CN114772756A - Phosphorus-free multifunctional microcapsule scale inhibitor and preparation method and application thereof - Google Patents
Phosphorus-free multifunctional microcapsule scale inhibitor and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/20—After-treatment of capsule walls, e.g. hardening
- B01J13/203—Exchange of core-forming material by diffusion through the capsule wall
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/20—After-treatment of capsule walls, e.g. hardening
- B01J13/206—Hardening; drying
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/20—After-treatment of capsule walls, e.g. hardening
- B01J13/22—Coating
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- C02F2303/04—Disinfection
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/14—Additives which dissolves or releases substances when predefined environmental conditions are reached, e.g. pH or temperature
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2307/00—Location of water treatment or water treatment device
- C02F2307/14—Treatment of water in water supply networks, e.g. to prevent bacterial growth
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Abstract
The invention discloses a phosphorus-free multifunctional microcapsule scale inhibitor and a preparation method and application thereof. The phosphorus-free multifunctional microcapsule scale inhibitor can solve the problems of strong water solubility and high loss of the conventional scale inhibitor, improve the lasting period of the phosphorus-free multifunctional microcapsule scale inhibitor, and has the effects of corrosion inhibition and sterilization.
Description
Technical Field
The invention belongs to the technical field of scale inhibitors, and particularly relates to a phosphorus-free multifunctional microcapsule scale inhibitor, and a preparation method and application thereof.
Background
In systems such as urban water supply, factory sewage treatment and oil wells, scaling, blockage, corrosion and other problems are often accompanied before the inner wall of a pipeline and common filtering equipment, and when the problems are serious, production delay can be caused, and even paralysis of the whole system can be caused. According to related reports, the loss caused by equipment scaling and corrosion can reach billions yuan every year in China, so that a reasonable and effective solution is urgently needed to be found.
At present, the common solution is mainly to release and solve the problems of scaling and corrosion in the system by putting one or more chemical agents, such as putting scale inhibitors or corrosion inhibitors. Based on this, the demand of our country for scale inhibitors increases with an increase of about 5.38%, however, the traditional scale inhibitors have the problems of eutrophication of phosphorus-containing water and soil, large use amount of organic solvents, short duration, high loss and the like, and are gradually far from the demand of modern green industry. Therefore, the development of the multifunctional, efficient and long-lasting phosphorus-free scale inhibitor is the key to solve the scaling problems of industrial production and urban water.
Disclosure of Invention
Aiming at the problems, the invention discloses a phosphorus-free multifunctional microcapsule scale inhibitor, a preparation method and application thereof, which aim to overcome the problems or at least partially solve the problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
the phosphorus-free multifunctional microcapsule scale inhibitor comprises a phosphorus-free multifunctional inner core and a microcapsule shell layer, wherein the phosphorus-free multifunctional inner core contains the phosphorus-free scale inhibitor and a corrosion-inhibiting antibacterial agent, and the microcapsule shell layer is a slow-release shell layer and is coated outside the phosphorus-free multifunctional inner core.
Preferably, the phosphorus-free scale inhibitor in the phosphorus-free multifunctional inner core comprises any one or a mixture of a plurality of polyepoxysuccinic acid, polyaspartic acid, acrylic acid sulfonic acid copolymer, benzotriazole, citrate, sodium molybdate and maleic anhydride; and/or the corrosion inhibition antibacterial agent in the phosphorus-free multifunctional inner core is heterocyclic base quaternary ammonium salt and comprises any one or a mixture of more of chlorinated-1-methylquinoline, chlorinated-1-naphthylmethylpyridine, brominated-1-ethylpyridine, chlorinated-1-naphthylmethylquinoline and brominated-1-ethylquinoline.
Preferably, the microcapsule shell is made of butadiene-styrene copolymer and is formed by condensation polymerization at an oil-water interface.
