CN116511006B - Surface hydrophilic TiO of tubular desalination device 2 Coating preparation process - Google Patents

Surface hydrophilic TiO of tubular desalination device 2 Coating preparation process Download PDF

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CN116511006B
CN116511006B CN202310554756.XA CN202310554756A CN116511006B CN 116511006 B CN116511006 B CN 116511006B CN 202310554756 A CN202310554756 A CN 202310554756A CN 116511006 B CN116511006 B CN 116511006B
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tubular
solution
coating
stirring
reaction kettle
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CN116511006A (en
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陈志莉
唐瑾
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Guilin University of Technology
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Guilin University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/04Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a surface receptive to ink or other liquid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141Plasma treatment
    • B05D3/142Pretreatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/70Additives characterised by shape, e.g. fibres, flakes or microspheres
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124Water desalination

Abstract

The invention relates to the technical field of tubular desalters, and discloses a surface hydrophilic TiO (titanium dioxide) of a tubular desalter 2 The coating preparation process comprises the following steps: (1) Dimethyl dimethoxy silane is used as a raw material to prepare dimethyl silicone oil solution; (2) obtaining an intermediate body fluid; (3) preparing a base solution; (4) obtaining complex microspheres; (5) 1-6g of complex microspheres are divided into ab parts; (6) obtaining calcined microspheres; (7) obtaining spray sol; (8) Carrying out plasma treatment on the surface of the pipe wall of the tubular desalination device; (9) The obtained spray-coated sol is uniformly coated on the wall surface of the tubular desalter, and is subjected to preliminary drying, high-temperature treatment and densification to form a coating; according to the invention, the surface of the tubular desalination device is covered with a layer of coating, so that the surface of the tubular desalination device can be effectively protected, and meanwhile, the surface of the coating has excellent hydrophilic performance.

Description

Surface hydrophilic TiO of tubular desalination device 2 Coating preparation process
Technical Field
The invention relates to the technical field of tubular desalters, in particular to a surface hydrophilic TiO (titanium dioxide) of a tubular desalter 2 A coating preparation process.
Background
The problem of shortage of fresh water resources is gradually revealed at present due to industrial pollution and the like, and the concept of saving water is very popular. However, even with water savings, fresh water resources still face a risk of depletion due to the limited availability of fresh water resources and the continued expansion of industrial production.
With the continuous development of society, population, resources and environment are three major problems facing the development of human society, wherein shortage of life source water resources is a global problem. In order to effectively alleviate the phenomenon, the sea water desalination technology at home and abroad is continuously applied in recent years.
The sea water desalination is to produce fresh water by utilizing sea water desalination, and at present, a plurality of sea water desalination technologies are mainly used in China, namely a reverse osmosis method and a distillation method, wherein the reverse osmosis method is also called an ultrafiltration method, and the method separates the sea water from the fresh water by utilizing a semipermeable membrane which only allows a solvent to permeate and does not allow a solute to permeate, but the reverse osmosis method has the defects of high cost and use cost, large one-time investment, large conventional consumption and the like. Distillation is a method in which seawater is heated to boil and vaporize the seawater, and then steam is condensed into fresh water. The distillation method is a desalination technology which is applied to the earliest artificial industrialization, and is characterized in that the distillation method is applicable to the seawater environment with serious pollution and high biological activity, the purity of produced water is high, and compared with the osmosis method, the distillation method has the advantages of low-grade heat utilization of power plants and other factories, low requirement on the quality of raw material seawater, and high production capacity of devices, and is one of the main stream technologies of the current seawater desalination.
Compared with a disc type desalination device, the tubular distillation sea water desalination system has the advantages of compact structure, convenience in transportation, low comprehensive cost and the like, so that the tubular distillation sea water desalination system is widely popularized and applied. However, the water yield of the existing tubular distillation seawater desalination system needs to be improved, and the continuous development of the tubular distillation seawater desalination system is restricted by low water yield.
