, a valve, etc. can be installed on this pipe.

[0054] At the bottom of the water bath heating container 3, a base 3B is installed. The base 3B supports the water bath heating container while stabilizing the water bath heating container in a stirring operation state.

[0055] In the present invention, on the outer wall of the heating cylinder 3C of the water bath heating container 3, a heating coil 3D (such as a resistance wire) is wound and immersed in tap water. That is, the heating coil 3D and the water required for water bath heating are installed between the outer wall of the heating cylinder 3C and the inner wall of the water bath cylinder 3A. The heating coil 3D provides a heat source to the tap water, and a heat insulating material is wound around the outer wall of the water bath cylinder 3A. During the production of the dispersion, if the measured temperature of the water bath heating container 3 is lower than the set water bath temperature as measured by a thermometer, it is necessary to heat the tap water by the heating coil 3D to provide a heat source for the production of the dispersion.

[0056] In the present invention, in order to monitor the temperature during the production process of the dispersion, a temperature sensor is installed in the water bath heating container 3 to measure the dissolution temperature during the production process of the dispersion.

[0057] Step Four: Solid-Liquid Separation; In the present invention, as shown in FIGS. 1, 2, and 6, in the solid-liquid separation process, a cleaning liquid is added and washed multiple times to remove organic impurities and inorganic impurities that may be adsorbed on the surface of the product remaining in the reaction, purify the product, and avoid secondary aggregation of the nano-alkali metal tungsten bronze particles in the dispersion.

[0058] In the present invention, the cleaning liquid is methanol (CH3OH), ethanol (CH3CH2OH), acetone (C3H6O); or a combination of methanol and deionized water; a combination of ethanol and deionized water; a combination of acetone and deionized water.

[0059] In step 41, an alkali metal tungsten bronze dispersion is added to the solid-liquid separator 4, and after standing for 20 to 100 minutes, a first precipitate and a first supernatant are obtained; and the first supernatant is discharged. In the present invention, the maximum amount of the alkali metal tungsten bronze dispersion added to the solid-liquid separator 4 is two-thirds of the capacity of the solid-liquid separator.

[0060] In step 42, a cleaning liquid is added to the solid-liquid separator 4, and the cleaning liquid is 2 to 5 times that of the first precipitate; the stirring speed of the solid-liquid separator is set to be 200 r / min to 600 r / min, and after stirring for 10 min to 60 min and then standing for 20 to 100 minutes, a second precipitate and a second supernatant are obtained; and the second supernatant is discharged; In step 43, a cleaning liquid is added to the solid-liquid separator 4, and the cleaning liquid is 2 to 5 times that of the second precipitate; the stirring speed of the solid-liquid separator is set to be 200 r / min to 600 r / min, and after stirring for 10 min to 60 min and then standing for 20 to 100 minutes, a third precipitate and a third supernatant are obtained; and the third supernatant is discharged; In step 47, a cleaning liquid is added to the solid-liquid separator 4, and the solvent is 2 to 5 times that of the third precipitate; the stirring speed of the solid-liquid separator is set to be 200 r / min to 600 r / min; after stirring for 10 min to 60 min, an alkali metal tungsten bronze dispersion is obtained.

[0061] The solid-liquid separator 4 designed according to the present invention is shown in FIG. 6. The solid-liquid separator 4 is a double-layer stainless steel round barrel. Inside the solid-liquid separator 4, a stirrer 4E is installed, and the stirrer 4E provides a stirring speed in the separation process of the dispersion, and the stirring speed is 200 r / min to 600 r / min.

[0062] Above the cylinder 4A of the solid-liquid separator 4, there are a DA supply port 4A1 (for injecting an alkali metal tungsten bronze dispersion), a DB supply port 4A2 (for injecting a cleaning liquid), and a DA discharge port 4A3 (for discharging the supernatant); below the cylinder 4A, there is a DB discharge port 4A4, and the DB discharge port 4A4 is for discharging the alkali metal tungsten bronze liquid. In Fig. 2, the DB discharge port 4A4 can communicate with a third stirrer through a connected pipe, and a pressure gauge, a flow meter, a valve, etc. can be installed on this pipe.

[0063] A base 4B is installed at the bottom of the solid-liquid separator 4. The base 4B supports the solid-liquid separator while stabilizing the solid-liquid separator in a stirring operation state.

[0064] Step Five: Manufacture of nano-alkali metal tungsten bronze powder by drying; In the present invention, in order to analyze the performance of the nano-alkali metal tungsten bronze liquid material manufactured in Step Four, it is necessary to perform a drying treatment on the nano-alkali metal tungsten bronze liquid to obtain nano-alkali metal tungsten bronze powder. The cesium tungsten bronze liquid manufactured in Step Four is dried by a vacuum resistance furnace, and the vacuum degree is set to 1×10 -2 Pa~1×10 -4 Pa, the drying temperature is 50°C~100°C, and the drying time is 180 min~720 min to obtain nano-alkali metal tungsten bronze powder.

[0065] As a result of analyzing the nano-alkali metal tungsten bronze powder manufactured by the method of the present invention by an XRD pattern, it meets the requirement of the chemical formula M x WO3 (0.2≦X≦0.33). As preferred components manufactured by the method of the present invention, Cs 0.30 WO3 powder, Rb 0.28 WO3 powder, K 0.32 WO3 powder and Na 0.33There is WO3 powder. According to the calculation of the charged raw materials and the production amount of the product, the industrial yield of the manufactured nano cesium tungsten bronze powder is 70% - 85%, the industrial yield of the nano rubidium tungsten bronze powder is 70% - 85%, the industrial yield of the nano potassium tungsten bronze powder is 60% - 80%, and the industrial yield of the nano sodium tungsten bronze powder is 50% - 75%.

[0066] As a result of analysis by SEM spectrum, the morphology of the nano alkali metal tungsten bronze powder manufactured by the method of the present invention is short rod-shaped or equiaxial. The length of the short rod-shaped structure is 10 - 150 nm, the diameter is 10 - 50 nm, and the size in each direction of the equiaxial structure is less than 100 nm.

[0067] In the present invention, Figure 1 is for introducing the process of the powder for industrially manufacturing nano alkali metal tungsten bronze by hydrolysis of low-temperature cation coordination tungsten salt. The difference in the process lies in the manufacture of the alkali metal tungsten bronze dispersion liquid by one-step low-temperature heating hydrolysis. The water bath synthesis of the pure-phase alkali metal tungsten bronze under low-temperature and pressureless conditions is achieved. The process conditions are mild, the product (nano alkali metal tungsten bronze powder) has good crystallinity, no subsequent firing is required, and the energy consumption is low.

[0068] In the industrial manufacture of the nano alkali metal tungsten bronze liquid in Figure 1, as shown in Figure 2, the nano alkali metal tungsten bronze liquid is applied to manufacture the nano alkali metal tungsten bronze paint, and the nano alkali metal tungsten bronze coating is manufactured on the glass plate with the nano alkali metal tungsten bronze paint. The glass curtain wall is manufactured with the glass carrying the nano alkali metal tungsten bronze coating, which leads to indoor temperature reduction. The process for industrially manufacturing the nano alkali metal tungsten bronze coating according to the present invention is as follows.

[0069] Step 1, manufacture of the alkali metal source solution; Step 11, add deionized water to the first stirring container; Step 12: Add the alkali metal source to the first stirring container; In the present invention, the alkali metal source includes a hydroxide corresponding to an alkali metal ion, a chloride salt, and a salt of one or a combination of two of nitrates, sulfates, and carbonates.

[0070] The hydroxide is cesium hydroxide, potassium hydroxide, or sodium hydroxide.

[0071] The chloride salt is cesium chloride, rubidium chloride, potassium chloride, or sodium chloride.

[0072] The nitrate is cesium nitrate, potassium nitrate, or sodium nitrate.

[0073] The sulfate is cesium sulfate, potassium sulfate, or sodium sulfate.

[0074] The carbonate is cesium carbonate, potassium carbonate, or sodium carbonate.

[0075] Step 13: Set the dissolution temperature to 10°C to 40°C and the stirring speed to 200 r / min to 600 r / min at normal pressure; after stirring for 10 min to 60 min, produce an alkali metal source solution.