A preparation method of a phosphorus-free multifunctional microcapsule scale inhibitor is used for preparing any one of the phosphorus-free multifunctional microcapsule scale inhibitors, and specifically comprises the following steps:
step S1, coating the shell of the microcapsule: firstly, dissolving the material of the microcapsule shell in a dissolving agent, and then dispersing the material of the phosphorus-free multifunctional inner core in the dissolving agent in which the material of the microcapsule shell is dissolved to form polymer emulsion dispersion liquid; then, dropwise adding an emulsion initiator into the polymer emulsion dispersion liquid, guiding the material of the shell layer of the microcapsule to agglomerate by using the emulsion initiator, and coating the phosphorus-free multifunctional inner core by using the property difference of the solution;
step S2, solidifying the shell layer of the microcapsule: placing the polymer emulsion dispersion liquid dropwise added with the emulsification initiator in the step S1 into a container filled with n-heptane, stirring, and curing the shell layer of the microcapsule;
step S3, microcapsule collection: and (4) depositing the solution stirred in the step (S2) to separate the microcapsules after shell layer solidification, and then cleaning and drying the separated microcapsules to obtain the multifunctional phosphorus microcapsule scale inhibitor.
Preferably, the preparation method of the phosphorus-free multifunctional microcapsule scale inhibitor further comprises a step S4, wherein the solvent recovery step comprises the following steps: and (4) heating and stirring the solution for separating the microcapsules in the step S3, and condensing and recovering n-heptane and the emulsification initiator by adopting a distillation mode.
Preferably, in the step S1, the microcapsule shell is made of 1 to 10g of butadiene-styrene copolymer, the solvent is 10 to 50mL of dichloromethane solution, and the emulsification initiator is 10 to 20mL of dimethyl siloxane.
Preferably, in the step S1, a mass ratio of the material of the phosphorus-free multifunctional inner core to the material of the microcapsule shell is 1:1 to 5: 1.
Preferably, in the step S1, the material of the phosphorus-free multifunctional core is sufficiently dispersed in a dissolving agent in which the material of the shell layer of the microcapsule is dissolved, at a rotation speed of 200 to 550 rpm.
Preferably, in the step S2, the stirring temperature is 20 to 60 ℃, the stirring speed is 200 to 550rpm, and the stirring time is not less than 1 hour.
The application of the phosphorus-free multifunctional microcapsule scale inhibitor is applied to scale inhibition, antibiosis and corrosion inhibition treatment of water systems such as urban water supply, factory sewage treatment and the like.
Compared with the prior art, the invention has the beneficial effects that: in the invention, the oil-water interface of the microcapsule shell is subjected to polycondensation reaction in a room temperature environment to form a slow-release microcapsule shell with certain mechanical strength and water resistance, and the microcapsule shell forms a coating for the phosphorus-free multifunctional inner core, so that the oil phase and the water phase are separated on the inner side and the outer side of the microcapsule shell, the influence of the external environment on the phosphorus-free multifunctional inner core is reduced, the problems of strong water solubility and high loss of a conventional scale inhibitor are solved, and the lasting period of the phosphorus-free multifunctional microcapsule scale inhibitor is prolonged.
In addition, by selecting the heterocyclic base quaternary ammonium salt as a corrosion inhibition antibacterial agent in the phosphorus-free multifunctional inner core, in an acidic use environment, the heterocyclic base quaternary ammonium salt can be dissociated into halogen anions and quaternary ammonium salt cations in an acidic solution, so that a compact protective film is formed on the surface of a metal, the surface of the metal part is protected, a corrosion inhibition effect is achieved, and the effect of sterilization can also be achieved by utilizing the interaction of the quaternary ammonium salt positive charges and cell walls carrying negative charges on the surface of bacteria.
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Various additional advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic diagram of the mechanism of the coating formation of a microcapsule shell layer on a phosphorus-free multifunctional inner core in the phosphorus-free multifunctional microcapsule scale inhibitor of the present invention;
FIG. 2 is a schematic diagram of the application mechanism of the phosphorus-free multifunctional microcapsule scale inhibitor of the present invention;
fig. 3 is a schematic flow diagram of a process for preparing a phosphorus-free multifunctional microcapsule scale inhibitor in an embodiment of the present invention;
FIG. 4 is a schematic structural diagram of a molecule and a functional group of polyaspartic acid selected as the phosphorus-free scale inhibitor;
FIG. 5 is a schematic diagram of a corrosion inhibition mechanism of a heterocyclic quaternary ammonium salt selected as a corrosion inhibition antibacterial agent;
FIG. 6 is a schematic diagram of the antibacterial mechanism of the heterocyclic quaternary ammonium salt selected as the corrosion-inhibiting antibacterial agent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the specific embodiments of the present invention and the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention discloses a phosphorus-free multifunctional microcapsule scale inhibitor applied to scale inhibition, antibiosis and corrosion inhibition treatment of water systems such as urban water supply, factory sewage treatment and the like.