Based on the above, we propose a surface hydrophilic TiO of a tubular desalination device 2 The preparation process of the coating is hoped to solve the defects in the prior art.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a surface hydrophilic TiO of a tubular desalination device 2 A coating preparation process.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions:
surface hydrophilic TiO of tubular desalination device 2 The coating preparation process comprises the following steps:
(1) Dimethyl dimethoxy silane is used as a raw material to prepare dimethyl silicone oil solution;
(2) Adding 2-3% nitric acid solution into the multi-layer silica sol, and then respectively adding absolute ethyl alcohol and dimethyl silicone oil solution under the condition of stirring to obtain intermediate body fluid;
wherein the volume ratio of the multi-layer silica sol to the absolute ethyl alcohol to the dimethyl silicone oil to the nitric acid solution is 2:2.5:1-3:0.5;
(3) And (3) preparing a base solution: adding cetyl trimethyl ammonium bromide into water, stirring uniformly to prepare cetyl trimethyl ammonium bromide solution, adding ammonia water and kerosene into the cetyl trimethyl ammonium bromide solution, and stirring at 500r/min for 1-1.5 hours to obtain base solution;
wherein the hexadecyl ammonium bromide solution is a saturated solution;
the mass fraction of the ammonia water is 20-24%;
wherein the volume ratio of ammonia water to cetyl trimethyl ammonium bromide solution to kerosene is 8:5:1.2;
(4) Slowly dripping intermediate body fluid into the base fluid, standing for 4-5 hours after dripping, filtering, adding absolute ethyl alcohol for soaking for 20-22 hours, filtering, and drying to obtain complex microspheres;
wherein the mixing volume ratio of the intermediate body fluid to the base fluid is 1:1.4-1.6;
(5) 1-6g of complex microspheres are divided into ab parts, wherein the mass ratio of a parts is 30%, and the mass ratio of b parts is 70%; the diameter of the complex microsphere is 0.2 mu m;
(6) Placing the obtained a parts of complex microspheres in a resistance furnace, and calcining to obtain calcined microspheres;
(7) Firstly, adding 90-110mL of absolute ethyl alcohol into a reaction kettle at room temperature, slowly adding 50-60mL of n-butyl titanate into the absolute ethyl alcohol, stirring for 10min, slowly dropwise adding 25-30mL of glacial acetic acid, continuously stirring, sequentially adding 3-5g of methyl methacrylate, b parts of complex microspheres and calcined microspheres into the absolute ethyl alcohol, and performing ultrasonic dispersion to obtain a mixed dispersion;
gradually dripping the mixed dispersion liquid into a reaction kettle, and then magnetically stirring to obtain spray-coating sol;
(8) Carrying out plasma treatment on the surface of the pipe wall of the tubular desalination device;
(9) And (3) primarily drying the surface of the pipe wall of the uniform pipe type desalter for spraying the sol, and then carrying out high-temperature treatment, densification and coating formation.
As a further technical scheme, the preparation method of the simethicone solution in the step (1) comprises the following steps:
and respectively adding dimethyl dimethoxy silane and ethanol solution into a reaction kettle, regulating the temperature to 40 ℃, preserving heat and stirring for 30min, regulating the pH value to 9.1 by adopting ammonia water, and continuing to preserving heat and stirring for 15 hours to obtain dimethyl silicone oil solution.
As a further technical scheme, the mass ratio of water to ethanol substances in the ethanol solution is 1:5;
the mass ratio of the materials mixed by the dimethyl dimethoxy silane and the ethanol solution is 1:2;
the concentration of the ammonia water is 1.2-1.5mol/L.
As a further technical scheme: the preparation method of the multilayer silica sol in the step (2) comprises the following steps:
firstly, adding 250ml of deionized water into a reaction kettle, then adding 15 mu L of saturated ammonia water and 0.21g of sodium hydroxide into the reaction kettle, regulating the temperature in the reaction kettle to 50-54 ℃, keeping the temperature and stirring for 5min, then adding 21.3g of silicon powder, continuously stirring for 3min, then dropwise adding sodium hydroxide solution, stirring at the speed of 120r/min for reaction for 4 hours, then standing for 1 hour, and filtering and removing impurities to obtain primary silica sol;
200mL of deionized water and 50mL of primary silica sol are sequentially added into a reaction kettle, the temperature of the reaction kettle is regulated to 60-64 ℃, then 15.8g of silica powder is added into the reaction kettle, the mixture is stirred for 3min, then sodium hydroxide solution is added dropwise, stirring reaction is carried out for 5 hours at the rotating speed of 150r/min, then the mixture is kept stand for 1 hour, and the multi-layer silica sol is obtained through filtration and impurity removal.
As a further technical scheme, the concentration of the sodium hydroxide solution is 0.75mol/L, and the dripping rate of the sodium hydroxide solution is 10mL/h.
As a further technical scheme, the kerosene in the step (3) has average molecular weight213.67 and an kinematic viscosity of 1.52mm at 40 DEG C 2 /s。
As a further technical scheme, the ultrasonic dispersion frequency in the step (7) is 35kHz, and the ultrasonic dispersion is performed for 10min.