[0076] The concentration of the alkali metal source in the produced alkali metal source solution is 0.5 mol / L to 5 mol / L.

[0077] Step Two: Production of a tungsten source solution; Step 21: Add the tungsten source to the second stirring container; In the present invention, the tungsten source is tungsten hexachloride (WCl6) or tungsten tetrachloride (WCl4).

[0078] Step 22: Add the alcohol solution to the second stirring container; In the present invention, the alcohol solution is one, two, or a combination of two or more of methanol (CH3OH), ethanol (CH3CH2OH), n-propanol (CH3(CH2)2OH), isopropanol (CH(CH3)2OH), and n-butanol (CH3(CH2)3OH).

[0079] In Step 23, under normal pressure, set the dissolution temperature to 15°C to 40°C and the stirring speed to 200 r / min to 600 r / min; after stirring for 10 min to 60 min, produce a tungsten source solution.

[0080] The tungsten source concentration of the produced tungsten source solution is 0.05 mol / L to 1 mol / L.

[0081] Step Three: Heat in a water bath to generate a nano-alkali metal tungsten bronze dispersion by hydrolysis; Dosage: To produce 1 kg of alkali metal tungsten bronze powder, 0.37 kg to 3.6 kg of alkali metal source solution and 3.68 kg to 73.6 kg of tungsten source solution are required.

[0082] Manufacture of an alkali metal tungsten bronze dispersion by low-temperature heating hydrolysis in the first step: Add an alkali metal source solution, a tungsten source solution, and deionized water to a water bath heating container; set the water bath temperature to 40°C to 90°C and the stirring speed of the water bath heating container to 200 r / min to 1000 r / min, and after stirring for 90 min to 2880 min, obtain a dispersion.

[0083] Step Four: Solid-liquid separation; In the present invention, the cleaning solution is methanol (CH3OH), ethanol (CH3CH2OH), acetone (C3H6O); or a combination of methanol and deionized water; a combination of ethanol and deionized water; a combination of acetone and deionized water.

[0084] Step 41: Add an alkali metal tungsten bronze dispersion to the solid-liquid separator, let it stand for 20 - 100 min, then obtain the first precipitate and the first supernatant; and discharge the first supernatant; Step 42: Add a cleaning solution to the solid-liquid separator, where the cleaning solution is 2 - 5 times the amount of the first precipitate; set the stirring speed of the solid-liquid separator to 200 r / min - 600 r / min, stir for 10 min - 60 min and then let it stand for 20 - 100 min, then obtain the second precipitate and the second supernatant; and discharge the second supernatant; Step 43: Add a cleaning solution to the solid-liquid separator, where the cleaning solution is 2 - 5 times the amount of the second precipitate; set the stirring speed of the solid-liquid separator to 200 r / min - 600 r / min, stir for 10 min - 60 min and then let it stand for 20 - 100 min, then obtain the third precipitate and the third supernatant; and discharge the third supernatant; Step 47: Add a cleaning solution to the solid-liquid separator, where the solvent is 0.5 - 2 times the amount of the third precipitate; set the stirring speed of the solid-liquid separator to 200 r / min - 600 r / min; after stirring for 10 min - 60 min, obtain an alkali metal tungsten bronze dispersion.

[0085] Step Five: Manufacture of an alkali metal tungsten bronze paint; Dosage (parts by weight): Alkali metal tungsten bronze dispersion : PVA : Deionized water = 1 : 2 - 15 : 80 - 130

[0086] Add an alkali metal tungsten bronze dispersion, PVA (polyvinyl alcohol), and deionized water to the third stirring container; set the stirring speed of the third stirring container to 100 r / min - 400 r / min; after stirring for 30 min - 120 min, obtain an alkali metal tungsten bronze paint; In the present invention, the structure of the third stirring container may be the same as that of the first stirring container.

[0087] Step Six: Manufacture of a glass curtain wall by a spray coating process; Inject the alkali metal tungsten bronze paint into the tank of the spray coater through a pipe, and set the spray coating distance H from the nozzle to the upper surface of the glass plate to be 0.5 - 2 cm; the flow rate of the alkali metal tungsten bronze paint is 1 - 7 ml / min.

[0088] The temperature of the hot air provided by the hot air blower is 22°C - 40°C, the speed of the conveyor roller is 10 r / min - 60 r / min, and after curing, a nano alkali metal tungsten bronze coating on the upper surface of the glass is manufactured.

[0089] In the present invention, in order to manufacture a glass curtain wall from the glass carrying the nano alkali metal tungsten bronze coating and realize a spray coating of a large size of the glass curtain wall, as shown in FIG. 7, a structure of an array nozzle arrangement is adopted. Ultrasonic atomizing nozzles 5C are arranged in an array on the plate 5A of the nozzle mechanism 5. The ultrasonic atomizing nozzles 5C communicate with the tank of the spray coater through a soft tube and communicate with the discharge port of the third stirring container through a tank pipe. A post 5B is installed at the center of the plate 5A, and the post 5B is fixed to the housing of the spray coater.

[0090] In the present invention, the nozzle diameter of the ultrasonic atomizing nozzle 5C is 10 - 30 mm, and the jet outlet diameter is 0.5 - 2 mm. The number of ultrasonic atomizing nozzles 5C installed on the plate 5A is determined by the size of the glass curtain wall to be manufactured, the nozzle diameter, and the jet outlet diameter.

[0091] Example 1 Cesium Tungsten Bronze Cs 0.30 Manufacture of WO3 As shown in Figure 2, Steps 1 to 4 of the present invention are an industrial manufacturing method of nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation coordination tungsten salt, and Steps 5 to 6 are a manufacturing method of a nano-alkali metal tungsten bronze coating. The nano-alkali metal tungsten bronze produced by the method of the present invention was made into a nano-alkali metal tungsten bronze paint, and then, a spray coating process was adopted to manufacture a nano-alkali metal tungsten bronze coating on a glass plate, and the glass carrying the nano-alkali metal tungsten bronze coating was applied to a glass curtain wall. In this example, it particularly refers to the manufacture and application of nano-cesium tungsten bronze and its coating. The specific manufacturing process is as follows.

[0092] Step 1, preparation of a cesium source solution; Dosage: In the cesium source solution, the cesium source concentration was 1 mol / L.

[0093] Cesium chloride (CsCl) and deionized water were added to a first stirring container; at normal pressure, the dissolution temperature was set to 25 °C and the stirring speed was set to 400 r / min, and after stirring for 5 min, a cesium source solution was prepared.

[0094] Step 2, preparation of a tungsten source solution; Dosage: The tungsten source concentration of the tungsten source solution was 0.1 mol / L.

[0095] WCl6 and CH3CH2OH were added to a second stirring container; at normal pressure, the dissolution temperature was set to 30 °C and the stirring speed was set to 300 r / min, and after stirring for 25 min, a tungsten source solution was prepared.

[0096] Step 3, heating in a water bath to generate a nano-cesium tungsten bronze dispersion by hydrolysis; Dosage: To produce 1 kg of cesium tungsten bronze powder, 0.61 kg of cesium source solution and 46.12 kg of tungsten source solution were required.

[0097] Manufacture of dispersion by low-temperature heating and hydrolysis in one process: Add the cesium source solution and the tungsten source solution to a water bath heating container; set the water bath temperature to 70 °C and the stirring speed of the water bath heating container to 500 r / min. After stirring for 240 min, a dispersion was obtained.

[0098] Step Four, solid-liquid separation; In Example 1, the cleaning solution was CH3CH2OH.

[0099] Step 41, add the dispersion to a solid-liquid separator, let it stand for 60 min, then obtain the first precipitate and the first supernatant; and discharge the first supernatant; Step 42, add the cleaning solution to the solid-liquid separator, where the cleaning solution is three times that of the first precipitate; set the stirring speed of the solid-liquid separator to 300 r / min, stir for 30 min and then let it stand for 90 min, then obtain the second precipitate and the second supernatant; and discharge the second supernatant; Step 43, add the cleaning solution to the solid-liquid separator, where the cleaning solution is three times that of the second precipitate; set the stirring speed of the solid-liquid separator to 300 r / min, stir for 60 min and then let it stand for 60 min, then obtain the third precipitate and the third supernatant; and discharge the third supernatant; Step 47, add deionized water to the solid-liquid separator, where the solvent is one time that of the third precipitate; set the stirring speed of the solid-liquid separator to 300 r / min; after stirring for 30 min, a cesium tungsten bronze dispersion was obtained.