The phosphorus-free multifunctional microcapsule scale inhibitor comprises a phosphorus-free multifunctional inner core and a microcapsule shell layer. Wherein, the non-phosphorus multifunctional inner core contains a non-phosphorus scale inhibitor and a corrosion-resistant antibacterial agent, and the microcapsule shell layer is a slow-release shell layer and is coated outside the non-phosphorus multifunctional inner core.
In the phosphorus-free multifunctional microcapsule scale inhibitor disclosed by the invention, a polycondensation reaction is carried out on an oil-water interface in a room temperature environment through the material of a microcapsule shell to form a slow-release microcapsule shell with certain mechanical strength and water resistance and coat a phosphorus-free multifunctional inner core, so that an oil phase and a water phase are isolated on two sides of the microcapsule shell, the influence of the phosphorus-free multifunctional inner core on the external environment is reduced, the lasting period of the scale inhibitor is prolonged, the effect of economically and efficiently treating a water system is achieved, meanwhile, the volatilization of water-soluble scale inhibitor components in the water-soluble scale inhibitor can be effectively inhibited, the phytotoxicity to an environmental water body is reduced, and the problems that the phosphorus-free multifunctional inner core is subjected to photolysis, hydrolysis or microbial degradation and the like are solved.
The phosphorus-free scale inhibitor in the phosphorus-free multifunctional inner core comprises any one or a mixture of polyepoxysuccinic acid, polyaspartic acid, acrylic acid sulfonic acid copolymer, benzotriazole, citrate, sodium molybdate and maleic anhydride. The corrosion-inhibiting antibacterial agent in the phosphorus-free multifunctional inner core is heterocyclic base quaternary ammonium salt, and comprises any one or a mixture of more of chlorinated-1-methylquinoline, chlorinated-1-naphthylmethylpyridine, brominated-1-ethylpyridine, chlorinated-1-naphthylmethylquinoline and brominated-1-ethylquinoline.
At the moment, in an acidic use environment, heterocyclic base quaternary ammonium salt is dissociated into halogen anions and quaternary ammonium salt cations in an acidic solution, so that a compact protective film is formed on the surface of a metal, the surface of the metal part is protected, a corrosion inhibition effect is achieved, and meanwhile, a sterilization effect can be achieved by utilizing the interaction of the positive charges of the quaternary ammonium salt and cell walls carrying negative charges on the surface of bacteria.
In addition, the shell layer of the microcapsule is made of butadiene-styrene copolymer, and a condensation polymerization reaction is formed at a room-temperature oil-water interface by a dimethyl siloxane induction method, so that a slow-release microcapsule shell layer with certain mechanical strength and water resistance is formed, the phosphorus-free multifunctional inner core is coated, and the oil phase and the water phase are isolated at two sides of the microcapsule shell layer.
With reference to fig. 1 and fig. 2, this embodiment discloses a method for preparing the above phosphorus-free multifunctional microcapsule scale inhibitor, which specifically includes the following steps:
and step S1, coating the microcapsule shell.
Firstly, 1-10 g of butadiene-styrene copolymer is taken as a material of a microcapsule shell layer and dissolved in a dissolving agent which is 10-50 mL of dichloromethane solution; then, dispersing the material of the phosphorus-free multifunctional inner core into a dichloromethane solution in which a butadiene-styrene copolymer is dissolved to form polymer emulsion dispersion liquid; then, 10-20 mL of dimethyl siloxane is used as an emulsification initiator and is dropwise added into the polymer emulsion dispersion liquid. At this time, dimethyl siloxane is used as an emulsion initiator to induce the butadiene-styrene copolymer as a wall material to be coagulated, and the solubility of the butadiene-styrene copolymer is lowered by the solubility difference to be precipitated, thereby coating the phosphorus-free scale-inhibiting core material.
Preferably, in this embodiment, the material of the phosphorus-free multifunctional core is dispersed in a dichloromethane solution in which a butadiene-styrene copolymer is dissolved, and the dichloromethane solution in which the butadiene-styrene copolymer is dissolved is maintained at a rotation speed of 200 to 550rpm, thereby improving the dispersion effect of the material of the phosphorus-free multifunctional core.