As a further technical solution, the plasma treatment in the step (8) is:
placing the material in a plasma vacuum treatment device, vacuumizing to 0.001-0.003Pa, introducing nitrogen, keeping the air pressure in the device at 0.72Pa, starting arc discharge treatment, wherein the current is 50A, the time is 10min, the working voltage is 1000V, and the frequency is 35kHz.
As a further technical scheme: the preliminary drying temperature in the step (9) is 100 ℃, and the drying time is 4 hours;
the high temperature treatment is carried out at 512 ℃ for 2 hours.
As a further technical scheme: the thickness of the coating layer in the step (9) is 100 μm.
According to the invention, the prepared complex microspheres are introduced and partially treated in one step, so that the complex microspheres and the calcined microspheres are introduced, the complex microspheres are of a solid structure, the calcined microspheres are of a complex pore structure, the complex microspheres are introduced into the spray coating sol, partial components can infiltrate into the calcined microspheres, after the subsequent high-temperature treatment, the inside of the complex microspheres can form a micro pore structure, and the inside of the pores of the calcined microspheres can further generate a new pore structure due to the secondary high-temperature treatment, and are combined with the original pore structure to form a more complex structure, so that stronger capillary force can be generated, water can be actively absorbed, thus wetting is more complete, the contact area of the formed coating to water is obviously improved, meanwhile, more hydroxyl structures can be introduced, the hydrophilic property of the coating is improved, the hydrophilic property of the surface of the coating is improved, the wettability of the surface of the coating is effectively improved, the surface of the coating prepared by the coating can be completely wetted, the surface of the coating can be more favorably used for the work of a tubular desalination device, the water yield of the tubular desalination device can be greatly increased by 30% per hour.
When water enters the surface of the coating, water molecules can be rapidly spread out, so that a uniform water film is formed on the surface of the coating, and the spreading of the water film can be beneficial to improving the evaporation area of the water and the evaporation efficiency.
After the water is uniformly spread on the surface of the pipe wall coating of the pipe type desalter, the heat exchange efficiency can be effectively improved, the evaporation efficiency of water can be more favorable, meanwhile, the energy can be saved, and the energy loss is reduced.
(III) beneficial effects
Compared with the prior art, the invention provides the surface hydrophilic TiO of the tubular desalination device 2 The coating preparation process has the following beneficial effects:
according to the invention, the surface of the tubular desalination device is covered with a layer of coating, so that the surface of the tubular desalination device can be effectively protected, meanwhile, the surface of the coating has excellent hydrophilic performance, water can be spread out on the surface of the tubular desalination device more uniformly to form a uniform water film, the evaporation efficiency of the tubular desalination device can be greatly improved, the water production efficiency of the tubular desalination device is improved, meanwhile, the self-cleaning performance of the surface of the coating is also remarkably improved through the great improvement of the hydrophilicity of the surface of the coating, and pollutants are not easy to adhere to the surface of the coating, so that the cleaning and maintenance work of the tubular desalination device is facilitated.
Drawings
FIG. 1 is a bar graph of contact angles for example and comparative coatings;
FIG. 2 is a graph comparing the effect of different plasma treatment times on coating adhesion;
FIG. 3 is a graph comparing the effect of different high temperature processing temperatures on coating contact angle.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Surface hydrophilic TiO of tubular desalination device 2 The coating preparation process comprises the following steps:
(1) Dimethyl dimethoxy silane is used as a raw material to prepare dimethyl silicone oil solution;
parameters of dimethyldimethoxysilane:
density of 0.8+ -0.1 g/cm 3
Boiling point 82.0+ -0.0deg.C at760mmHg;
melting point-80 ℃;
molecular formula C4H12O2Si;
molecular weight 120.222;
flash point-34.8+ -6.0deg.C;
accurate mass 120.060654;
PSA 18.46000;
LogP-0.45;
transparent liquid with appearance like smell of alcohol;
vapor pressure 89.0.+ -. 0.1mmHgat25 ℃;
refractive index 1.376;
storage conditions
Storing in dry inert gas, sealing, storing in shady and dry place;
stability of
Stable at normal temperature and normal pressure, and avoids strong oxide and moisture contact;
the preparation method of the simethicone solution comprises the following steps:
respectively adding dimethyl dimethoxy silane and ethanol solution into a reaction kettle, adjusting the temperature to 40 ℃, preserving heat and stirring for 30min, then adjusting the pH value to 9.1 by adopting ammonia water, and continuing to preserving heat and stirring for 15 hours to obtain dimethyl silicone oil solution; the mass ratio of water to ethanol substances in the ethanol solution is 1:5;
the mass ratio of the materials mixed by the dimethyl dimethoxy silane and the ethanol solution is 1:2;
the concentration of the ammonia water is 1.2-1.5mol/L.