[0100] Characteristics and performance of cesium tungsten bronze powder manufactured by the method of Example 1 Dry the cesium tungsten bronze dispersion manufactured in Step Four in a vacuum resistance furnace at a drying temperature of 60 °C and under vacuum drying for 240 min to obtain Cs 0.30 WO3 cesium tungsten bronze powder, that is, powder was obtained. According to the calculation of the charged raw materials and the production amount of the product, the industrial yield of Cs 0.30 The industrial yield of WO3 powder was as high as 80%.

[0101] In the XRD pattern shown in FIG. 8, all the diffraction peaks of the cesium tungsten bronze powder produced by the method of Example 1 belong to Cs 0.30 WO3, indicating that pure-phase cesium tungsten bronze was synthesized.

[0102] In the SEM spectrum shown in FIG. 9, the Cs 0.30 WO3 powder produced by the method of Example 1 was in the form of short rods, the length of the short rod structure was 10 - 140 nm, and the diameter was 10 - 20 nm.

[0103] In the Uv-Vis-NIR spectrum shown in FIG. 13, the Cs 0.30 WO3 powder produced by the method of Example 1 had excellent near-infrared shielding performance, high visible light transmittance, and good ultraviolet shielding performance.

[0104] In the FTIR spectrum shown in FIG. 14, the Cs 0.30 WO3 powder produced by the method of Example 1 had certain mid- and far-infrared shielding performance.

[0105] In the Uv-Vis-NIR spectrum shown in FIG. 15, the composite film of the Cs 0.30 WO3 powder and PVA produced by the method of Example 1 had high near-infrared absorption performance, ultraviolet shielding performance, and high visible light transmittance performance.

[0106] Step Five: Production of cesium tungsten bronze paint; Dosage (parts by weight): Cesium tungsten bronze dispersion: PVA: Deionized water = 1:5:94 Add cesium tungsten bronze dispersion, PVA, and deionized water to the third stirring container; set the stirring speed of the third stirring container to 300 r / min; after stirring for 60 min, cesium tungsten bronze paint was obtained.

[0107] Step Six: Production of glass curtain wall by spray coating process; Inject the cesium tungsten bronze paint into the tank of the spray coater through a pipe, and set the spray coating distance H from the nozzle to the upper surface of the glass plate to be 1 cm; the flow rate of the cesium tungsten bronze paint was 4 ml / min.

[0108] The temperature of the hot air provided by the hot air blower was 35°C, the speed of the conveyor roller was 50 r / min, and after curing, a cesium tungsten bronze coating on the upper surface of the glass was manufactured.

[0109] The cesium tungsten bronze coating on the upper surface of the glass shown in Fig. 16 was irradiated onto the glass at a distance of 20 cm from the upper surface of the glass with a 50 W halogen lamp during the measurement of the photothermal conversion and heat insulation performance. Compared with the quartz glass without a heat insulation coating or with only a PVA coating, the glass with a heat insulation coating on the upper surface manufactured in Example 1 reduced the temperature inside the box by 13°C, and the drop width was 18.6%. The Cs 0.3 The heat insulation principle of the WO3 coating is that the cesium tungsten bronze in the coating absorbs near-infrared light and converts it into heat outside the box to achieve the heat insulation effect. Therefore, the Cs 0.3 WO3 coating manufactured by the method of Example 1 had high photothermal conversion performance and heat insulation performance.

[0110] When the glass with a Cs 0.3 WO3 coating on the upper surface manufactured in Example 1 was reversed so that the heat insulation coating on the upper surface of the glass was placed inside the box, the Cs 0.3 WO3 coating can be used to have high photothermal conversion performance and heat insulation performance and can store heat inside the box. By adjusting the relative position of the heat insulation coating manufactured in Example 1, effective heat management can be carried out.

[0111] The one-step low-temperature hydrothermal hydrolysis method adopted in the present invention utilizes the forced hydrolysis of metal salts under acidic conditions to generate uniform dispersed nanoparticles. Compared with the hydrothermal method and the solvothermal method, the reaction temperature of the hydrolysis method in the present invention is lower, the yield is higher, there is no pressure in the reaction, and it is safer. Both the hydrothermal method and the solvothermal method were syntheses carried out by utilizing the chemical reaction of substances in a solution under certain temperature (100°C to 1000°C) and pressure (1 MPa to 100 MPa) conditions.

[0112] Example 2 Rubidium tungsten bronze Rb 0.28 Production of WO3 As shown in Figure 1, the method for industrially producing nanorubidium tungsten bronze by hydrolysis of the low-temperature cation coordination tungsten salt of the present invention includes the following production steps.

[0113] Step 1, production of rubidium source solution; Dosage: The rubidium source concentration in the rubidium source solution was 1 mol / L.

[0114] Rubidium chloride (RbCl) and deionized water were added to the first stirring container; at normal pressure, the dissolution temperature was set to 25°C and the stirring speed was set to 400 r / min. After stirring for 20 min, the rubidium source solution was produced.

[0115] Step 2, production of tungsten source solution; Dosage: The tungsten source concentration of the tungsten source solution was 0.1 mol / L.

[0116] WCl6 and CH3CH2OH were added to the second stirring container; at normal pressure, the dissolution temperature was set to 40°C and the stirring speed was set to 300 r / min. After stirring for 50 min, the tungsten source solution was produced.

[0117] Step 3, heating in a water bath and generating a nanorubidium tungsten bronze dispersion by hydrolysis; Dosage: To produce 1 kg of cesium tungsten bronze powder, 0.61 kg of rubidium source solution and 49.2 kg of tungsten source solution were required.

[0118] Preparation of dispersion by low-temperature heating and hydrolysis in one step: The rubidium source solution and the tungsten source solution were added to a water bath heating container; the water bath temperature was set to 70 °C, the stirring speed of the water bath heating container was set to 500 r / min, and after stirring for 600 min, a dispersion was obtained.

[0119] Step 4, solid-liquid separation; In Example 2, the cleaning solution was CH3CH2OH.

[0120] Step 41, the dispersion was added to a solid-liquid separator, and after standing for 40 min, the first precipitate and the first supernatant were obtained; then the first supernatant was discharged; Step 42, the cleaning solution was added to the solid-liquid separator, and the cleaning solution was 3.5 times that of the first precipitate; the stirring speed of the solid-liquid separator was set to 400 r / min, stirred for 20 min and then stood for 80 min, and then the second precipitate and the second supernatant were obtained; then the second supernatant was discharged; Step 43, the cleaning solution was added to the solid-liquid separator, and the cleaning solution was 3 times that of the second precipitate; the stirring speed of the solid-liquid separator was set to 400 r / min, stirred for 20 min and then stood for 80 min, and then the third precipitate and the third supernatant were obtained; then the third supernatant was discharged; Step 47, the cleaning solution was added to the solid-liquid separator, and the solvent was 1 time that of the third precipitate; the stirring speed of the solid-liquid separator was set to 400 r / min; after stirring for 30 min, a rubidium tungsten bronze dispersion was obtained.

[0121] Characteristics and performance of rubidium tungsten bronze produced by the method of Example 2 The rubidium tungsten bronze dispersion produced in Step 4 was dried in a vacuum resistance furnace at a drying temperature of 60 °C and vacuum drying for 480 min to obtain rubidium tungsten bronze powder, i.e., Rb 0.28WO3 powder was obtained. According to the calculation of the charged raw materials and the production amount of the product, Rb 0.28 The industrial yield of the WO3 powder was as high as 75%.

[0122] In the XRD pattern shown in Fig. 8, all the diffraction peaks of the rubidium tungsten bronze powder produced by the method of Example 2 belonged to Rb 0.28 WO3, indicating that pure-phase rubidium tungsten bronze was synthesized.