In addition, in step S1, the mass ratio of the material of the phosphorus-free multifunctional core to the material of the microcapsule shell is controlled to be 1:1 to 5:1, so as to obtain the phosphorus-free multifunctional microcapsule scale inhibitor with a suitable size. In other embodiments, the mass ratio of the material of the phosphorus-free multifunctional inner core to the material of the microcapsule shell can be specifically adjusted according to different use environments, and the proportional relationship of the phosphorus-free scale inhibitor and the corrosion-inhibiting antibacterial agent in the phosphorus-free multifunctional inner core can also be correspondingly adjusted according to different use environments, such as the content of bacteria and scale, so as to achieve the optimal use effect.
And step S2, solidifying the microcapsule shell layer.
And (4) dropping the dichloromethane solution of dimethyl siloxane in the step S1, namely placing the polymer emulsion dispersion liquid dropping the emulsification initiator into a container filled with n-heptane for stirring, and carrying out shell layer solidification of the microcapsules.
Preferably, not less than 250mL of sufficient n-heptane is added into a container of the selected flask, and in the stirring process, the stirring temperature is controlled to be 20-60 ℃, the stirring speed is controlled to be 200-550 rpm, and the stirring time is not less than 1 hour, so that the curing efficiency and effect of the shell layer of the microcapsule are improved.
In step S3, microcapsules are collected.
And (4) depositing the solution stirred in the step (S2) to fully separate the microcapsules after shell layer solidification, and cleaning and drying the separated microcapsules to obtain the multifunctional phosphorus microcapsule scale inhibitor. The deposition time is not less than 30min, the microcapsules are cleaned for several times by respectively using n-heptane and deionized water until no solvent remains, and then the microcapsules are dried at a low temperature of 20-60 ℃ to obtain the final phosphorus-free multifunctional microcapsule scale inhibitor product.
Preferably, the preparation method of the phosphorus-free multifunctional microcapsule scale inhibitor further comprises a step S4 of recovering the solvent. Specifically, the solution from which the microcapsules are separated in step S3 is heated and stirred, and n-heptane and dimethyl siloxane are condensed and recovered by distillation for recycling, thereby reducing the preparation cost.
As shown in fig. 3, in step S1 of this embodiment, Polyaspartic Acid (PASP) is selected as the phosphorus-free scale inhibitor in the phosphorus-free multifunctional inner core, and its scale inhibition mechanism and water solubility are specifically: PASP molecules have active groups such as (-CO-NH-), carboxyl (-COOH) and the like, wherein the carboxyl (-COOH) on a long chain is ionized in water to form carboxyl negative ions, and can perform a complex reaction with various ions, so that polyaspartic acid has a scale inhibition characteristic in an aqueous solution, and meanwhile, oxygen and nitrogen atoms in a structural unit of the polyaspartic acid easily form hydrogen bonds with water molecules, so that the polyaspartic acid has good water solubility.
Referring to fig. 4 to 6, in step S1 of this embodiment, the heterocyclic quaternary ammonium salt molecules are selected as the corrosion-inhibiting antibacterial agent in the acidification pipeline to prolong the service life of the pipeline equipment system by utilizing the advantages of small reagent consumption, high synthesis efficiency, and the like. The heterocyclic quaternary ammonium salt molecules are dissociated in an acid solution to form halogen anions and quaternary ammonium salt cations, and a compact protective film is formed on the surface of the metal, so that a corrosion inhibition effect is achieved; meanwhile, the positive charges of the quaternary ammonium salt interact with cell walls carrying negative charges on the surfaces of bacteria, so that the sterilization effect can be achieved. Research shows that the whole process of the protective film adsorbed on the metal surface is determined by the chemical structure of the corrosion inhibitor, the property of the metal, the charged surface, the distribution of charges in a reagent and other factors, and heterocyclic quaternary ammonium salt molecules have more pi electrons, large delocalization energy and large conjugated systems, so that the heterocyclic quaternary ammonium salt is more beneficial to being adsorbed on the metal surface and has better corrosion inhibition performance.
Next, the phosphorus-free multifunctional microcapsule scale inhibitor prepared in the above embodiment is subjected to scale inhibition performance test, static corrosion inhibition performance test and antibacterial performance test, respectively.