(2) Adding 2-3% nitric acid solution into the multi-layer silica sol, and then respectively adding absolute ethyl alcohol and dimethyl silicone oil solution under the condition of stirring to obtain intermediate body fluid;
wherein the volume ratio of the multi-layer silica sol to the absolute ethyl alcohol to the dimethyl silicone oil to the nitric acid solution is 2:2.5:1-3:0.5;
the preparation method of the multilayer silica sol comprises the following steps:
firstly, adding 250ml of deionized water into a reaction kettle, then adding 15 mu L of saturated ammonia water and 0.21g of sodium hydroxide into the reaction kettle, regulating the temperature in the reaction kettle to 50-54 ℃, keeping the temperature and stirring for 5min, then adding 21.3g of silicon powder, continuously stirring for 3min, then dropwise adding sodium hydroxide solution, stirring at the speed of 120r/min for reaction for 4 hours, then standing for 1 hour, and filtering and removing impurities to obtain primary silica sol;
sequentially adding 200mL of deionized water and 50mL of primary silica sol into a reaction kettle, regulating the temperature of the reaction kettle to 60-64 ℃, then adding 15.8g of silica powder into the reaction kettle, stirring for 3min, then dropwise adding sodium hydroxide solution, stirring and reacting for 5 hours at a rotating speed of 150r/min, then standing for 1 hour, and filtering and removing impurities to obtain multi-layer silica sol; the concentration of the sodium hydroxide solution is 0.75mol/L, and the dripping rate of the sodium hydroxide solution is 10mL/h.
(3) And (3) preparing a base solution: adding cetyl trimethyl ammonium bromide into water, stirring uniformly to prepare cetyl trimethyl ammonium bromide solution, adding ammonia water and kerosene into the cetyl trimethyl ammonium bromide solution, and stirring at 500r/min for 1-1.5 hours to obtain base solution;
wherein the hexadecyl ammonium bromide solution is a saturated solution;
cetyl ammonium bromide parameters:
melting point 248-251 ℃ (litz);
molecular formula C19H42BrN;
molecular weight 364.448;
a flash point of 244 ℃;
accurate mass 363.250061;
LogP 3.17790;
white powder with appearance;
storage conditions
Storing in shade and dry place for sealing and preserving.
Stability of
1. Cannot be blended with anions.
2. It is not suitable to heat at 120 ℃ or higher for a long time.
Water solubility 13g/L (20 ℃);
the mass fraction of the ammonia water is 20-24%;
wherein the volume ratio of ammonia water to cetyl trimethyl ammonium bromide solution to kerosene is 8:5:1.2;
kerosene with average molecular weight of 213.67 and kinematic viscosity of 1.52mm at 40deg.C 2 /s。
(4) Slowly dripping intermediate body fluid into the base fluid, standing for 4-5 hours after dripping, filtering, adding absolute ethyl alcohol for soaking for 20-22 hours, filtering, and drying to obtain complex microspheres;
wherein the mixing volume ratio of the intermediate body fluid to the base fluid is 1:1.4-1.6;
(5) 1-6g of complex microspheres are divided into ab parts, wherein the mass ratio of a parts is 30%, and the mass ratio of b parts is 70%;
(6) Placing the obtained a parts of complex microspheres in a resistance furnace, and calcining to obtain calcined microspheres;
(7) Firstly, adding 90-110mL of absolute ethyl alcohol into a reaction kettle at room temperature, slowly adding 50-60mL of n-butyl titanate into the absolute ethyl alcohol, stirring for 10min, slowly dripping 25-30mL of glacial acetic acid, continuously stirring, sequentially adding 3-5g of methyl methacrylate, b parts of complex microspheres and calcined microspheres into the absolute ethyl alcohol, performing ultrasonic dispersion, wherein the ultrasonic dispersion frequency is 35kHz, and the ultrasonic dispersion time is 10min to obtain mixed dispersion;
gradually dripping the mixed dispersion liquid into a reaction kettle, and then magnetically stirring to obtain spray-coating sol;
(8) Carrying out plasma treatment on the surface of the pipe wall of the tubular desalination device; the plasma treatment is as follows:
placing the material in a plasma vacuum treatment device, vacuumizing to 0.001-0.003Pa, introducing nitrogen, keeping the air pressure in the device at 0.72Pa, starting arc discharge treatment, wherein the current is 50A, the time is 10min, the working voltage is 1000V, and the frequency is 35kHz.