[0123] In the SEM spectrum shown in Fig. 9, the morphology of the Rb 0.28 WO3 powder produced by the method of Example 2 was short rod-shaped, the length of the short rod-shaped structure was 10 - 100 nm, and the diameter was 15 - 30 nm.

[0124] As measured by the Uv-Vis-NIR spectrum, the Rb 0.28 WO3 powder produced by the method of Example 2 had excellent near-infrared shielding performance, high visible light transmittance and good ultraviolet shielding performance.

[0125] As measured by the FTIR spectrum, the Rb 0.28 WO3 powder produced by the method of Example 2 had certain mid- and far-infrared shielding performance.

[0126] In the Uv-Vis-NIR spectrum shown in Fig. 15, the composite film of the Rb 0.28 WO3 powder and PVA produced by the method of Example 2 had high near-infrared absorption performance, ultraviolet shielding performance and high visible light transmittance performance.

[0127] Step Five: Manufacture of rubidium tungsten bronze paint; Dosage (parts by weight): Rubidium tungsten bronze dispersion: PVA: Deionized water = 1:6:94 Add the rubidium tungsten bronze dispersion, PVA, and deionized water to the third stirring container; set the stirring speed of the third stirring container to 300 r / min; after stirring for 50 min, rubidium tungsten bronze paint was obtained.

[0128] Project Six: Manufacture of Glass Curtain Wall by Spray Coating Process; Inject the rubidium tungsten bronze paint into the tank of the spray coater through a pipe, and set the spray coating distance H from the nozzle to the upper surface of the glass plate to 2 cm; the flow rate of the rubidium tungsten bronze paint was 3.5 ml / min.

[0129] The temperature of the hot air provided by the hot air blower was 40°C, the speed of the conveyor roller was 40 r / min, and after curing, a rubidium tungsten bronze coating on the upper surface of the glass was manufactured.

[0130] The rubidium tungsten bronze coating on the upper surface of the glass shown in Fig. 16 was irradiated onto the glass at a distance of 20 cm from the upper surface of the glass with a 50 W halogen lamp during the measurement of the photothermal conversion and heat insulation performance. Compared with the quartz glass without the heat insulation coating or with only the PVA coating, the glass with the heat insulation coating on the upper surface manufactured in Example 2 reduced the temperature inside the box by 15.5°C, and the reduction range was 22.1%. The Rb 0.28 The heat insulation principle of the WO3 coating is that the rubidium tungsten bronze in the coating absorbs near-infrared light and converts it into heat outside the box to achieve the heat insulation effect. Therefore, the Rb 0.28 WO3 coating manufactured by the method of Example 2 had high photothermal conversion performance and heat insulation performance.

[0131] When the glass with the Cs 0.3 WO3 coating on the upper surface manufactured in Example 2 was reversed so that the heat insulation coating on the upper surface of the glass was placed inside the box, the Rb 0.28 WO3 coating can be used to have high photothermal conversion performance and heat insulation performance and can store heat inside the box. By adjusting the relative position of the heat insulation coating manufactured in Example 2, effective heat management can be carried out.

[0132] Example 3 Potassium Tungsten Bronze K0.32 Production of WO3 As shown in Figure 1, the industrial production method of nanosized potassium tungsten bronze by hydrolysis of the low-temperature cation coordination tungsten salt of the present invention includes the following production steps.

[0133] Step 1: Preparation of potassium source solution; Dosage: The concentration of the potassium source in the potassium source solution was 2 mol / L.

[0134] Potassium chloride (KCl) and deionized water were added to the first stirring container; at normal pressure, the dissolution temperature was set to 25 °C and the stirring speed was set to 400 r / min. After stirring for 20 min, a potassium source solution was prepared.

[0135] Step 2: Preparation of tungsten source solution; Dosage: The concentration of the tungsten source in the tungsten source solution was 0.1 mol / L.

[0136] WCl6 and CH3CH2OH were added to the second stirring container; at normal pressure, the dissolution temperature was set to 40 °C and the stirring speed was set to 300 r / min. After stirring for 50 min, a tungsten source solution was prepared.

[0137] Step 3: Heating in a water bath to generate a nanosized potassium tungsten bronze dispersion by hydrolysis; Dosage: To produce 1 kg of potassium tungsten bronze powder, 0.85 kg of potassium source solution and 49.2 kg of tungsten source solution were required.

[0138] Preparation of the dispersion by low-temperature heating hydrolysis in the first step: The potassium source solution and the tungsten source solution were added to a water bath heating container; the water bath temperature was set to 70 °C and the stirring speed of the water bath heating container was set to 500 r / min. After stirring for 720 min, a dispersion was obtained.

[0139] Step 4: Solid-liquid separation; In Example 3, the cleaning solution was C3H6O.

[0140] In Step 41, the dispersion liquid was added to the solid-liquid separator, and after standing for 90 min, the first precipitate and the first supernatant were obtained; then the first supernatant was discharged; In Step 42, the cleaning liquid was added to the solid-liquid separator, and the cleaning liquid was 4 times that of the first precipitate; the stirring speed of the solid-liquid separator was set to 300 r / min, stirred for 50 min and then left standing for 60 min, and then the second precipitate and the second supernatant were obtained; then the second supernatant was discharged; In Step 43, the cleaning liquid was added to the solid-liquid separator, and the cleaning liquid was 4 times that of the second precipitate; the stirring speed of the solid-liquid separator was set to 300 r / min, stirred for 40 min and then left standing for 40 min, and then the third precipitate and the third supernatant were obtained; then the third supernatant was discharged; In Step 47, the cleaning liquid was added to the solid-liquid separator, and the solvent was 1.5 times that of the third precipitate; the stirring speed of the solid-liquid separator was set to 300 r / min; after stirring for 60 min, a potassium tungsten bronze dispersion liquid was obtained.

[0141] Characteristics and performance of potassium tungsten bronze produced by the method of Example 3 The potassium tungsten bronze dispersion liquid produced in Step Four was dried by a vacuum resistance furnace at a drying temperature of 60 °C and dried in vacuum for 480 min to obtain potassium tungsten bronze powder, that is, K 0.32 WO3 powder was obtained. According to the calculation of the charged raw materials and the production amount of the product, the industrial yield of K 0.32 WO3 powder was as high as 75%.

[0142] In the XRD pattern shown in Fig. 8, all the diffraction peaks of the potassium tungsten bronze powder produced by the method of Example 3 belong to K 0.32 WO3, indicating that pure-phase potassium tungsten bronze was synthesized.

[0143] In the SEM spectrum shown in Fig. 9, the morphology of the K 0.32 WO3 powder produced by the method of Example 3 was equiaxed, and the size distribution of the equiaxed structure was 15 - 100 nm.

[0144] When measured by the Uv-Vis-NIR spectrum, the K 0.32 WO3 powder produced by the method of Example 3 had excellent near-infrared shielding performance, high visible light transmittance and good ultraviolet shielding performance.

[0145] When measured by the FTIR spectrum, the K 0.32 WO3 powder produced by the method of Example 3 had certain mid- and far-infrared shielding performance.

[0146] In the Uv-Vis-NIR spectrum shown in Fig. 15, the composite film of the K 0.32 WO3 powder and PVA produced by the method of Example 3 had high near-infrared absorption performance, ultraviolet shielding performance and high visible light transmittance performance.

[0147] Step Five: Manufacture of potassium tungsten bronze paint; Dosage (parts by weight): Potassium tungsten bronze dispersion: PVA: Deionized water = 1:5:100 Add potassium tungsten bronze dispersion, PVA, and deionized water to the third stirring container; set the stirring speed of the third stirring container to 400 r / min; after stirring for 40 min, potassium tungsten bronze paint was obtained.

[0148] Step Six: Manufacture of glass curtain wall by spray coating process; Inject potassium tungsten bronze paint into the tank of the spray coater through a pipe, and set the spray coating distance H from the nozzle to the upper surface of the glass plate to be 1.5 cm; the flow rate of the potassium tungsten bronze paint was 3 ml / min.

[0149] The temperature of the hot air provided by the hot air blower was 40 °C, the speed of the conveyor roller was 60 r / min, and after curing, a potassium tungsten bronze coating on the upper surface of the glass was manufactured.