Testing scale inhibition performance by gel breaking method at room temperature3The content was varied. Specifically, the phosphorus-free multifunctional microcapsule scale inhibitor is added into 1L of simulated formation water containing scale impurities and having the same components according to concentration gradients of 10mg/L, 25mg/L, 50mg/L, 75mg/L and 100mg/L, and then the scale inhibition efficiency is determined after 4h of stabilization at the temperature of 25 ℃, and specific test results are shown in the following table 1.
TABLE 1
As can be seen from table 1, the phosphorus-free multifunctional core was discharged by means of extrusion gel breaking at room temperature to confirm the scale inhibition ability. Wherein, the scale inhibitor efficiency of the phosphorus-free multifunctional microcapsule scale inhibitor shows a trend of obviously increasing along with the increase of the concentration of the phosphorus-free scale inhibitor in the phosphorus-free multifunctional inner core. In addition, in the test process, when the extrusion gel breaking operation is not adopted, the scale inhibition efficiency is about 1% after 4 hours of adding the phosphorus-free multifunctional microcapsule scale inhibitor, so that the prepared phosphorus-free multifunctional microcapsule scale inhibitor has a slow release effect and effectively relieves the problem of water solubility loss of the phosphorus-free multifunctional inner core. In other embodiments, of course, according to different use requirements, other materials may be selected to prepare the microcapsule shell layer, for example, natural rubber materials, so as to change the slow release speed of the phosphorus-free multifunctional microcapsule scale inhibitor.
And (3) testing static corrosion inhibition performance, namely evaluating the corrosion inhibition performance of the phosphorus-free multifunctional microcapsule scale inhibitor according to the static weightlessness of a rotating hanging piece method (GB/T18175-2014) for testing the corrosion inhibition performance of the water treatment agent. The experiment selects A3 steel as a test piece, and is carried out under the conditions of normal pressure and 90 ℃, so as to obtain the corrosion rate v (g.m) of 15 percent (mass fraction) hydrochloric acid solution added with corrosion inhibitors with different concentrations-2·h-1) Thus calculating the corresponding corrosion inhibition ratio IE (%). Wherein the surface area of the A3 steel test piece is 1cm2Adding a certain amount of prepared hydrochloric acid solution with the mass fraction of 15% and the calibrated concentration into a three-neck flask, respectively adding 0, 0.1%, 0.2%, 0.3%, 0.4%, 0.5% and 1.0% of phosphorus-free multifunctional microcapsule scale inhibitor relative to the mass fraction of hydrochloric acid, placing the three-neck flask into a water bath after the phosphorus-free multifunctional microcapsule scale inhibitor is extruded, crushed, released and dissolved, slowly raising the temperature to 90 ℃, hanging a test piece single piece to enable the acid solution to be in contact with the whole surface of the test piece, recording the time, and keeping static and constant temperature. And after 4h, disconnecting the power supply, taking out the test piece, washing the test piece with distilled water, scrubbing with a brush, finally soaking and cleaning with absolute ethyl alcohol and acetone, drying with a blower by cold air, placing on clean filter paper in the order from small to large, and weighing (accurate to 0.0001g) after the interlayer is wrapped.
Experiments are carried out on the phosphorus-free multifunctional microcapsule scale inhibitor containing six different quaternary ammonium salt corrosion inhibitors, and a test experiment for maintaining the corrosion inhibition performance of A3 steel sheets for 4 hours in a 15% hydrochloric acid reagent containing 90 ℃ is carried out, wherein specific corrosion inhibition data are shown in Table 2.
TABLE 2
According to the data in Table 2, it can be seen that the corrosion rate of the A3 steel test piece without the multifunctional microcapsule scale inhibitor is 1195.17g m-2·h-1With the increase of the content of the phosphorus-free multifunctional microcapsule scale inhibitor with the core material with the corrosion inhibition function, the corrosion speed is obviously reduced, the corrosion inhibition effect is obviously increased, and the effect of inhibiting corrosion and protecting a metal pipeline can be achieved.