The material that tubular desalination ware adopted is stainless steel material, through carrying out plasma treatment to tubular desalination ware pipe wall, when carrying out plasma treatment, nitrogen gas molecule can be ionized and produce a large amount of ion bodies that contain active nitrogen ion, these ion bodies that produce can be moved to tubular desalination ware pipe wall surface acceleration, and the continuous impact tubular desalination ware pipe wall surface under the electric field effect, can clear away tubular desalination ware pipe wall surface impurity, simultaneously, still have some active nitrogen ion can abstract the electron and become nitrogen atom and directly be absorbed by tubular desalination ware pipe wall surface, and can progressively diffuse to tubular desalination ware pipe wall inlayer tissue, tubular desalination ware pipe wall surface tissue is under continuous ion bombardment, superficial tissue activity obtains by a wide margin improvement, thereby it can more firmly combine with the titanium dioxide coating that forms.
(9) The obtained spray-coated sol is uniformly coated on the wall surface of the tubular desalter, and is subjected to preliminary drying, high-temperature treatment and densification to form a coating; the primary drying temperature is 100 ℃, and the drying time is 4 hours;
the high temperature treatment is carried out at 512 ℃ for 2 hours.
In the subsequent drying process, the liquid is gradually evaporated, so that a solid framework is left, the internal long chains are continuously combined and solidified due to the aggregation among particles and the continuous deposition of small surface particles, and then high-temperature treatment is carried out, so that particles in the framework are further condensed, grown and approached, residual liquid medium and organic matters are removed, and combined water is promoted to be removed, so that the network space is more compact and stable, and a more stable coating is formed.
The coating thickness was 100. Mu.m.
The following are specific examples:
example 1
Surface hydrophilic TiO of tubular desalination device 2 The coating preparation process comprises the following steps:
(1) Dimethyl dimethoxy silane is used as a raw material to prepare dimethyl silicone oil solution;
the preparation method of the simethicone solution comprises the following steps:
respectively adding dimethyl dimethoxy silane and ethanol solution into a reaction kettle, adjusting the temperature to 40 ℃, preserving heat and stirring for 30min, then adjusting the pH value to 9.1 by adopting ammonia water, and continuing to preserving heat and stirring for 15 hours to obtain dimethyl silicone oil solution; the mass ratio of water to ethanol substances in the ethanol solution is 1:5;
the mass ratio of the materials mixed by the dimethyl dimethoxy silane and the ethanol solution is 1:2;
the concentration of the ammonia water is 1.3mol/L.
(2) Adding 2.6% nitric acid solution into the multilayer silica sol, and then respectively adding absolute ethyl alcohol and dimethyl silicone oil solution under the condition of stirring to obtain intermediate body fluid;
wherein the volume ratio of the multi-layer silica sol to the absolute ethyl alcohol to the simethicone solution to the nitric acid solution is 2:2.5:2:0.5;
the preparation method of the multilayer silica sol comprises the following steps:
firstly, adding 250ml of deionized water into a reaction kettle, then adding 15 mu L of saturated ammonia water and 0.21g of sodium hydroxide into the reaction kettle, regulating the temperature in the reaction kettle to 52 ℃, keeping the temperature and stirring for 5min, then adding 21.3g of silicon powder, continuously stirring for 3min, then dropwise adding sodium hydroxide solution, stirring at a speed of 120r/min for reaction for 4 hours, then standing for 1 hour, and filtering and removing impurities to obtain primary silica sol;
sequentially adding 200mL of deionized water and 50mL of primary silica sol into a reaction kettle, regulating the temperature of the reaction kettle to 61 ℃, then adding 15.8g of silica powder into the reaction kettle, stirring for 3min, then dropwise adding sodium hydroxide solution, stirring at a rotating speed of 150r/min for reaction for 5 hours, then standing for 1 hour, and filtering to remove impurities to obtain multi-layer silica sol; the concentration of the sodium hydroxide solution is 0.75mol/L, and the dripping rate of the sodium hydroxide solution is 10mL/h.
