CN111115854A - Scale inhibitor coated mesoporous microsphere, preparation method thereof, water heater and liner - Google Patents
Scale inhibitor coated mesoporous microsphere, preparation method thereof, water heater and liner Download PDFInfo
- Publication number
- CN111115854A CN111115854A CN201811276892.2A CN201811276892A CN111115854A CN 111115854 A CN111115854 A CN 111115854A CN 201811276892 A CN201811276892 A CN 201811276892A CN 111115854 A CN111115854 A CN 111115854A
- Authority
- CN
- China
- Prior art keywords
- scale inhibitor
- coated
- water
- liner
- mesoporous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 139
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000004005 microsphere Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 49
- 238000000576 coating method Methods 0.000 claims abstract description 49
- 239000003921 oil Substances 0.000 claims abstract description 44
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 38
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 230000005764 inhibitory process Effects 0.000 claims abstract description 28
- 239000007762 w/o emulsion Substances 0.000 claims abstract description 28
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004202 carbamide Substances 0.000 claims abstract description 21
- 239000012153 distilled water Substances 0.000 claims abstract description 19
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 9
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 68
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 57
- 239000012071 phase Substances 0.000 claims description 52
- 239000011148 porous material Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 40
- 239000006185 dispersion Substances 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 210000003298 dental enamel Anatomy 0.000 claims description 25
- 239000000839 emulsion Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 12
- 239000008346 aqueous phase Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 8
- 239000012875 nonionic emulsifier Substances 0.000 claims description 8
- 230000001680 brushing effect Effects 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 230000002401 inhibitory effect Effects 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 229910021389 graphene Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000027455 binding Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses a mesoporous microsphere coated with a scale inhibitor and a preparation method thereof, a water heater and a liner, wherein the preparation method comprises the following steps: s1, taking at least one of tetraethyl orthosilicate, tetrabutyl titanate, sodium silicate and silane coupling agent as a precursor, one of urea, sodium hydroxide, potassium hydroxide, hydrochloric acid and carboxylic acid as a catalyst, at least one of cyclohexane, cyclopentane and n-heptane as an oil phase, distilled water as a water phase, and mixing an emulsifier and a scale inhibitor to prepare a water-in-oil emulsion system; s2, separating out solid after the water-in-oil emulsion system reacts; and S3, drying the solid to obtain the mesoporous microsphere coated with the scale inhibitor. According to the preparation method of the mesoporous microsphere coated with the scale inhibitor, the mesoporous microsphere coated with the scale inhibitor can be prepared, and the mesoporous microsphere can be coated on the inner surface of the liner of the water heater, so that a scale inhibition coating is formed on the inner surface of the liner, and the liner has a scale inhibition function.
Description
Technical Field
The invention relates to a mesoporous microsphere coated with a scale inhibitor and a preparation method thereof, a pore structure material coated with the scale inhibitor and a preparation method thereof, an inner container of a water heater and a preparation method thereof, and the water heater.
Background
Scale is a big threat to the water treatment industry, and how to better remove or inhibit the formation of scale has been a hot topic of the water-related industry. With the development of scientific technology, treatment methods typified by electricity, magnetism, ultrasound, resins, additives, and the like are gradually developed. For an electric water heater, the water storage type electric water heater has an inner container, which has a more serious scale problem and a larger volume. In view of the operating condition of the water storage type electric water heater, the existing scale inhibition and scale inhibition schemes are not accepted by the market due to large volume, high cost, potential safety hazard and frequent maintenance.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. The inner container of the water heater provided by the invention has a descaling function.
Therefore, the invention provides a preparation method of a mesoporous microsphere coated with a scale inhibitor.
The invention also provides another preparation method of the mesoporous microsphere coated with the scale inhibitor.
The invention also provides the mesoporous microsphere coated with the scale inhibitor, which is prepared by the preparation method of the mesoporous microsphere coated with the scale inhibitor.
The invention also provides a preparation method of the scale inhibitor-coated porous structure material.
The invention also provides a pore structure material coated with the scale inhibitor, which is prepared by the preparation method of the pore structure material coated with the scale inhibitor.
The invention also provides a preparation method for preparing the inner container of the water heater by using the mesoporous microsphere or pore structure material.
The invention also provides another preparation method for preparing the inner container of the water heater by using the mesoporous microsphere or pore structure material.
The invention also provides the inner container of the water heater prepared by the preparation method.
The invention also provides a water heater with the inner container.
The preparation method of the scale inhibitor-coated mesoporous microsphere according to the first aspect of the invention comprises the following steps:
s1, taking at least one of tetraethyl orthosilicate, tetrabutyl titanate, sodium silicate and silane coupling agent as a precursor, one of urea, sodium hydroxide, potassium hydroxide, hydrochloric acid and carboxylic acid as a catalyst, at least one of cyclohexane, cyclopentane and n-heptane as an oil phase and distilled water as a water phase, and preparing a water-in-oil emulsion system by mixing an emulsifier and a scale inhibitor, wherein the emulsifier is a cationic emulsifier or a nonionic emulsifier;
s2, separating out solid after the water-in-oil emulsion system reacts;
and S3, drying the solid to obtain the mesoporous microsphere coated with the scale inhibitor.
According to the preparation method of the mesoporous microsphere coated with the scale inhibitor, the mesoporous microsphere coated with the scale inhibitor can be prepared, and the mesoporous microsphere can be coated on the inner surface of the liner of the water heater, so that a scale inhibition coating is formed on the inner surface of the liner, and the liner has a scale inhibition function.
In some embodiments, in the step S1, the catalyst, the emulsifier, the scale inhibitor and the distilled water are configured into an aqueous phase dispersion according to a mass ratio of (0.3-2): (0.6-1): 6-10): 30, the precursor and the oil phase are configured into an oil phase dispersion according to a volume ratio of (1-5): 12, the aqueous phase dispersion is stirred and an oil phase dispersion with the same volume as the aqueous phase dispersion is added, and the high-speed stirring is performed for not less than 30min, so as to obtain the water-in-oil emulsion system.
In some embodiments, the precursor is tetraethyl orthosilicate, the catalyst is urea, the oil phase is cyclohexane, and the emulsifier is cetyltrimethyl ammonium bromide.
In some embodiments, in the step S2, the water-in-oil emulsion system is placed in a water bath at 60 ℃ to 90 ℃ for stirring reaction for 8h to 16 h.
In some embodiments, the step S2 further includes: and adding ethanol into the solid separated after the reaction for cleaning, and then centrifuging and separating.