[0150] The potassium tungsten bronze coating on the upper surface of the glass shown in Fig. 16 was irradiated onto the glass at a distance of 20 cm from the upper surface of the glass with a 50 W halogen lamp in the measurement of photothermal conversion and heat insulation performance. Compared with the quartz glass without a heat insulation coating or with only a PVA coating, the glass with a heat insulation coating on the upper surface manufactured in Example 3 reduced the temperature inside the box by 7.5 °C, and the reduction range was 10.7%. The K 0.32 The heat insulation principle of the WO3 coating is that potassium tungsten bronze in the coating absorbs near-infrared light and converts it into heat outside the box to achieve the heat insulation effect. Therefore, the K 0.32 WO3 coating manufactured by the method of Example 3 had high photothermal conversion performance and heat insulation performance.

[0151] When the glass with a K 0.32 WO3 coating on the upper surface manufactured in Example 3 was reversed so that the heat insulation coating on the upper surface of the glass was placed inside the box, the K 0.32 WO3 coating can be utilized to have high photothermal conversion performance and heat insulation performance and store heat inside the box. By adjusting the relative position of the heat insulation coating manufactured in Example 3, effective heat management can be achieved.

[0152] Example 4 Preparation of sodium tungsten bronze Na 0.33 WO3 As shown in Fig. 1, the method for industrially manufacturing nanosodium tungsten bronze by hydrolysis of the low-temperature cation coordination tungsten salt of the present invention includes the following manufacturing steps.

[0153] Step 1, preparation of a sodium source solution; Dosage: The concentration of the sodium source in the sodium source solution was 2 mol / L.

[0154] Sodium chloride (NaCl) and deionized water were added to the first stirring container; at normal pressure, the dissolution temperature was set to 25 °C and the stirring speed was set to 400 r / min. After stirring for 10 min, a sodium source solution was prepared.

[0155] Step Two: Production of Tungsten Source Solution; Dosage: The tungsten source concentration of the tungsten source solution was 0.1 mol / L.

[0156] WCl6 and CH3CH2OH were added to a second stirring container; at normal pressure, the dissolution temperature was set to 40 °C and the stirring speed was set to 300 r / min. After stirring for 50 min, a tungsten source solution was produced.

[0157] Step Three: Heating in a water bath and generating a nano-sodium tungsten bronze dispersion by hydrolysis; Dosage: To produce 1 kg of sodium tungsten bronze powder, 2.32 kg of sodium source solution and 61.5 kg of tungsten source solution were required.

[0158] Production of the dispersion by low-temperature heating hydrolysis in the first step: The sodium source solution and the tungsten source solution were added to a water bath heating container; the water bath temperature was set to 70 °C and the stirring speed of the water bath heating container was set to 500 r / min. After stirring for 1440 min, a dispersion was obtained.

[0159] Step Four: Solid-liquid separation; In Example 4, the cleaning solution was CH3OH.

[0160] Step 41: The dispersion was added to a solid-liquid separator. After standing for 20 min, a first precipitate and a first supernatant were obtained; and the first supernatant was discharged; Step 42: The cleaning solution was added to the solid-liquid separator, and the cleaning solution was 4.5 times that of the first precipitate; the stirring speed of the solid-liquid separator was set to 200 r / min. After stirring for 20 min and then standing for 20 min, a second precipitate and a second supernatant were obtained; and the second supernatant was discharged; Step 43: Add cleaning liquid to the solid-liquid separator, where the cleaning liquid is 4.5 times that of the second precipitate; set the stirring speed of the solid-liquid separator to 200 r / min, stir for 50 min and then let it stand for 70 min to obtain the third precipitate and the third supernatant; and then discharge the third supernatant. Step 47: Add cleaning liquid to the solid-liquid separator, where the solvent is 5 times that of the third precipitate; set the stirring speed of the solid-liquid separator to 200 r / min; after stirring for 20 min, a sodium tungsten bronze dispersion was obtained.

[0161] Characteristics and performance of sodium tungsten bronze manufactured by the method of Example 4 The sodium tungsten bronze dispersion produced in Step Four was dried in a vacuum resistance furnace at a drying temperature of 60 °C and under vacuum for 480 min to obtain sodium tungsten bronze powder, i.e., Na 0.33 WO3 powder. According to the calculation of the charged raw materials and the production volume of the product, the industrial yield of Na 0.33 WO3 powder was as high as 60%.

[0162] In the XRD pattern shown in Figure 8, all the diffraction peaks of the sodium tungsten bronze powder manufactured by the method of Example 4 belong to Na 0.33 WO3, indicating that pure-phase sodium tungsten bronze was synthesized.

[0163] In the SEM spectrum shown in Figure 9, the morphology of the Na 0.33 WO3 powder manufactured by the method of Example 4 is short rod-shaped, the length of the short rod-shaped structure is 20 - 150 nm, and the diameter is 20 - 50 nm.

[0164] As measured by the Uv-Vis-NIR spectrum, the Na 0.33 WO3 powder manufactured by the method of Example 4 has excellent near-infrared shielding performance, high visible light transmittance and good ultraviolet shielding performance.

[0165] As measured by the FTIR spectrum, the Na 0.33The WO3 powder had far-infrared shielding performance under certain conditions.

[0166] In the Uv-Vis-NIR spectrum shown in Fig. 15, the composite film of the Na 0.33 WO3 powder and PVA prepared by the method of Example 4 had high near-infrared absorption performance, ultraviolet shielding performance, and high visible light transmittance performance.

[0167] Step Five: Manufacture of sodium tungsten bronze paint; Dosage (parts by weight): Sodium tungsten bronze dispersion: PVA: Deionized water = 1.5: 7: 120 Add the sodium tungsten bronze dispersion, PVA, and deionized water to the third stirring container; set the stirring speed of the third stirring container to 300 r / min; after stirring for 100 min, obtain the sodium tungsten bronze paint.

[0168] Step Six: Manufacture of a glass curtain wall by a spray coating process; Inject the sodium tungsten bronze paint into the tank of the spray coater through a pipe, and set the spray coating distance H from the nozzle to the upper surface of the glass plate to 1 cm; the flow rate of the sodium tungsten bronze paint was 2 ml / min.

[0169] After curing at a hot air temperature of 40°C provided by a hot air blower and a conveyor roller speed of 50 r / min, a heat insulation coating on the upper surface of the glass was manufactured.

[0170] To achieve spray coating of a large-sized glass curtain wall, in the present invention, a structure of an array nozzle arrangement as shown in Fig. 7 was adopted. Ultrasonic atomizing nozzles 5C were arranged in an array on the plate 5A of the nozzle mechanism 5. The ultrasonic atomizing nozzles 5C communicated with the tank of the spray coater through a soft tube. A post 5B was installed at the center of the plate 5A, and the post 5B was fixed to the housing of the spray coater.

[0171] In the present invention, the nozzle diameter of the ultrasonic atomizing nozzle 5C was 20 mm, and the jet outlet diameter was 1.5 mm. The number of ultrasonic atomizing nozzles 5C installed on the plate 5A was determined according to the size of the glass curtain wall to be manufactured, the nozzle diameter, and the jet outlet diameter.

[0172] For the sodium tungsten bronze coating on the upper surface of the glass shown in FIG. 16, in the measurement of photothermal conversion and heat insulation performance, the glass was irradiated with a 50 W halogen lamp at a distance of 20 cm from the upper surface of the glass. Compared with the quartz glass without the heat insulation coating or with only the PVA coating, the glass with the heat insulation coating on the upper surface manufactured in Example 4 reduced the temperature inside the box by 10 °C, and the reduction width was 14.3%. The Na 0.33 The heat insulation principle of the WO3 coating is that the sodium tungsten bronze in the coating absorbs near-infrared light and converts it into heat outside the box to achieve the heat insulation effect. Therefore, the Na 0.33 WO3 coating manufactured by the method of Example 4 had high photothermal conversion performance and heat insulation performance.

[0173] When the glass with the Na 0.33 WO3 coating on the upper surface manufactured in Example 4 was reversed so that the heat insulation coating on the upper surface of the glass was placed inside the box, the Na 0.33 WO3 coating can be used to have high photothermal conversion performance and heat insulation performance and store heat inside the box. By adjusting the relative position of the heat insulation coating manufactured in Example 4, effective heat management can be performed.