The antibacterial performance test judges the concentration of bacteria by a filter core containing the phosphorus-free multifunctional microcapsule scale inhibitor by adopting a colony counting method, and 2 times of biological repetition and 3 times of technical repetition are carried out. The volume of 30L of the bacteria liquid water is controlled to completely pass through the filter element within 3-5h, so that the subsequent sampling is convenient. The sterilization work is carried out on the test equipment in a circulating mode of tap water, distilled water and high-temperature steam, so that the basic bacteria in the equipment can be eliminated during the test, and the baseline is stable. The filtering effect is shown in percentage form, and the calculation formula is [ log ═10(concentration before filtration) -log10(concentration after filtration)]/log10(concentration before filtration) 100%. The test strain is Brevundimonas diminuta standard strain ATCC 19146. The filter element containing the phosphorus-free multifunctional microcapsule scale inhibitor is compared with a blank filter element set for comparison, and specific test data are shown in table 3.
TABLE 3
According to the antibacterial test result, the filter element containing the multifunctional microcapsule slow-release scale inhibitor has good filtering effect which can be 105The order of CFU/mL is reduced to 101CFU/mL, reduced by 4 orders of magnitude, the initial filtration effect is 67.36%, and as time increases, the filtration effect after 30L bacterial suspension is filtered81.49% of fruits; the blank filter element has almost no filtering effect, and the concentration of the bacterial suspension is continuously 105Of the order of CFU/mL.
While the foregoing is directed to embodiments of the present invention, other modifications and variations of the present invention may be devised by those skilled in the art in light of the above teachings. It should be understood by those skilled in the art that the foregoing detailed description is for the purpose of better explaining the present invention, and the scope of the present invention should be determined by the scope of the appended claims.
Claims (10)
1. The phosphorus-free multifunctional microcapsule scale inhibitor is characterized by comprising a phosphorus-free multifunctional inner core and a microcapsule shell, wherein the phosphorus-free multifunctional inner core contains the phosphorus-free scale inhibitor and a corrosion-inhibiting antibacterial agent, and the microcapsule shell is a slow release shell and is coated outside the phosphorus-free multifunctional inner core.
2. The phosphorus-free multifunctional microcapsule scale inhibitor according to claim 1, wherein the phosphorus-free scale inhibitor in the phosphorus-free multifunctional inner core comprises any one or more of polyepoxysuccinic acid, polyaspartic acid, acrylic acid sulfonic acid copolymer, benzotriazole, citrate, sodium molybdate and maleic anhydride; and/or the corrosion inhibition antibacterial agent in the phosphorus-free multifunctional inner core is heterocyclic base quaternary ammonium salt and comprises any one or a mixture of more of chlorinated-1-methylquinoline, chlorinated-1-naphthylmethylpyridine, brominated-1-ethylpyridine, chlorinated-1-naphthylmethylquinoline and brominated-1-ethylquinoline.
3. The phosphorus-free multifunctional microcapsule scale inhibitor of claim 1, wherein the microcapsule shell is made of butadiene-styrene copolymer and is formed by condensation polymerization at an oil-water interface.
4. A preparation method of a phosphorus-free multifunctional microcapsule scale inhibitor, which is used for preparing the phosphorus-free multifunctional microcapsule scale inhibitor of any one of claims 1 to 3, and specifically comprises the following steps:
step S1, coating the shell of the microcapsule: firstly, dissolving the material of the microcapsule shell in a dissolving agent, and then dispersing the material of the phosphorus-free multifunctional inner core in the dissolving agent in which the material of the microcapsule shell is dissolved to form polymer emulsion dispersion liquid; then, dropwise adding an emulsion initiator into the polymer emulsion dispersion liquid, guiding the material of the shell layer of the microcapsule to coagulate by using the emulsion initiator, and coating the phosphorus-free multifunctional inner core through the solution performance difference;
step S2, solidifying the shell layer of the microcapsule: placing the polymer emulsion dispersion liquid dropwise added with the emulsification initiator in the step S1 into a container filled with n-heptane for stirring, and carrying out microcapsule shell layer curing;
step S3, microcapsule collection: and (4) depositing the solution stirred in the step (S2) to separate the microcapsules after shell layer solidification, and then cleaning and drying the separated microcapsules to obtain the phosphorus-free multifunctional microcapsule scale inhibitor.
5. The preparation method of the phosphorus-free multifunctional microcapsule scale inhibitor according to claim 4, further comprising a step S4 of recovering a solvent: and (4) heating and stirring the solution for separating the microcapsules in the step S3, and condensing and recovering n-heptane and the emulsification initiator by adopting a distillation mode.