The preparation method of the scale inhibitor-coated mesoporous microsphere according to the second aspect of the present invention comprises the following steps:
s10, placing the mesoporous microspheres in a sealing device and vacuumizing;
s20, adding an aqueous solution with the scale inhibitor concentration of 5% -10% into the closed device;
s30, vacuumizing the sealing device again until the mesoporous microspheres become dry, and obtaining the mesoporous microspheres coated with the scale inhibitor.
In some embodiments, the mesoporous microspheres are mesoporous silica microspheres.
The scale inhibitor-coated mesoporous microsphere according to the third aspect of the present invention is prepared by the method for preparing the scale inhibitor-coated mesoporous microsphere according to the first or second aspect of the present invention.
The preparation method of the scale inhibitor-coated pore structure material according to the fourth aspect of the present invention comprises the following steps:
s01, taking at least one of tetraethyl orthosilicate, tetrabutyl titanate, sodium silicate and silane coupling agent as a precursor, one of urea, sodium hydroxide, potassium hydroxide, hydrochloric acid and carboxylic acid as a catalyst, at least one of cyclohexane, cyclopentane and n-heptane as an oil phase and distilled water as a water phase, and preparing a double-continuous emulsion system by mixing an emulsifier and a scale inhibitor, wherein the emulsifier is a cationic emulsifier or a nonionic emulsifier;
s02, separating out solid after the reaction of the bicontinuous emulsion system;
and S03, drying the solid to obtain the pore structure material coated with the scale inhibitor.
In some embodiments, in the step S1, the catalyst, the emulsifier, the scale inhibitor, and the distilled water are configured into an aqueous phase dispersion according to a mass ratio of (0.3-2): (0.6-1): (6-10): 10, the precursor and the oil phase are configured into an oil phase dispersion according to a volume ratio of (1-5): 5, the aqueous phase dispersion is stirred and the oil phase dispersion is added, and the stirring at a high speed is not less than 30min, so as to obtain the bicontinuous aqueous emulsion system.
In some embodiments, the precursor is tetraethyl orthosilicate, the catalyst is urea, the oil phase is cyclohexane, and the emulsifier is cetyltrimethyl ammonium bromide.
In some embodiments, in the step S02, the bicontinuous emulsion system is placed in a water bath at 60 ℃ to 90 ℃ to be stirred and reacted for 8 hours to 16 hours.
In some embodiments, the step S02 further includes: and (3) adding ethanol into the solid separated after the reaction for cleaning, and then carrying out centrifugal separation.
According to the scale inhibitor-coated pore structure material of the fifth aspect of the present invention, the scale inhibitor-coated pore structure material is prepared by the method for preparing the scale inhibitor-coated pore structure material of the fourth aspect of the present invention.
According to the sixth aspect of the invention, the preparation method of the inner container of the water heater comprises the following steps: coating the mesoporous microspheres coated with the scale inhibitor according to the third aspect of the invention or the pore structure material coated with the scale inhibitor according to the fifth aspect of the invention on the inner surface of the liner, spraying a mixed solution of ammonia and at least one of tetraethyl orthosilicate, tetrabutyl titanate, sodium silicate and a silane coupling agent, and drying the liner.
According to a seventh aspect of the present invention, there is provided a method for manufacturing an inner container of a water heater, the method comprising the steps of:
s11, brushing an ethanol solution containing 3-isocyanatopropyl triethoxysilane and ammonia water on the inner surface of the inner container, and drying the inner container;
s22, soaking the mesoporous microsphere coated with the scale inhibitor according to claim 8 or the pore structure material coated with the scale inhibitor according to claim 14 into an ethanol solution containing 3-aminopropyltriethoxysilane and ammonia water to obtain a modified scale inhibiting material;
s33, brushing the modified scale inhibition coating on the inner surface of the inner container, and drying the inner container.
In some embodiments, the liner is an enamel liner.
According to the inner container of the water heater in the eighth aspect, the inner container is manufactured by the manufacturing method of the inner container of the water heater in the sixth aspect or the seventh aspect.
The water heater according to the ninth aspect of the invention comprises the liner of the water heater according to the eighth aspect of the invention.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
Firstly, a water heater according to an embodiment of a ninth aspect of the present invention is briefly described, where the hot water in the embodiment of the present invention may be an instant water heater, an electric water heater, a gas water heater, a wall-mounted furnace, and the like, and the following description only takes the water heater as an example for description.
The water heater of the embodiment of the invention comprises: according to the liner of the water heater in the embodiment of the eighth aspect of the invention, the liner of the water heater in the embodiment can be manufactured by adopting the preparation method of the liner in the sixth aspect or the seventh aspect of the invention. Two methods for manufacturing the inner container of the water heater are respectively described below.
According to a sixth aspect of the present invention, there is provided a method of manufacturing an inner container, the method comprising: coating the mesoporous microspheres coated with the scale inhibitor according to the third aspect of the invention or the pore structure material coated with the scale inhibitor according to the fifth aspect of the invention on the inner surface of the liner, spraying a mixed solution of ammonia and at least one of tetraethyl orthosilicate, tetrabutyl titanate, sodium silicate and a silane coupling agent, and drying the liner. Therefore, the scale inhibition coating can be formed on the inner surface of the inner container, so that the inner container has a scale inhibition function.
In other words, the preparation method comprises the following steps: spraying a mesoporous microsphere or a pore structure material coated with a scale inhibitor on the inner surface of the liner, and then spraying a mixed solution containing ammonia water to the corresponding position of the inner surface, wherein the mixed solution contains ammonia water, and one, two, three or more of tetraethyl orthosilicate, tetrabutyl titanate, sodium silicate and a silane coupling agent. Therefore, the mixed solution can bond the mesoporous microsphere or the pore structure material to the inner surface of the liner, thereby enhancing the bonding force between the coating of the mesoporous microsphere or the pore structure material coated with the scale inhibitor and the liner and avoiding the coating from falling off.
Preferably, the scale inhibitor-coated mesoporous microsphere or pore structure material coated on the inner surface of the liner is a micron-scale coating. That is to say, the thickness of the coating layer containing the mesoporous microspheres or the pore structure materials coated with the scale inhibitor on the inner surface of the liner is micron-sized, for example, the coating thickness can be between 30 microns and 200 microns, although the invention is not limited thereto, and the coating thickness can also be less than 30 microns or more than 200 microns. For example, coating thicknesses of 50 microns, 100 microns, 150 microns, and the like.
Preferably, the mixed liquid is sprayed at a low speed, so that the impact of the mixed liquid on the mesoporous microspheres or porous structural materials on the inner surface of the liner can be reduced, and the mesoporous microspheres or porous structural materials coated with the scale inhibitor are prevented from falling.