(3) And (3) preparing a base solution: adding cetyl trimethyl ammonium bromide into water, stirring uniformly to prepare cetyl trimethyl ammonium bromide solution, adding ammonia water and kerosene into the cetyl trimethyl ammonium bromide solution, and stirring at 500r/min for 1.2 hours to obtain base solution;
wherein the hexadecyl ammonium bromide solution is a saturated solution;
(4) Slowly dripping intermediate body fluid into the base fluid, standing for 4.5 hours after dripping, filtering, adding absolute ethyl alcohol for soaking for 21 hours, filtering, and drying to obtain complex microspheres; wherein the mixing volume ratio of the intermediate body fluid to the base fluid is 1:1.5;
(5) 1g of complex microspheres are divided into ab parts, wherein the mass ratio of a parts is 30%, and the mass ratio of b parts is 70%;
(6) Placing the obtained a parts of complex microspheres in a resistance furnace, and calcining to obtain calcined microspheres;
(7) Firstly, adding 110mL of absolute ethyl alcohol into a reaction kettle at room temperature, slowly adding 55mL of n-butyl titanate into the absolute ethyl alcohol, stirring for 10min, slowly dripping 25mL of glacial acetic acid, continuously stirring, sequentially adding 3g of methyl methacrylate, b parts of complex microspheres and calcined microspheres into the absolute ethyl alcohol, performing ultrasonic dispersion, wherein the ultrasonic dispersion frequency is 35kHz, and the ultrasonic dispersion time is 10min, so as to obtain a mixed dispersion; gradually dripping the mixed dispersion liquid into a reaction kettle, and then magnetically stirring to obtain spray-coating sol;
(8) Carrying out plasma treatment on the surface of the pipe wall of the tubular desalination device; the plasma treatment is as follows: placing the mixture in a plasma vacuum treatment device, vacuumizing to 0.001Pa, introducing nitrogen, keeping the air pressure in the device at 0.72Pa, and starting arc discharge treatment with current of 50A, time of 10min, working voltage of 1000V and frequency of 35kHz.
(9) The obtained spray-coated sol is uniformly coated on the wall surface of the tubular desalter, and is subjected to preliminary drying, high-temperature treatment and densification to form a coating; the primary drying temperature is 100 ℃, and the drying time is 4 hours; the high temperature treatment is carried out at 512 ℃ for 2 hours. The coating thickness was 100. Mu.m.
Example 2
Based on the embodiment 1, the total weight of the complex microsphere is adjusted to be 2g, and the rest technical schemes are unchanged.
Example 3
Based on the embodiment 1, the total weight of the complex microsphere is adjusted to be 3g, and the rest technical schemes are unchanged.
Example 4
Based on the embodiment 1, the total weight of the complex microsphere is adjusted to be 4g, and the rest technical schemes are unchanged.
Example 5
Based on the embodiment 1, the total weight of the complex microsphere is adjusted to be 5g, and the rest technical schemes are unchanged.
Example 6
Based on the embodiment 1, the total weight of the complex microsphere is adjusted to 6g, and the rest technical schemes are unchanged.
Comparative example 1:
on the basis of the embodiment 1, no complex microsphere is introduced, and the rest technical schemes are unchanged.
Comparative example 2:
based on the example 1, b parts of complex microspheres are not introduced, and the rest technical schemes are unchanged.
Comparative example 3
Based on example 1, no calcined microsphere is introduced, and the rest technical schemes are unchanged.
Sample preparation, using 304 stainless steel (10 cm. Times.3 cm. Times.5 mm) as the sample, test sample preparation was performed using the example and comparative example processes, respectively, and then the following tests were performed:
measuring the contact angle (ContactAngel, CA) of the water on the surfaces of the coatings of the examples and the comparative examples by using a DSA25 optical contact angle measuring instrument of KRUSS company of Germany, respectively measuring the water once at 5 different positions on the same coating, and taking the final average value;
TABLE 1
As can be seen from table 1, the contact angle of the coating prepared according to the present invention is greatly reduced, and excellent hydrophilic properties can be exhibited.
Based on example 4, the effect of different high temperature treatments on the hydrophilic properties of the coating was compared;
TABLE 2
As can be seen from table 2, the coating contact angle decreased first and then increased as the high temperature treatment temperature increased.
Detecting the adhesion performance of the coating of the embodiment by adopting a scratch method, and detecting the binding force of the coating;
TABLE 3 Table 3
Binding force/N
Example 1 73.5
Example 2 72.8
Example 3 72.0
Example 4 72.4
Example 5 73.1
Example 6 73.6
As can be seen from Table 3, the coating formed by the invention has stronger bonding force with the outer wall of the tubular desalter tube.
The microhardness of the example is tested by a 401MVD digital display fiber Vickers hardness tester, the test load is 25gf, the holding time is 10s, in order to reduce the measurement error in the experiment, the average value is taken after 10 times of measurement, and the final microhardness value is determined;
TABLE 4 Table 4
As can be seen from Table 4, the coatings prepared according to the present invention have a higher surface hardness.