[0174] Example 5 Production of cesium tungsten bronze Cs 0.23 Production of WO3 As shown in FIG. 2, the method for manufacturing a nanocesium tungsten bronze coating by applying the industrial production by hydrolysis of the low-temperature cation coordination tungsten salt of the present invention and the spray coating process includes the following production steps.

[0175] Step 1: Preparation of cesium source solution; Dosage: The concentration of the cesium source in the cesium source solution was 0.2 mol / L.

[0176] CsOH and deionized water were added to the first stirring container; at normal pressure, the dissolution temperature was set to 40 °C and the stirring speed was set to 400 r / min. After stirring for 20 min, the cesium source solution was prepared.

[0177] Step 2: Preparation of tungsten source solution; Dosage: The concentration of the tungsten source in the tungsten source solution was 0.15 mol / L.

[0178] WCl6 and CH3(CH2)2OH were added to the second stirring container; at normal pressure, the dissolution temperature was set to 30 °C and the stirring speed was set to 500 r / min. After stirring for 20 min, the tungsten source solution was prepared.

[0179] Step 3: Generation of nano cesium tungsten bronze dispersion by heating in a water bath and hydrolysis; Dosage: To produce 1 kg of cesium tungsten bronze powder, 6.5 kg of cesium source solution and 36.32 kg of tungsten source solution were required.

[0180] Preparation of dispersion by low-temperature heating and hydrolysis in Step 1: The cesium source solution and the tungsten source solution were added to a water bath heating container; the water bath temperature was set to 80 °C and the stirring speed of the water bath heating container was set to 500 r / min. After stirring for 360 min, a dispersion was obtained.

[0181] Step 4: Solid-liquid separation; In Example 5, the cleaning solution was CH3CH2OH.

[0182] Step 41: The dispersion was added to a solid-liquid separator and allowed to stand for 100 min, then the first precipitate and the first supernatant were obtained; and the first supernatant was discharged; Step 42: Add cleaning liquid to the solid-liquid separator, where the amount of the cleaning liquid is 3.5 times that of the first precipitate; set the stirring speed of the solid-liquid separator to 400 r / min, stir for 30 min, then let it stand for 40 min to obtain the second precipitate and the second supernatant; and then discharge the second supernatant. Step 43: Add cleaning liquid to the solid-liquid separator, where the amount of the cleaning liquid is 3.5 times that of the second precipitate; set the stirring speed of the solid-liquid separator to 400 r / min, stir for 80 min, then let it stand for 70 min to obtain the third precipitate and the third supernatant; and then discharge the third supernatant. Step 47: Add deionized water to the solid-liquid separator, where the amount of the solvent is 4 times that of the third precipitate; set the stirring speed of the solid-liquid separator to 500 r / min; after stirring for 50 min, a cesium tungsten bronze dispersion was obtained.

[0183] Step Five: Manufacture of cesium tungsten bronze paint. Dosage (parts by weight): Cesium tungsten bronze dispersion: PVA: Deionized water = 1:5:100 Add cesium tungsten bronze dispersion, PVA, and deionized water to the third stirring container; set the stirring speed of the third stirring container to 400 r / min; after stirring for 90 min, cesium tungsten bronze paint was obtained.

[0184] Step Six: Manufacture of glass curtain wall by spray coating process. Inject cesium tungsten bronze paint into the tank of the spray coater through a pipe, and set the spray coating distance H from the nozzle to the upper surface of the glass plate to 1 cm; the flow rate of the cesium tungsten bronze paint was 7 ml / min.

[0185] The temperature of the hot air provided by the hot air blower was 35°C, the speed of the conveying roller was 20 r / min, and after curing, a heat insulation coating on the upper surface of the glass was manufactured.

[0186] In order to achieve a large-sized spray coating for a glass curtain wall, the present invention adopts a structure of an array nozzle arrangement as shown in FIG. 7. Ultrasonic atomizing nozzles 5C are arranged in an array on a plate 5A of a nozzle mechanism 5. The ultrasonic atomizing nozzles 5C communicate with a tank of a spray coater via a soft tube. A post 5B is installed at the center of the plate 5A, and the post 5B is fixed to a housing of the spray coater.

[0187] In the present invention, the nozzle diameter of the ultrasonic atomizing nozzle 5C was 10 mm, and the jet outlet diameter was 1 mm. The number of ultrasonic atomizing nozzles 5C installed on the plate 5A was determined according to the size of the glass curtain wall to be manufactured, the nozzle diameter, and the jet outlet diameter.

[0188] Characteristics and Performance of Cesium Tungsten Bronze Produced by the Method of Example 5 When analyzed by an XRD pattern, all the diffraction peaks of the cesium tungsten bronze powder produced by the method of Example 5 belonged to Cs 0.23 WO3, indicating that a pure-phase cesium tungsten bronze was synthesized.

[0189] When analyzed by an SEM spectrum, the Cs 0.23 WO3 powder produced by the method of Example 5 had a short rod shape. The length of the short rod structure was 30 - 140 nm, and the diameter was 15 - 40 nm.

[0190] When analyzed by a Uv-Vis-NIR spectrum, the Cs 0.23 WO3 powder produced by the method of Example 5 had high near-infrared absorption performance, ultraviolet shielding performance, and high visible light transmittance performance.

[0191] When measured by the photothermal conversion and heat insulation performance of the heat insulation coating on the upper surface of the glass, the heat insulation coating produced in Example 5 had high photothermal conversion performance and heat insulation performance.

[0192] Example 6 Sodium Tungsten Bronze Na0.30 Production of WO3 The present invention synthesizes a sodium tungsten bronze alkoxide precursor by employing a combined use of a hydrolysis method and a coprecipitation method, and synthesizes sodium tungsten bronze at a low temperature in the original liquid phase, and includes the following manufacturing steps.

[0193] As shown in Figure 2, a method for manufacturing a nanosodium tungsten bronze coating by a spray coating process by applying industrially manufactured nanosodium tungsten bronze by hydrolysis of a low-temperature cation coordination tungsten salt of the present invention includes the following manufacturing steps.

[0194] Step 1, production of a sodium source solution; Dosage: The concentration of the sodium source in the sodium source solution was 2 mol / L.

[0195] NaCl and deionized water were added to a first stirring container; at normal pressure, the dissolution temperature was set to 40 °C and the stirring speed was set to 300 r / min. After stirring for 15 minutes, a sodium source solution was produced.

[0196] Step 2, production of a tungsten source solution; Dosage: The concentration of the tungsten source in the tungsten source solution was 0.075 mol / L.

[0197] WCl6 and CH3CH2OH were added to a second stirring container; at normal pressure, the dissolution temperature was set to 35 °C and the stirring speed was set to 400 r / min. After stirring for 25 minutes, a tungsten source solution was produced.

[0198] Step 3, heating in a water bath to generate a nanosodium tungsten bronze dispersion by hydrolysis; Dosage: For the production of 1 kg of cesium tungsten bronze powder, 2.2 kg of sodium source solution and 55.42 kg of tungsten source solution were required.

[0199] Manufacture of dispersion by low-temperature heating and hydrolysis in one process: Add the sodium source solution and the tungsten source solution to a water bath heating container; set the water bath temperature to 74 °C and the stirring speed of the water bath heating container to 400 r / min. After stirring for 1500 min, a dispersion was obtained.

[0200] Step Four, solid-liquid separation; In Example 6, the cleaning solution was CH3CH2OH.

[0201] Step 41, add the dispersion to a solid-liquid separator, let it stand for 30 min, then obtain the first precipitate and the first supernatant; and discharge the first supernatant; Step 42, add the cleaning solution to the solid-liquid separator, where the cleaning solution is twice that of the first precipitate; set the stirring speed of the solid-liquid separator to 500 r / min, stir for 40 min and then let it stand for 40 min, then obtain the second precipitate and the second supernatant; and discharge the second supernatant; Step 43, add the cleaning solution to the solid-liquid separator, where the cleaning solution is twice that of the second precipitate; set the stirring speed of the solid-liquid separator to 400 r / min, stir for 50 min and then let it stand for 50 min, then obtain the third precipitate and the third supernatant; and discharge the third supernatant; Step 47, add deionized water to the solid-liquid separator, where the solvent is three times that of the third precipitate; set the stirring speed of the solid-liquid separator to 300 / min; after stirring for 60 min, a sodium tungsten bronze dispersion was obtained.