Preferably, the time for spraying the mixed solution is not less than 2min, so that enough adhesive force between the mesoporous microsphere or the porous structure material coated with the scale inhibitor and the inner container can be ensured.
In some embodiments, the drying liner can be a liner which is naturally dried or a drying liner. For example, the liner can be placed in a furnace for drying, specifically, the furnace temperature can be set to 70 ℃, and the liner is placed in the furnace for not less than 1 hour, so that the liner can be dried and the coating can be fixed.
According to the preparation method of the inner container provided by the embodiment of the invention, the inner surface of the inner container can be provided with the coating of the mesoporous microspheres or hole structural materials coated with the scale inhibitor, so that the inner container has a scale inhibition function, and further the generation of scale is inhibited.
A method of making an inner bladder in accordance with an embodiment of the seventh aspect of the present invention, the method comprising:
s11, brushing an ethanol solution containing 3-isocyanate propyl triethoxysilane and ammonia water on the inner surface of the inner container, and drying the inner container;
s22, soaking the mesoporous microsphere coated with the scale inhibitor according to the third aspect of the invention or the pore structure material coated with the scale inhibitor according to the fifth aspect of the invention into an ethanol solution containing 3-aminopropyltriethoxysilane and ammonia water to obtain the modified scale inhibition coating,
s33, brushing the modified scale inhibition coating on the inner surface of the inner container, and drying the inner container.
According to the preparation method of the inner container provided by the embodiment of the invention, the inner surface of the inner container can be provided with the coating of the mesoporous microspheres or hole structural materials coated with the scale inhibitor, so that the inner container has a scale inhibition function, and further the generation of scale is inhibited.
In step S11, the ethanol solution containing 3-isocyanatopropyltriethoxysilane and ammonia is brushed and the inner container is dried to make the surface of the inner container carry isocyanate groups, thereby facilitating adhesion with the modified scale inhibiting coating obtained in step S22. Of course, the present invention is not limited thereto, and other solutions may be applied to the inner surface of the inner container, as long as the solution can make the inner surface of the inner container have some kind of groups capable of being bonded with the modified scale inhibition coating in step S22.
In addition, in step S11, the inner surface of the inner container may be brushed several times with an ethanol solution containing 3-isocyanatopropyltriethoxysilane and ammonia water and the inner container may be dried. For example, the inner surface of the inner container is coated with ethanol solution with 3-isocyanate propyl triethoxysilane and ammonia water, and the hot bar is stretched into the inner container for baking. Repeating the steps for three times to enable the surface of the inner container to be provided with isocyanate groups.
In step S22, the mesoporous microsphere or the porous structure material coated with the scale inhibitor is immersed in an ethanol solution containing 3-aminopropyltriethoxysilane and ammonia water, so as to modify the mesoporous microsphere or the porous structure material in the solution to make it sticky, thereby facilitating bonding with the isocyanate group in step S11.
In step S33, the modified scale inhibiting coating brushed on the inner surface of the inner container finally forms a coating with a thickness of micrometer scale on the inner surface of the inner container. For example, the coating thickness may be between 30 microns and 200 microns, although the invention is not limited thereto and the coating thickness may be less than 30 microns or greater than 200 microns. For example, coating thicknesses of 50 microns, 100 microns, 150 microns, and the like.
In addition, in step S33, the drying liner may be a liner that is naturally dried or a drying liner. For example, the liner can be placed in a furnace for drying, specifically, the furnace temperature can be set to 70 ℃, and the liner is placed in the furnace for not less than 10min, so that the fixing of the coating can be completed.
Preferably, the inner container of the water heater is an enamel inner container, that is, the inner container of the water heater can be subjected to enamel treatment. However, the invention is not limited thereto, and the inner container of the water heater may not be enameled. Wherein, the mesoporous microsphere or the pore structure material coated with the scale inhibitor is coated on the enamel surface of the liner. Or brushing a modified solution (ethanol solution containing 3-isocyanate propyl triethoxysilane and ammonia water) on the enamel surface of the inner container.
It should be noted that, according to the method for preparing the inner container of the sixth aspect of the present invention, the mesoporous microspheres coated with the scale inhibitor are directly sprayed on the inner surface of the inner container, or the pore structure material coated with the scale inhibitor is directly assembled on the inner surface of the inner container, and then the additive with binding action (for example, the mixed solution of at least one of tetraethyl orthosilicate, tetrabutyl titanate, sodium silicate and silane coupling agent and ammonia water) is sprayed on the inner surface of the inner container. Of course, the invention is not limited to this, and the mesoporous microsphere or porous structure material coated with the scale inhibitor and the additive with the binding effect can be sprayed or bound on the inner surface of the liner together.
According to the method for preparing the inner container of the seventh aspect of the invention, the inner surface of the inner container is coated with a substance with a bonding effect (such as the ethanol solution containing 3-isocyanatopropyltriethoxysilane and ammonia water) in advance, and then the mesoporous microspheres coated with the scale inhibitor or the pore structure material coated with the scale inhibitor is sprayed.
The scale inhibition process of the liner prepared by the preparation method of the liner according to the sixth aspect or the seventh aspect of the invention is described below.
According to the inner container of the water heater of the eighth aspect of the invention, when the electric water heater is used, the inner container is filled with water, and the inner surface of the inner container is surrounded by the water. At the moment, water slowly diffuses into the mesoporous microsphere layer or the pore structure material layer through the mesoporous or pore structure, so that the scale inhibitor is slowly dissolved and diffuses into the whole inner container along with the water. Along with the starting work of the water heater, the water temperature rises, and the dissolution and diffusion of the scale inhibitor are accelerated. The scale inhibitor interacts with the scale forming ions in the water to finally achieve the purpose of inhibiting scale.
The scale inhibitor-coated mesoporous microsphere according to the third aspect of the present invention and the preparation method thereof, and the scale inhibitor-coated pore structure material according to the fifth aspect of the present invention and the preparation method thereof are described in detail below.
According to the scale inhibitor-coated mesoporous microsphere of the third aspect of the present invention, the mesoporous microsphere can be prepared by the method for preparing the scale inhibitor-coated mesoporous microsphere of the first or second aspect of the present invention. The mesoporous microspheres can be in a macroporous, hollow or multi-stage pore structure, and can be made of a pure silica material, or one or more composite materials such as silica, alumina, carbon nanotubes, graphene, graphite, graphene oxide, diatomite and the like.