After immersing the sample of example coating in 5wt.% NaCl solution for 200 hours at a temperature of 80 ℃, the coating change was observed;
TABLE 5
Coating variation
Example 1 No change
Example 2 No change
Example 3 No change
Example 4 No change
Example 5 No change
Example 6 No change
As can be seen from Table 5, the coatings prepared according to the present invention have excellent corrosion resistance.
The coating is formed on the surface of the pipe wall of the pipe type desalter by adopting the method of the embodiment, wherein the sample pipe type desalter produces 2052mL of water per hour (heating power is 250W), and compared with the sample pipe type desalter, the water yield per hour is:
TABLE 6
As can be seen from Table 6, the invention can effectively improve the water production efficiency of the tubular desalination device by covering the surface of the tubular wall of the tubular desalination device with a layer of coating.
After forming a coating on the surface of the tubular desalter by the method of example 4, comparing the wettability of different water inflow amounts to the outer wall of the tubular desalter, as shown in Table 7;
TABLE 7
Speed of water intake (mL/h) Wetting area ratio (%)
720 72.6
1440 85.7
2880 98.3
5760 99.8
As can be seen from Table 7, when the water inflow speed reaches 2880mL/h, the wetting area ratio of the outer wall of the tubular desalination device can reach more than 98%, which shows that the wettability reaches a higher level at the moment, so that the water inflow speed of the tubular desalination device is not lower than 2880mL/h on the basis of the coating of the invention.
In the sol system, van der Waals force is directly related to particle size of colloidal particles, the ratio of surface charge to particle size of colloidal particles can be used to replace the charge-to-mass ratio, and the particle size and the surface charge of the spray-coated sol particles of example 4 are measured by using a Zetasizer Nano series of nanometer particle size and Zeta potentiometer of the Markov company in the United kingdom, as shown in Table 8;
TABLE 8
As can be seen from Table 8, the colloidal particles of the present invention have a charge-to-mass ratio of more than 0.6, and a relatively high stability of the sol.
Fig. 1 is a bar graph of contact angles for example and comparative coatings.
Based on example 4, the effect of different plasma treatment times on the coating binding force was compared, as shown in fig. 2.
Based on example 4, the effect of different high temperature treatment temperatures on the coating contact angle was compared, as shown in fig. 3.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

1. Surface hydrophilic TiO of tubular desalination device 2 The coating preparation process is characterized by comprising the following steps of:
(1) Dimethyl dimethoxy silane is used as a raw material to prepare dimethyl silicone oil solution;
(2) Adding 2-3% nitric acid solution into the multi-layer silica sol, and then respectively adding absolute ethyl alcohol and dimethyl silicone oil solution under the condition of stirring to obtain intermediate body fluid;
wherein the volume ratio of the multi-layer silica sol to the absolute ethyl alcohol to the dimethyl silicone oil to the nitric acid solution is 2:2.5:1-3:0.5;
the preparation method of the multilayer silica sol comprises the following steps:
firstly, adding 250ml of deionized water into a reaction kettle, then adding 15 mu L of saturated ammonia water and 0.21g of sodium hydroxide into the reaction kettle, regulating the temperature in the reaction kettle to 50-54 ℃, keeping the temperature and stirring for 5min, then adding 21.3g of silicon powder, continuously stirring for 3min, then dropwise adding sodium hydroxide solution, stirring at the speed of 120r/min for reaction for 4 hours, then standing for 1 hour, and filtering and removing impurities to obtain primary silica sol;
sequentially adding 200mL of deionized water and 50mL of primary silica sol into a reaction kettle, regulating the temperature of the reaction kettle to 60-64 ℃, then adding 15.8g of silica powder into the reaction kettle, stirring for 3min, then dropwise adding sodium hydroxide solution, stirring and reacting for 5 hours at a rotating speed of 150r/min, then standing for 1 hour, and filtering and removing impurities to obtain multi-layer silica sol;
(3) And (3) preparing a base solution: adding cetyl trimethyl ammonium bromide into water, stirring uniformly to prepare cetyl trimethyl ammonium bromide solution, adding ammonia water and kerosene into the cetyl trimethyl ammonium bromide solution, and stirring at 500r/min for 1-1.5 hours to obtain base solution;
wherein the hexadecyl ammonium bromide solution is a saturated solution;
the mass fraction of the ammonia water is 20-24%;