[0202] Manufacture of sodium tungsten bronze powder by drying The sodium tungsten bronze dispersion produced in Step Four was dried in a vacuum resistance furnace at a drying temperature of 70 °C and under vacuum for 300 min to obtain sodium tungsten bronze powder, i.e., Na 0.30 WO3 powder was obtained. According to the calculation of the charged raw materials and the production volume of the product, the industrial yield of Na 0.30 WO3 powder was 65%.

[0203] Step Five, manufacture of sodium tungsten bronze paint; Dosage (parts by weight): Sodium tungsten bronze dispersion: PVA: Deionized water = 1.5: 7: 120 The sodium tungsten bronze dispersion, PVA, and deionized water were added to the third stirring container; the stirring speed of the third stirring container was set to 300 r / min; after stirring for 100 min, a sodium tungsten bronze paint was obtained.

[0204] Step Six: Manufacture of a glass curtain wall by a spray coating process; The sodium tungsten bronze paint was injected into the tank of the spray coater through a pipe, and the spray coating distance H from the nozzle to the upper surface of the glass plate was set to 1.5 cm; the flow rate of the sodium tungsten bronze paint was 1 ml / min.

[0205] After curing at a hot air temperature of 40 °C provided by a hot air blower and a conveyor roller speed of 50 r / min, a heat insulation coating on the upper surface of the glass was manufactured.

[0206] In order to realize spray coating of a large-sized glass curtain wall, in the present invention, a structure of an array nozzle arrangement as shown in FIG. 7 was adopted. Ultrasonic atomizing nozzles 5C were arranged in an array on a plate 5A of a nozzle mechanism 5. The ultrasonic atomizing nozzles 5C communicated with the tank of the spray coater through a soft tube. A post 5B was installed at the center of the plate 5A, and the post 5B was fixed to the housing of the spray coater.

[0207] In the present invention, the nozzle diameter of the ultrasonic atomizing nozzle 5C was 20 mm, and the jet outlet diameter was 1.5 mm. The number of ultrasonic atomizing nozzles 5C installed on the plate 5A was determined according to the size of the glass curtain wall to be manufactured, the nozzle diameter, and the jet outlet diameter.

[0208] Characteristics and performance of sodium tungsten bronze manufactured by the method of Example 6 As analyzed by an XRD pattern, all diffraction peaks of the sodium tungsten bronze powder manufactured by the method of Example 6 were Na0.30 It was shown that a pure-phase sodium tungsten bronze belonging to WO3 was synthesized.

[0209] When analyzed by SEM spectrum, the Na produced by the method of Example 6 0.30 The form of the WO3 powder was short rod-shaped, the length of the short rod-shaped structure was 30 to 140 nm, and the diameter was 15 to 40 nm.

[0210] When analyzed by Uv-Vis-NIR spectrum, the Na produced by the method of Example 6 0.30 The WO3 powder had high near-infrared absorption performance, ultraviolet shielding performance and high visible light transmittance performance.

[0211] When measured by the photothermal conversion and heat insulation performance of the upper surface of the glass, the heat insulation coating produced in Example 6 had high photothermal conversion performance and heat insulation performance.

[0212] The above description is only the preferred embodiment of the present invention. Those skilled in the art can make some modifications and refinements without departing from the principle of the present invention, and these modifications and refinements should be considered to be within the protection scope of the present invention.

Claims

1. An industrial production method of nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation coordination tungsten salt, comprising the following steps: Step 1, preparation of an alkali metal source solution; Step 11, adding deionized water to the first stirring container; Inside the first stirring container (1), a stirrer is installed. Above the cylinder (1A) of the first stirring container (1), an alkali metal source supply port (1A1), a deionized water supply port (1A2), and an exhaust port (1A3) are installed; below the cylinder (1A), an alkali metal source solution discharge port (1A4) is installed; Step 12, adding an alkali metal source to the first stirring container; The alkali metal source contains one or a combination of two of the hydroxides, chloride salts, nitrates, sulfates, and carbonates corresponding to alkali metal ions; The hydroxide is cesium hydroxide, potassium hydroxide, or sodium hydroxide; The chloride salt is cesium chloride, rubidium chloride, potassium chloride, or sodium chloride; The nitrate is cesium nitrate, potassium nitrate, or sodium nitrate; The sulfate is cesium sulfate, potassium sulfate, or sodium sulfate; The carbonate is cesium carbonate, potassium carbonate, or sodium carbonate; Step 13, set at normal pressure so that the dissolution temperature is 10°C to 40°C and the stirring speed is 200 r / min to 600 r / min; after stirring for 1 min to 15 min, an alkali metal source solution is prepared; The alkali metal ion concentration of the prepared alkali metal source solution is 0.02 mol / L to 10 mol / L; Step 2, preparation of a tungsten source solution; Step 21, adding a tungsten source to the second stirring container; The tungsten source is tungsten hexachloride or tungsten tetrachloride; Inside the second stirring container (2), a stirrer (2E) is installed; above the cylinder (2A) of the second stirring container (2), a tungsten source supply port (2A1), an alcohol source supply port (2A2), and an exhaust port (2A3) are installed; below the cylinder (2A), a tungsten source mixed solution discharge port (2A4) is installed; between the outer wall of the inner housing (2C) of the second stirring container (2) and the inner wall of the cylinder (2A), a resistance wire (2D) is installed; Step 22, adding an alcohol solution to the second stirring container; The alcohol solution is one, two, or a combination of more than two of methanol, ethanol, n-propanol, isopropanol, and n-butanol; In step 23, set the dissolution temperature to 10°C to 40°C and the stirring speed to 200 r / min to 600 r / min at normal pressure; after stirring for 10 min to 60 min, produce a tungsten source solution; The tungsten source concentration of the produced tungsten source solution is 0.02 mol / L to 1 mol / L; Step three, heating in a water bath and generating a nano-alkali metal tungsten bronze dispersion by hydrolysis; Dosage: To produce 1 kg of nano-alkali metal tungsten bronze powder, 0.18 kg to 90 kg of an alkali metal source solution and 3.68 kg to 184 kg of a tungsten source solution are required; Manufacture of an alkali metal tungsten bronze dispersion by low-temperature heating hydrolysis in one step: Add an alkali metal source solution, a tungsten source solution, and deionized water to a water bath heating container (3); set the water bath temperature to 40 to 95°C and the stirring speed to 200 r / min to 1000 r / min, and after stirring for 90 min to 2880 min, obtain an alkali metal tungsten bronze dispersion; The water bath heating container (3) is divided into a heating cylinder (3C) and a water bath cylinder (3A), and a heating coil (3D) is installed between the heating cylinder (3C) and the water bath cylinder (3A). There is tap water in the water bath cylinder (3A); a stirrer (3E) is installed inside the heating cylinder (3C); above the water bath heating container (3), a CA supply port (3A1), a CB supply port (3A2), a CC supply port (3A3), and an exhaust port (3A4) are installed; Step four, solid-liquid separation; The cleaning solution is methanol, ethanol, acetone; or a combination of methanol and deionized water; a combination of ethanol and deionized water; a combination of acetone and deionized water; In step 41, add the alkali metal tungsten bronze dispersion to a solid-liquid separator (4), let it stand for 20 to 100 min, and then obtain a first precipitate and a first supernatant; discharge the first supernatant; In step 42, add a cleaning solution to the solid-liquid separator (4), where the cleaning solution is 2 to 5 times that of the first precipitate; set the stirring speed of the solid-liquid separator to 200 r / min to 600 r / min, stir for 10 min to 60 min, and then let it stand for 20 to 100 min to obtain a second precipitate and a second supernatant; discharge the second supernatant; Step 43: Add cleaning liquid to the solid-liquid separator (4), where the amount of the cleaning liquid is 2 to 5 times that of the precipitate from the second time; set the stirring speed of the solid-liquid separator to be 200 r / min to 600 r / min, stir for 10 min to 60 min, and then let it stand for 20 to 100 min to obtain the third precipitate and the supernatant of the third time; discharge the supernatant of the third time; Step 47: Add cleaning liquid to the solid-liquid separator (4), where the amount of the solvent is 2 to 5 times that of the precipitate from the third time; set the stirring speed of the solid-liquid separator to be 200 r / min to 600 r / min; after stirring for 10 min to 60 min, obtain a nano-alkali metal tungsten bronze dispersion; Inside the solid-liquid separator (4), a stirrer (4E) is installed; above the cylinder (4A) of the solid-liquid separator (4), a DA supply port (4A1), a DB supply port (4A2), and a DA discharge port (4A3) are installed; below the cylinder (4A), a DB discharge port (4A4) is installed; Step Five: Manufacture of nano-alkali metal tungsten bronze powder by drying; The alkali metal tungsten bronze solution produced in Step 4 is dried in a vacuum resistance furnace, and the vacuum degree is set to 1×10 －２ Pa to 1×10 －４ Pa, the drying temperature is 50°C to 100°C, and the drying time is 180 min to 720 min to obtain alkali metal tungsten bronze powder. An industrial manufacturing method of nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt.