The following describes a preparation method of the scale inhibitor-coated mesoporous microsphere according to the first aspect of the present invention, the preparation method comprising the steps of:
s1, taking at least one of tetraethyl orthosilicate, tetrabutyl titanate, sodium silicate and silane coupling agent as a precursor, one of urea, sodium hydroxide, potassium hydroxide, hydrochloric acid and carboxylic acid as a catalyst, at least one of cyclohexane, cyclopentane and n-heptane as an oil phase and distilled water as a water phase, and preparing a water-in-oil emulsion system by mixing an emulsifier and a scale inhibitor, wherein the emulsifier is a cationic emulsifier or a nonionic emulsifier;
s2, separating out solid after the water-in-oil emulsion system reacts;
and S3, drying the solid to obtain the mesoporous microsphere coated with the scale inhibitor.
That is, in step S1, the precursor may be one of tetraethyl orthosilicate, tetrabutyl titanate, sodium silicate, and a silane coupling agent, and the precursor may also be a combination of two or more thereof. The catalyst can be alkaline catalyst, such as urea, sodium hydroxide, potassium hydroxide, etc., or acidic catalyst, such as hydrochloric acid, carboxylic acid, etc. The oil phase is a cycloparaffin such as: cyclohexane, cyclopentane, the oil phase can be n-heptane, of course, the oil phase can be formed by combining two or more oil substances. The emulsifier can be a cationic emulsifier, and the emulsifier can also be a nonionic emulsifier.
According to the preparation method of the scale inhibitor-coated mesoporous microsphere provided by the embodiment of the invention, the scale inhibitor-coated mesoporous microsphere can be prepared, and the mesoporous microsphere can be coated on the inner surface of the liner of the water heater, so that a scale inhibition coating is formed on the inner surface of the liner, and the liner has a scale inhibition function.
In one embodiment of the invention, in step S1, the catalyst, the emulsifier, the scale inhibitor and the distilled water are prepared into an aqueous dispersion according to the mass ratio of (0.3-2): (0.6-1): 6-10): 30, the precursor and the oil phase are prepared into an oil phase dispersion according to the volume ratio of (1-5): 12, the aqueous dispersion is stirred and an oil phase dispersion with the same volume as the aqueous phase dispersion is added, and the high-speed stirring is carried out for not less than 30min, so as to obtain the water-in-oil emulsion system.
In step S1, in one specific example, the precursor may be tetraethyl orthosilicate, the catalyst may be urea, the oil phase may be cyclohexane, and the emulsifier may be cetyltrimethyl ammonium bromide.
In step S2, the water-in-oil emulsion system can be placed in a water bath at 60-90 ℃ to be stirred and reacted for 8-16 h. Of course, the invention is not limited thereto and the water bath temperature of the water-in-oil emulsion system may also be less than 60 ℃ or greater than 90 ℃ as long as the water in the water bath does not boil. For example, the water bath temperature of the water-in-oil emulsion system may be 50 ℃, 55 ℃, 65 ℃, 75 ℃, 80 ℃, 85 ℃, 95 ℃ and the like. In addition, the time for stirring the water-in-oil emulsion system in the water bath is not limited thereto, i.e., the stirring reaction time may be less than 8 hours or more than 16 hours. For example, the water-in-oil emulsion system may be stirred in a water bath for reaction times of 7h, 9h, 11h, 13h, 15h, 17h, 19h, 20h, and so forth.
For example, the water-in-oil emulsion system can be placed in a water bath at 70 ℃ and stirred for 16 hours.
Since some impurities may be adhered to the solid separated after the water-in-oil emulsion system is reacted, in some examples, the step S2 may further include: washing the solid separated after the water-in-oil emulsion system reacts with ethanol, and then centrifuging and separating. Therefore, the impurities can be cleaned by using ethanol, and the purer mesoporous microspheres coated with the scale inhibitor can be obtained.
Preferably, ethanol may be added several times to wash the solids separated after the reaction. For example, when the water-in-oil emulsion system is reacted, the solid is separated by centrifugation, ultrasonic cleaning is carried out by adding ethanol, and centrifugal separation is carried out, and then ultrasonic cleaning is carried out by adding ethanol, and centrifugal separation is carried out, and the steps are repeated for a plurality of times.
In some embodiments, in step S3, the drying solid may be air drying or drying. For example, when a dry solid is employed, the solid may be dried in a forced air oven at 80 ℃.
A method for preparing scale inhibitor-coated mesoporous microspheres according to an embodiment of the second aspect of the present invention is described below, the method comprising:
s10, placing the mesoporous microspheres in a sealing device and vacuumizing;
s20, adding an aqueous solution with the scale inhibitor concentration of 5% -10% into the closed device;
s30, vacuumizing the sealing device again until the mesoporous microspheres become dry, and obtaining the mesoporous microspheres coated with the scale inhibitor.
Wherein, when preparing the water solution of the scale inhibitor, the addition amount of the scale inhibitor is converted by the volume of the scale inhibitor and the porosity of the microsphere.
Preferably, the mesoporous microspheres are silica microspheres.
According to the preparation method of the scale inhibitor-coated mesoporous microsphere provided by the embodiment of the invention, the scale inhibitor-coated mesoporous microsphere can be prepared, and the mesoporous microsphere can be coated on the inner surface of the liner of the water heater, so that a scale inhibition coating is formed on the inner surface of the liner, and the liner has a scale inhibition function.
The pore structure material coated with the scale inhibitor according to the fifth aspect of the present invention can be prepared by the method for preparing the pore structure material coated with the scale inhibitor according to the fourth aspect of the present invention. The holes in the hole structure material can be in a macroporous, hollow or multistage hole structure, and the hole structure material can be a pure silicon dioxide material, and also can be one or more composite materials such as silicon dioxide, aluminum oxide, carbon nanotubes, graphene, graphite, graphene oxide, diatomite and the like.
The following describes a method for preparing a scale inhibitor-coated pore structure material according to the third aspect of the present invention, the method comprising the steps of:
s01, taking at least one of tetraethyl orthosilicate, tetrabutyl titanate, sodium silicate and silane coupling agent as a precursor, one of urea, sodium hydroxide, potassium hydroxide, hydrochloric acid and carboxylic acid as a catalyst, at least one of cyclohexane, cyclopentane and n-heptane as an oil phase and distilled water as a water phase, and preparing a double-continuous emulsion system by mixing an emulsifier and a scale inhibitor, wherein the emulsifier is a cationic emulsifier or a nonionic emulsifier;
s02, separating out solid after the reaction of the bicontinuous emulsion system;
and S03, drying the solid to obtain the pore structure material coated with the scale inhibitor.