wherein the volume ratio of ammonia water to cetyl trimethyl ammonium bromide solution to kerosene is 8:5:1.2;
(4) Slowly dripping intermediate body fluid into the base fluid, standing for 4-5 hours after dripping, filtering, adding absolute ethyl alcohol for soaking for 20-22 hours, filtering, and drying to obtain complex microspheres;
wherein the mixing volume ratio of the intermediate body fluid to the base fluid is 1:1.4-1.6;
(5) 1-6g of complex microspheres are divided into ab parts, wherein the mass ratio of a parts is 30%, and the mass ratio of b parts is 70%;
(6) Placing the obtained a parts of complex microspheres in a resistance furnace, and calcining to obtain calcined microspheres;
(7) Firstly, adding 90-110mL of absolute ethyl alcohol into a reaction kettle at room temperature, slowly adding 50-60mL of n-butyl titanate into the absolute ethyl alcohol, stirring for 10min, slowly dropwise adding 25-30mL of glacial acetic acid, continuously stirring, sequentially adding 3-5g of methyl methacrylate, b parts of complex microspheres and calcined microspheres into the absolute ethyl alcohol, and performing ultrasonic dispersion to obtain a mixed dispersion;
gradually dripping the mixed dispersion liquid into a reaction kettle, and then magnetically stirring to obtain spray-coating sol;
(8) Carrying out plasma treatment on the surface of the pipe wall of the tubular desalination device;
(9) Uniformly coating the obtained spray sol on the surface of the pipe wall of the pipe type desalination device, performing preliminary drying, performing high-temperature treatment, and performing densification to form a coating;
the primary drying temperature is 100 ℃, and the drying time is 4 hours;
the high temperature treatment is carried out at 512 ℃ for 2 hours.
2. Surface hydrophilic TiO of tubular desalinator according to claim 1 2 The coating preparation process is characterized in that the preparation method of the simethicone solution in the step (1) comprises the following steps:
and respectively adding dimethyl dimethoxy silane and ethanol solution into a reaction kettle, regulating the temperature to 40 ℃, preserving heat and stirring for 30min, regulating the pH value to 9.1 by adopting ammonia water, and continuing to preserving heat and stirring for 15 hours to obtain dimethyl silicone oil solution.
3. A tubular desalinator surface hydrophilic TiO according to claim 2 2 The coating preparation process is characterized in that the mass ratio of water to ethanol substances in the ethanol solution is 1:5;
the mass ratio of the materials mixed by the dimethyl dimethoxy silane and the ethanol solution is 1:2;
the concentration of the ammonia water is 1.2-1.5mol/L.
4. Surface hydrophilic TiO of tubular desalinator according to claim 1 2 A coating preparation process is characterized in that the hydrogen hydroxideThe sodium solution concentration was 0.75mol/L, and the sodium hydroxide solution dropwise added rate was 10mL/h.
5. Surface hydrophilic TiO of tubular desalinator according to claim 1 2 The coating preparation process is characterized in that the kerosene in the step (3) has an average molecular weight of 213.67 and an kinematic viscosity of 1.52mm at 40 DEG C 2 /s。
6. Surface hydrophilic TiO of tubular desalinator according to claim 1 2 The coating preparation process is characterized in that the ultrasonic dispersion frequency in the step (7) is 35kHz, and the ultrasonic dispersion time is 10min.
7. Surface hydrophilic TiO of tubular desalinator according to claim 1 2 A coating preparation process, characterized in that in step (8) the plasma treatment is:
placing the material in a plasma vacuum treatment device, vacuumizing to 0.001-0.003Pa, introducing nitrogen, keeping the air pressure in the device at 0.72Pa, starting arc discharge treatment, wherein the current is 50A, the time is 10min, the working voltage is 1000V, and the frequency is 35kHz.
8. Surface hydrophilic TiO of tubular desalinator according to claim 1 2 The coating preparation process is characterized in that: the thickness of the coating layer in the step (9) is 100 μm.
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CN115627460A (en) * 2022-10-31 2023-01-20 合肥中聚和成电子材料有限公司 SiO doped with corrosion inhibitor 2 Preparation method of anticorrosive coating of microsphere and anticorrosive coating prepared by using same

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Publication number Priority date Publication date Assignee Title
CN101164881A (en) * 2007-10-11 2008-04-23 北京科技大学 Low cost method for preparing SiO2 aerogel micro-sphere
JP2009242115A (en) * 2008-03-28 2009-10-22 Jgc Catalysts & Chemicals Ltd Silica sol and production method of the same
JP2014055075A (en) * 2012-09-11 2014-03-27 Japan Fine Ceramics Center Method of manufacturing porous silica particle and porous silica particle for vacuum heat insulation material
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