2. Synthesize nano-alkali metal tungsten bronze by applying low-temperature hydrothermal decomposition of a process, and its components are Cs ｘ WO ３ , Rb ｘ WO ３ , K ｘ WO ３ , Na ｘ WO ３ , where X = 0.2 - 0.33 An industrial manufacturing method of nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt according to Claim 1, characterized in that...

3. As components of the produced preferable nano-alkali metal tungsten bronze powder, Cs ０．３０ WO ３ powder, Rb ０．２８ WO ３ powder, K ０．３２ WO ３ powder or Na ０．３３ WO ３ powder exists. An industrial manufacturing method of nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt according to Claim 1, characterized in that...

4. The morphology of the manufactured nano-alkali metal tungsten bronze powder is short rod-shaped or equiaxial, the length of the short rod-shaped structure is 10 to 150 nm, the diameter is 10 to 50 nm, and the size in each direction of the equiaxial structure is less than 100 nm. An industrial manufacturing method of nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt according to Claim 1, characterized in that...

5. The industrial yield of the manufactured nano-cesium tungsten bronze powder is 70% to 85%, the industrial yield of the nano-rubidium tungsten bronze powder is 70% to 85%, the industrial yield of the nano-potassium tungsten bronze powder is 60% to 80%, and the industrial yield of the nano-sodium tungsten bronze powder is 50% to 75%. An industrial manufacturing method of nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt according to Claim 1, characterized in that...

6. An industrial manufacturing method of a nano-alkali metal tungsten bronze coating using a nano-alkali metal tungsten bronze solution according to claim 1, comprising the following steps: Step 1: Preparation of an alkali metal source solution; Step 11: Add deionized water to the first stirring container; Step 12: Add an alkali metal source to the first stirring container; The alkali metal source includes one or a combination of two of the hydroxides, chloride salts, and nitrates, sulfates, and carbonates corresponding to alkali metal ions; The hydroxide is cesium hydroxide, potassium hydroxide, or sodium hydroxide; The chloride salt is cesium chloride, rubidium chloride, potassium chloride, or sodium chloride; The nitrate is cesium nitrate, potassium nitrate, or sodium nitrate; The sulfate is cesium sulfate, potassium sulfate, or sodium sulfate; The carbonate is cesium carbonate, potassium carbonate, or sodium carbonate; Step 13: Set the dissolution temperature to 10°C to 40°C and the stirring speed to 200 r / min to 600 r / min at normal pressure; after stirring for 1 min to 15 min, prepare an alkali metal source solution; The alkali metal ion concentration of the prepared alkali metal source solution is 0.05 mol / L to 5 mol / L; Step 2: Preparation of a tungsten source solution; Step 21: Add a tungsten source to the second stirring container; The tungsten source is tungsten hexachloride or tungsten tetrachloride; Step 22: Add an alcohol solution to the second stirring container; The alcohol solution is one, two, or a combination of multiple of methanol, ethanol, n-propanol, isopropanol, and n-butanol; Step 23: Set the dissolution temperature to 15°C to 40°C and the stirring speed to 200 r / min to 600 r / min at normal pressure; after stirring for 10 min to 60 min, prepare a tungsten source solution; The tungsten source concentration of the prepared tungsten source solution is 0.05 mol / L to 1 mol / L; Step 3: Generate a nano-alkali metal tungsten bronze dispersion by heating in a water bath and hydrolysis; Dosage: To produce 1 kg of nano-alkali metal tungsten bronze powder, 0.23 kg to 36 kg of an alkali metal source solution and 3.68 kg to 123 kg of a tungsten source solution are required; Manufacture of an alkali metal tungsten bronze dispersion by low-temperature heating and hydrolysis of a process: Add an alkali metal source solution, a tungsten source solution, and deionized water to a water bath heating container; set the water bath temperature to 40°C to 90°C, stir at a stirring speed of 200 r / min to 1000 r / min for 90 min to 2880 min, and then obtain a dispersion; Step Four, solid-liquid separation; The cleaning solution is methanol, ethanol, acetone; or a combination of methanol and deionized water; a combination of ethanol and deionized water; a combination of acetone and deionized water; Step 41, add the alkali metal tungsten bronze dispersion to a solid-liquid separator, let it stand for 20 to 100 min, and then obtain the first precipitate and the first supernatant; discharge the first supernatant; Step 42, add a cleaning solution to the solid-liquid separator, where the cleaning solution is 2 to 5 times that of the first precipitate; set the stirring speed of the solid-liquid separator to 200 r / min to 600 r / min, stir for 10 min to 60 min, and then let it stand for 20 to 100 min to obtain the second precipitate and the second supernatant; discharge the second supernatant; Step 43, add a cleaning solution to the solid-liquid separator, where the cleaning solution is 2 to 5 times that of the second precipitate; set the stirring speed of the solid-liquid separator to 200 r / min to 600 r / min, stir for 10 min to 60 min, and then let it stand for 20 to 100 min to obtain the third precipitate and the third supernatant; discharge the third supernatant; Step 47, add a cleaning solution to the solid-liquid separator, where the solvent is 0.5 to 2 times that of the third precipitate; set the stirring speed of the solid-liquid separator to 200 r / min to 600 r / min; after stirring for 10 min to 60 min, obtain an alkali metal tungsten bronze dispersion; Step Five, manufacture of an alkali metal tungsten bronze paint; Dosage: alkali metal tungsten bronze dispersion: PVA: deionized water = 1: 2 to 15: 80 to 130; Add the alkali metal tungsten bronze dispersion, PVA, and deionized water to a third stirring container; set the stirring speed of the third stirring container to 100 r / min to 400 r / min; after stirring for 30 min to 120 min, obtain an alkali metal tungsten bronze paint; Step Six, manufacture of a glass curtain wall by a spray coating process; Inject the alkali metal tungsten bronze paint into the tank of the spray coater through a pipe, and set the spray coating distance H from the nozzle to the upper surface of the glass plate to be 0.5 - 2 cm; the flow rate of the alkali metal tungsten bronze paint is 1 - 7 ml / min; The temperature of the hot air provided by the hot air blower is 22°C - 40°C, the speed of the conveyor roller is 10 r / min - 60 r / min, and after curing, a nano alkali metal tungsten bronze coating on the upper surface of the glass is manufactured. An industrial manufacturing method of a nano alkali metal tungsten bronze coating with a nano alkali metal tungsten bronze solution, characterized by the above.

7. Apply the manufactured nano alkali metal tungsten bronze coating to the glass curtain wall. An industrial manufacturing method of a nano alkali metal tungsten bronze coating with a nano alkali metal tungsten bronze solution according to Claim 6, characterized by the above.

8. The glass supported by nano alkali metal tungsten bronze reduces the temperature in the box by 10°C - 15.5°C, and the drop width is 10% - 25%. An industrial manufacturing method of a nano alkali metal tungsten bronze coating with a nano alkali metal tungsten bronze solution according to Claim 6, characterized by the above.

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