That is, in step S01, the precursor may be one of tetraethyl orthosilicate, tetrabutyl titanate, sodium silicate, and a silane coupling agent, and the precursor may also be a combination of two or more thereof. The catalyst can be alkaline catalyst, such as urea, sodium hydroxide, potassium hydroxide, etc., or acidic catalyst, such as hydrochloric acid, carboxylic acid, etc. The oil phase is a cycloparaffin such as: cyclohexane, cyclopentane, the oil phase can be n-heptane, of course, the oil phase can be formed by combining two or more oil substances. The emulsifier can be a cationic emulsifier, and the emulsifier can also be a nonionic emulsifier.
According to the preparation method of the pore structure material coated with the scale inhibitor, the pore structure material coated with the scale inhibitor can be prepared, and the pore structure material can be coated on the inner surface of the liner of the water heater, so that a scale inhibition coating is formed on the inner surface of the liner, and the liner has a scale inhibition function. The hole structure material in the embodiment of the invention is a block material or a film.
In one embodiment of the invention, in step S01, the catalyst, the emulsifier, the scale inhibitor and the distilled water are prepared into an aqueous phase dispersion according to the mass ratio of (0.3-2): (0.6-1): 6-10): 10, the precursor and the oil phase are prepared into an oil phase dispersion according to the volume ratio of (1-5): 5, the aqueous phase dispersion is stirred and the oil phase dispersion is added, and the high-speed stirring is carried out for not less than 30min, so as to obtain the bicontinuous aqueous emulsion system.
In step S01, in one specific example, the precursor may be tetraethyl orthosilicate, the catalyst may be urea, the oil phase may be cyclohexane, and the emulsifier may be cetyltrimethyl ammonium bromide.
In step S02, the bicontinuous emulsion system is placed in a water bath at 60-90 ℃ to be stirred and reacted for 8-16 h. Of course, the present invention is not so limited and the temperature of the water bath of the bicontinuous emulsion system may also be less than 60 c or greater than 90 c, provided that the water in the water bath does not boil. For example, the temperature of the water bath in the bicontinuous emulsion system may be 50 ℃, 55 ℃, 65 ℃, 75 ℃, 80 ℃, 85 ℃, 95 ℃ or the like. In addition, the time for the stirring reaction of the bicontinuous emulsion system in the water bath is not limited thereto, i.e., the stirring reaction time may be less than 8 hours or more than 16 hours. For example, the bicontinuous emulsion system may be stirred in a water bath for reaction times of 7h, 9h, 11h, 13h, 15h, 17h, 19h, 20h, and so forth.
For example, the bicontinuous emulsion system may be placed in a 70 ℃ water bath and reacted for 16 hours with stirring.
In some examples, the step S02 may further include: and (3) adding ethanol into the solid separated after the reaction of the bicontinuous emulsion system for cleaning, and then carrying out centrifugal separation. Therefore, the impurities can be cleaned by using ethanol, and a purer hole structure material coated with the scale inhibitor is obtained.
Preferably, ethanol may be added several times to wash the solids separated after the reaction. For example, when the bicontinuous emulsion system has reacted, the solids are centrifuged off, ethanol is added for ultrasonic cleaning and centrifuged again, and this is repeated a plurality of times.
In some embodiments, in step S03, the drying solid may be air drying or drying. For example, when a dry solid is employed, the solid may be dried in a forced air oven at 80 ℃.
The following describes a method for manufacturing the liner of the water heater according to four embodiments of the present invention.
In a first embodiment, the method for preparing the inner container of the water heater in the embodiment of the invention comprises the following steps:
step 1, preparing mesoporous silica microspheres coated with scale inhibitor: tetraethyl orthosilicate (TEOS) is used as a precursor, urea is used as a catalyst, cyclohexane is used as an oil phase, distilled water is used as a water phase, and Cetyl Trimethyl Ammonium Bromide (CTAB) is used as an emulsifier to prepare a water-in-oil emulsion system. The method comprises the following specific steps: preparing a dispersion liquid by using urea, CTAB, a scale inhibitor and distilled water according to a mass ratio of (0.3-2): 0.6-1): 6-10): 30, using the dispersion liquid as a water phase, adding an oil phase dispersion liquid with the same volume (the volume ratio of TEOS to cyclohexane is (1-5): 12) while stirring, and stirring at a high speed for 30min to obtain a water-in-oil emulsion system. Stirring the water-in-oil emulsion system in a water bath at 70 ℃ for 16 hours for reaction, centrifuging to separate out solids, adding ethanol for ultrasonic dispersion, centrifuging for three times, and drying the obtained final solids in a blast drying oven at 80 ℃ for later use;
step 2, coating the mesoporous silica microspheres coated with the scale inhibitor on the surface of the enamel liner: the enamel inner container of the electric water heater is sprayed with the mesoporous silica microspheres coated with the scale inhibitor on the surface of the enamel inner container in a spraying mode to form a coating with the thickness of micron level, and then mixed liquid of TEOS and ammonia water is sprayed for 2min at low speed. Setting the furnace temperature at 70 ℃, placing the inner container in the furnace, placing for 1h, and taking out to finish the fixation of the coating.
The scale inhibition process of the inner container of the water heater provided by the embodiment of the invention is realized as follows: when the electric water heater is used, the inner container is filled with water, and the enamel surface is surrounded by the water. At the moment, water slowly diffuses into the mesoporous microsphere layer through the mesopores, so that the scale inhibitor is slowly dissolved and diffuses to the whole inner container along with the water. Along with the starting work of the water heater, the water temperature rises, and the dissolution and diffusion of the scale inhibitor are accelerated. The scale inhibitor interacts with the scale forming ions in the water to finally achieve the purpose of inhibiting scale.
In a second embodiment, the method for preparing the inner container of the water heater in the embodiment of the invention comprises the following steps:
step 1, preparing mesoporous silica microspheres coated with scale inhibitor: tetraethyl orthosilicate (TEOS) is used as a precursor, urea is used as a catalyst, cyclohexane is used as an oil phase, distilled water is used as a water phase, and Cetyl Trimethyl Ammonium Bromide (CTAB) is used as an emulsifier to prepare a water-in-oil emulsion system. The method comprises the following specific steps: preparing a dispersion liquid by using urea, CTAB, a scale inhibitor and distilled water according to a mass ratio of (0.3-2): 0.6-1): 6-10): 30, using the dispersion liquid as a water phase, adding an oil phase dispersion liquid with the same volume (the volume ratio of TEOS to cyclohexane is (1-5): 12) while stirring, and stirring at a high speed for 30min to obtain a water-in-oil emulsion system. Stirring the water-in-oil emulsion system in a water bath at 70 ℃ for 16 hours for reaction, centrifuging to separate out solids, adding ethanol for ultrasonic dispersion and centrifuging for three times to obtain final solids, and drying the final solids in a blast drying oven at 80 ℃;
step 2, using an ethanol solution of 3-aminopropyltriethoxysilane and ammonia water to soak and modify the mesoporous silica microspheres for 2 hours at the temperature of 60 ℃, and storing;
step 3, surface treatment of the enamel inner container of the water heater: the enameled inner container of electric water heater is coated with 3-isocyanate propyl triethoxy silane and alcohol solution of ammonia water by brush coating, and the hot rod is stretched into the inner container for baking. Repeating for three times to make the surface of the inner container carry isocyanate groups;
step 4, coating the mesoporous silica microspheres coated with the scale inhibitor on the surface of the enamel liner: coating the microsphere dispersion liquid on the surface of an enamel liner in a brush coating mode to form a coating with the thickness of micron level, setting the furnace temperature at 70 ℃, placing the liner in the furnace, standing for 10min, and taking out to finish the fixation of the coating.
The scale inhibition process of the liner prepared by the preparation method of the embodiment is the same as that of the embodiment one, and the description is omitted here.
In a third embodiment, the preparation method of the inner container of the water heater in the embodiment of the invention comprises the following steps:
step 1, preparing mesoporous silica microspheres coated with scale inhibitor: preparing mesoporous silica microspheres, placing the mesoporous silica microspheres in a closed device, and vacuumizing. Pouring an aqueous solution of a scale inhibitor with the concentration of 5-10% into the mesoporous silica microspheres subjected to vacuum treatment, and continuously vacuumizing until the microspheres are dry, so that the final mesoporous silica microspheres coated with the scale inhibitor are obtained for later use;
step 2, coating the mesoporous silica microspheres coated with the scale inhibitor on the surface of the enamel liner: the enameled inner container of the electric water heater is sprayed with the microspheres on the surface of the enameled inner container in a spraying mode to form a micron-level coating, and then mixed solution of TEOS and ammonia water is sprayed at a low speed for 2 min. Setting the furnace temperature at 70 ℃, placing the inner container in the furnace, standing for 1h, and taking out to finish the fixation of the coating.
The scale inhibition process of the liner prepared by the preparation method of the third embodiment is the same as that of the first embodiment, and is not described again here.
With respect to the preparation methods of the inner containers in the first, second and third embodiments, it should be further noted that the mesoporous silica microspheres prepared in step 1 may be silica microspheres with a macroporous, hollow, and multi-stage pore structure, and the size and components of the mesoporous silica microspheres are not specifically limited in this application.
It should be noted that the microspheres carrying the scale inhibitor may be not surface-modified or may be surface-modified. The mesoporous microspheres can be formed by spraying additives with bonding function on the surface of the inner container enamel, or formed by fixing the mesoporous microspheres after self-assembly on the surface of the enamel in advance, or formed by spraying materials with bonding function on the surface of the inner container enamel in advance.
In addition, the coating of the mesoporous microspheres can be the coating of the whole inner container, or the partial coating, or the surface modification coating of partial parts and the combination of multiple coating modes.
In addition, the service life and the release speed of the scale inhibition coating of the inner container of the water heater can be realized by adjusting the spraying amount and the spraying area of the mesoporous microspheres.
In a fourth embodiment, the method for preparing the inner container of the water heater in the embodiment of the invention comprises the following steps:
step 1, preparing a block or film containing the scale inhibitor: tetraethyl orthosilicate (TEOS) is used as a precursor, urea is used as a catalyst, cyclohexane is used as an oil phase, distilled water is used as a water phase, and Cetyl Trimethyl Ammonium Bromide (CTAB) is used as an emulsifier to prepare a bicontinuous emulsion system. The method comprises the following specific steps: preparing aqueous dispersion liquid by using urea, CTAB, a scale inhibitor and distilled water according to the mass ratio of (0.3-2) to (0.6-1) to (6-10) to 10, adding oil phase dispersion liquid with a proper volume (the volume ratio of TEOS to cyclohexane is (1-5) to 5) while stirring, and stirring at a high speed for 30min to obtain a bicontinuous emulsion system. Standing the bicontinuous emulsion system in a water bath at 70 ℃ for reaction for 16 hours to obtain a final solid, and drying the final solid in a forced air drying oven at 80 ℃ for later use;
step 2, combining the block or film containing the scale inhibitor with the surface of the enamel liner: and (3) gluing the enamel surface or the surfaces of the block material and the film, and adhering the block material or the film to the enamel surface of the water heater liner.
The implementation of the scale inhibition process of the inner container of the water heater in the embodiment of the invention is the same as that in the first embodiment, and the description is omitted here.
It should be noted that the block or film containing the scale inhibitor prepared in step 1 may be a simple silica material, or may be one or more composite materials of silica and alumina, carbon nanotubes, graphene, graphite, graphene oxide, diatomaceous earth, and the like. The block or film containing the scale inhibitor can be in a mesoporous structure, and can also be a silica microsphere in a macroporous, hollow and multistage porous structure, and the size and the components of the mesoporous microsphere are not specifically limited in the application.
It should be noted that the bulk or film carrying the scale inhibitor may be either unmodified or surface-modified. The block or film can be coated with a substance with adhesive action on the enamel surface in advance and then adhered, or can be sprayed on the enamel surface of the liner together with an additive with adhesive action, or can be directly adhered on the inner surface of the enamel.
In addition, the bonding of the bulk materials or the films can be the bonding of the whole inner container, or the partial bonding, or the surface modification bonding of partial parts and the combination of a plurality of bonding modes.
In addition, the service life and the release speed of the scale inhibition coating of the inner container of the water heater can be realized by adjusting the bonding amount and the bonding area of the block material or the film.
According to the inner container prepared by the preparation method of the inner container of the water heater, disclosed by the embodiments of the invention, the slow-release scale inhibitor is combined with the enamel layer of the water heater, so that on one hand, the filter material is slowly released through the mesopores, and the efficient utilization of the scale inhibitor is realized. On the other hand, the water heater is combined with the enamel layer of the water heater, a series of slow release devices are cancelled, and maintenance is not needed.
In the description of the present invention, it is to be understood that the terms "thickness," "upper," "lower," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in an orientation or positional relationship indicated for convenience in describing the present invention and to simplify description, but are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be construed as limiting the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (19)
1. A preparation method of mesoporous microspheres coated with scale inhibitors is characterized by comprising the following steps:
s1, taking at least one of tetraethyl orthosilicate, tetrabutyl titanate, sodium silicate and silane coupling agent as a precursor, one of urea, sodium hydroxide, potassium hydroxide, hydrochloric acid and carboxylic acid as a catalyst, at least one of cyclohexane, cyclopentane and n-heptane as an oil phase and distilled water as a water phase, and preparing a water-in-oil emulsion system by mixing an emulsifier and a scale inhibitor, wherein the emulsifier is a cationic emulsifier or a nonionic emulsifier;
s2, separating out solid after the water-in-oil emulsion system reacts;
and S3, drying the solid to obtain the mesoporous microsphere coated with the scale inhibitor.
2. The method for preparing mesoporous microspheres coated with scale inhibitors according to claim 1, wherein in step S1, the catalyst, the emulsifier, the scale inhibitors, and the distilled water are prepared into an aqueous dispersion according to a mass ratio of (0.3-2), (0.6-1), (6-10): 30, the precursor and the oil phase are prepared into an oil phase dispersion according to a volume ratio of (1-5): 12, the aqueous dispersion is stirred and an oil phase dispersion with the same volume as the aqueous dispersion is added, and the water-in-oil emulsion system is obtained by stirring at a high speed for not less than 30 min.
3. The method for preparing the mesoporous microsphere coated with the scale inhibitor according to claim 1, wherein the precursor is tetraethyl orthosilicate, the catalyst is urea, the oil phase is cyclohexane, and the emulsifier is hexadecyl trimethyl ammonium bromide.
4. The method for preparing mesoporous microspheres coated with scale inhibitors according to claim 1, wherein in step S2, the water-in-oil emulsion system is placed in a water bath at 60-90 ℃ and stirred for 8-16 h.
5. The method for preparing the mesoporous microsphere coated with the scale inhibitor according to claim 1, wherein the step S2 further comprises: and adding ethanol into the solid separated after the reaction for cleaning, and then carrying out centrifugal separation.
6. A preparation method of mesoporous microspheres coated with scale inhibitors is characterized by comprising the following steps:
s10, placing the mesoporous microspheres in a sealing device and vacuumizing;
s20, adding an aqueous solution with the scale inhibitor concentration of 5% -10% into the closed device;
s30, vacuumizing the sealing device again until the mesoporous microspheres become dry, and obtaining the mesoporous microspheres coated with the scale inhibitor.
7. The method for preparing the mesoporous microsphere coated with the scale inhibitor according to claim 6, wherein the mesoporous microsphere is a mesoporous silica microsphere.
8. A scale inhibitor-coated mesoporous microsphere, which is prepared by the method for preparing the scale inhibitor-coated mesoporous microsphere according to any one of claims 1 to 7.
9. A preparation method of a pore structure material coated with a scale inhibitor is characterized by comprising the following steps:
s01, taking at least one of tetraethyl orthosilicate, tetrabutyl titanate, sodium silicate and silane coupling agent as a precursor, one of urea, sodium hydroxide, potassium hydroxide, hydrochloric acid and carboxylic acid as a catalyst, at least one of cyclohexane, cyclopentane and n-heptane as an oil phase and distilled water as a water phase, and preparing a double-continuous emulsion system by mixing an emulsifier and a scale inhibitor, wherein the emulsifier is a cationic emulsifier or a nonionic emulsifier;
s02, separating out solid after the reaction of the bicontinuous emulsion system;
and S03, drying the solid to obtain the pore structure material coated with the scale inhibitor.
10. The method for preparing the pore structure material coated with the scale inhibitor according to claim 9, wherein in the step S01, the catalyst, the emulsifier, the scale inhibitor and the distilled water are prepared into an aqueous dispersion according to a mass ratio of (0.3-2): (0.6-1): (6-10): 10, the precursor and the oil phase are prepared into an oil phase dispersion according to a volume ratio of (1-5): 5, the aqueous phase dispersion is stirred and added, and the stirring at a high speed is carried out for not less than 30min, so as to obtain the bicontinuous aqueous emulsion system.
11. The method for preparing the pore structure material coated with the scale inhibitor according to claim 9, wherein the precursor is tetraethyl orthosilicate, the catalyst is urea, the oil phase is cyclohexane, and the emulsifier is cetyltrimethyl ammonium bromide.
12. The method for preparing the pore structure material coated with the scale inhibitor according to claim 9, wherein in the step S02, the bicontinuous emulsion system is placed in a water bath at 60-90 ℃ to be stirred and reacted for 8-16 h.
13. The method for preparing the pore structure material coated with the scale inhibitor according to claim 9, wherein the step S02 further comprises: and adding ethanol into the solid separated after the reaction for cleaning, and then carrying out centrifugal separation.
14. A pore structure material coated with a scale inhibitor, which is characterized by being prepared by the preparation method of the pore structure material coated with the scale inhibitor according to any one of claims 9 to 13.
15. A preparation method of an inner container of a water heater is characterized by comprising the following steps:
coating the mesoporous microsphere coated with the scale inhibitor according to claim 8 or the pore structure material coated with the scale inhibitor according to claim 14 on the inner surface of the liner, spraying a mixed solution of ammonia and at least one of tetraethyl orthosilicate, tetrabutyl titanate, sodium silicate and a silane coupling agent, and drying the liner.
16. The preparation method of the inner container of the water heater is characterized by comprising the following steps:
s11, brushing an ethanol solution containing 3-isocyanate propyl triethoxysilane and ammonia water on the inner surface of the inner container, and drying the inner container;
s22, soaking the mesoporous microsphere coated with the scale inhibitor according to claim 8 or the pore structure material coated with the scale inhibitor according to claim 14 into an ethanol solution containing 3-aminopropyltriethoxysilane and ammonia water to obtain a modified scale inhibiting material;
s33, brushing the modified scale inhibition coating on the inner surface of the inner container, and drying the inner container.
17. The method for preparing the liner of the water heater as claimed in claim 15 or 16, wherein the liner is an enamel liner.
18. A liner of a water heater, characterized in that the liner is made by the method for making the liner of the water heater according to any one of claims 15-17.
19. A water heater comprising the liner of claim 18.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811276892.2A CN111115854A (en) | 2018-10-30 | 2018-10-30 | Scale inhibitor coated mesoporous microsphere, preparation method thereof, water heater and liner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811276892.2A CN111115854A (en) | 2018-10-30 | 2018-10-30 | Scale inhibitor coated mesoporous microsphere, preparation method thereof, water heater and liner |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111115854A true CN111115854A (en) | 2020-05-08 |
Family
ID=70484363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811276892.2A Pending CN111115854A (en) | 2018-10-30 | 2018-10-30 | Scale inhibitor coated mesoporous microsphere, preparation method thereof, water heater and liner |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111115854A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194260A (en) * | 2020-10-13 | 2021-01-08 | 泗县金皖泵业有限公司 | Treatment process for reducing scale generation rate in high-temperature water pump |
| CN113880103A (en) * | 2020-07-01 | 2022-01-04 | 中国石油化工股份有限公司 | Beta molecular sieve and synthetic method and application thereof |
| CN114057305A (en) * | 2021-12-03 | 2022-02-18 | 澳门大学 | Scale inhibitor slow-release bead, preparation method and application |
| CN115196643A (en) * | 2022-08-18 | 2022-10-18 | 中谱科技(福州)有限公司 | Silicon dioxide microsphere and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007984A (en) * | 2007-01-26 | 2007-08-01 | 北京化工大学 | Nano loaded control release type perfume and its preparation method |
| CN101250374A (en) * | 2008-04-03 | 2008-08-27 | 同济大学 | Nano hollow silica dioxide micro-sphere/polyurethane composite aqueous paint and preparation method thereof |
| US20110200658A1 (en) * | 2008-03-13 | 2011-08-18 | Syngenta Crop Protection, Inc. | Microencapsulation |
| CN102398907A (en) * | 2010-09-08 | 2012-04-04 | 清华大学 | Method for preparing mesoporous silicon oxide microballoons |
| CN105820607A (en) * | 2016-04-15 | 2016-08-03 | 安徽开林新材料股份有限公司 | Anticorrosive coating of titanium sol modified aluminum electrode and preparation method thereof |
| CN106497326A (en) * | 2016-10-25 | 2017-03-15 | 东北石油大学 | A kind of new scale inhibition coating |
| CN107141848A (en) * | 2017-07-04 | 2017-09-08 | 重庆立道表面技术有限公司 | High anticorrosive nano-coating and anticorrosion process |
| CN108355588A (en) * | 2018-01-03 | 2018-08-03 | 成都高界科技有限公司 | A method of synthesizing microballoon on super-double-hydrophobic surface |
-
2018
- 2018-10-30 CN CN201811276892.2A patent/CN111115854A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007984A (en) * | 2007-01-26 | 2007-08-01 | 北京化工大学 | Nano loaded control release type perfume and its preparation method |
| US20110200658A1 (en) * | 2008-03-13 | 2011-08-18 | Syngenta Crop Protection, Inc. | Microencapsulation |
| CN101250374A (en) * | 2008-04-03 | 2008-08-27 | 同济大学 | Nano hollow silica dioxide micro-sphere/polyurethane composite aqueous paint and preparation method thereof |
| CN102398907A (en) * | 2010-09-08 | 2012-04-04 | 清华大学 | Method for preparing mesoporous silicon oxide microballoons |
| CN105820607A (en) * | 2016-04-15 | 2016-08-03 | 安徽开林新材料股份有限公司 | Anticorrosive coating of titanium sol modified aluminum electrode and preparation method thereof |
| CN106497326A (en) * | 2016-10-25 | 2017-03-15 | 东北石油大学 | A kind of new scale inhibition coating |
| CN107141848A (en) * | 2017-07-04 | 2017-09-08 | 重庆立道表面技术有限公司 | High anticorrosive nano-coating and anticorrosion process |
| CN108355588A (en) * | 2018-01-03 | 2018-08-03 | 成都高界科技有限公司 | A method of synthesizing microballoon on super-double-hydrophobic surface |
Non-Patent Citations (2)
| Title |
|---|
| 张春莉: "钛硅中空微球的制备及催化性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 施利毅: "《多孔材料 奇妙的微结构》", 31 January 2018, 上海科学普及出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880103A (en) * | 2020-07-01 | 2022-01-04 | 中国石油化工股份有限公司 | Beta molecular sieve and synthetic method and application thereof |
| CN112194260A (en) * | 2020-10-13 | 2021-01-08 | 泗县金皖泵业有限公司 | Treatment process for reducing scale generation rate in high-temperature water pump |
| CN112194260B (en) * | 2020-10-13 | 2022-09-06 | 安徽金晥泵业科技股份有限公司 | Treatment process for reducing scale generation rate in high-temperature water pump |
| CN114057305A (en) * | 2021-12-03 | 2022-02-18 | 澳门大学 | Scale inhibitor slow-release bead, preparation method and application |
| CN115196643A (en) * | 2022-08-18 | 2022-10-18 | 中谱科技(福州)有限公司 | Silicon dioxide microsphere and preparation method and application thereof |
| CN115196643B (en) * | 2022-08-18 | 2024-05-28 | 中谱科技(福州)有限公司 | Silica microsphere and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111115854A (en) | Scale inhibitor coated mesoporous microsphere, preparation method thereof, water heater and liner | |
| CN102719129B (en) | Preparation method of silica aerogel aqueous heat-insulating coating | |
| CN104115305A (en) | Separator containing an organic-inorganic adhesion promoter component | |
| CN104861757B (en) | Cladded type ceramic hollow microballon and method and purposes | |
| WO2006068020A1 (en) | Method for producing porous silica based particles and porous silica based particles produced by using the method | |
| CN101143989A (en) | Hydrophobic coating and application thereof | |
| CN103933871A (en) | Preparation method of all-silicon MFI type molecular sieve membrane with high stability | |
| KR20110069119A (en) | Adsorber element and method for producing an adsorber element | |
| CN102336414B (en) | Method for preparing high quality SAPO-34 zeolite membrane by clear sol method | |
| JP4883967B2 (en) | Method for producing porous silica-based particles and porous silica-based particles obtained from the method | |
| CN106008943B (en) | The preparation technology of acid-organosilicon crylic acid saturated polyester hybrid resin | |
| CN106366860A (en) | Novel nano ceramic thermal insulation material | |
| CN102741369B (en) | Surface coatings having anti-ice properties | |
| JP4984566B2 (en) | Method for producing zeolite separation membrane | |
| CN109293933A (en) | Super-hydrophobic automatic cleaning polymer and preparation method thereof based on zeolite imidazole ester skeleton | |
| CN107649111A (en) | A kind of preparation method of modified silica-gel | |
| CN105038498A (en) | Aerosil-floating bead composite thermal-insulation heat-preserving paint and preparation method thereof | |
| CN105038496A (en) | Nanometer Al2O3 composite aerosil thermal-insulation heat-preserving paint and preparation method thereof | |
| CN106753203A (en) | A kind of depickling type organic silicon adhesive and preparation method thereof | |
| CN109852332A (en) | A kind of surface treating agent and its preparation method and application | |
| CN110540768B (en) | Concrete anticorrosive coating and preparation method thereof | |
| CN105038500A (en) | Urushiol-modified aerosil super thermal-insulation heat-preserving paint and preparation method thereof | |
| CN109970075B (en) | Method for synthesizing A-type molecular sieve membrane at low temperature | |
| AU2009326144A1 (en) | Silicate isocyanate | |
| RU2409427C2 (en) | Device to apply and wipe liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200508 |