6. The preparation method of the phosphorus-free multifunctional microcapsule scale inhibitor according to claim 5, wherein in the step S1, the microcapsule shell is made of 1-10 g of butadiene-styrene copolymer, the solvent is 10-50 mL of dichloromethane solution, and the emulsification initiator is 10-20 mL of dimethyl siloxane.
7. The preparation method of the phosphorus-free multifunctional microcapsule scale inhibitor according to claim 6, wherein in the step S1, the mass ratio of the material of the phosphorus-free multifunctional inner core to the material of the microcapsule shell is 1: 1-5: 1.
8. The method for preparing the phosphorus-free multifunctional microcapsule scale inhibitor according to claim 6, wherein in the step S1, the material of the phosphorus-free multifunctional core is fully dispersed in the solvent in which the material of the microcapsule shell is dissolved at a rotation speed of 200 to 550 rpm.
9. The preparation method of the phosphorus-free multifunctional microcapsule scale inhibitor according to claim 6, wherein in the step S2, the stirring temperature is 20-60 ℃, the stirring speed is 200-550 rpm, and the stirring time is not less than 1 hour.
10. The application of the phosphorus-free multifunctional microcapsule scale inhibitor according to any one of claims 1 to 3, which is applied to scale inhibition, antibiosis and corrosion inhibition treatment of water systems such as urban water supply, factory sewage treatment and the like.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115228437A (en) * | 2022-08-18 | 2022-10-25 | 四川轻化工大学 | Surface modification method for making surface of activated carbon positive |
| CN118388059A (en) * | 2024-06-26 | 2024-07-26 | 西安水创新材料科技有限公司 | Solid slightly-soluble controllable release scale inhibitor and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2261293C1 (en) * | 2004-04-14 | 2005-09-27 | Открытое акционерное общество "НАПОР" | Method of preparing corrosion inhibitor-bactericide for hydrogen sulfide-containing and acidic media |
| CN108002554A (en) * | 2017-11-09 | 2018-05-08 | 王林双 | The preparation method and slow-release scale inhibitor of a kind of slow-release scale inhibitor |
| CN108251097A (en) * | 2017-12-28 | 2018-07-06 | 中国石油大学(北京) | A kind of microcapsule degelling agent and its preparation method and application |
| CN108483685A (en) * | 2018-05-25 | 2018-09-04 | 安徽智博新材料科技有限公司 | A kind of preparation method of industrial circulating cooling water slow-release research of non-phosphorus scale inhibitor |
| CN108569777A (en) * | 2018-04-24 | 2018-09-25 | 常州市蒽盗钟情生物科技有限公司 | A kind of scale inhibitor microcapsules and preparation method thereof |
| CN110273157A (en) * | 2018-03-14 | 2019-09-24 | 中国石油化工股份有限公司 | Corrosion inhibiter and preparation method with sterilization scale inhibition function |
-
2022
- 2022-04-20 CN CN202210418397.0A patent/CN114772756A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2261293C1 (en) * | 2004-04-14 | 2005-09-27 | Открытое акционерное общество "НАПОР" | Method of preparing corrosion inhibitor-bactericide for hydrogen sulfide-containing and acidic media |
| CN108002554A (en) * | 2017-11-09 | 2018-05-08 | 王林双 | The preparation method and slow-release scale inhibitor of a kind of slow-release scale inhibitor |
| CN108251097A (en) * | 2017-12-28 | 2018-07-06 | 中国石油大学(北京) | A kind of microcapsule degelling agent and its preparation method and application |
| CN110273157A (en) * | 2018-03-14 | 2019-09-24 | 中国石油化工股份有限公司 | Corrosion inhibiter and preparation method with sterilization scale inhibition function |
| CN108569777A (en) * | 2018-04-24 | 2018-09-25 | 常州市蒽盗钟情生物科技有限公司 | A kind of scale inhibitor microcapsules and preparation method thereof |
| CN108483685A (en) * | 2018-05-25 | 2018-09-04 | 安徽智博新材料科技有限公司 | A kind of preparation method of industrial circulating cooling water slow-release research of non-phosphorus scale inhibitor |
Non-Patent Citations (1)
| Title |
|---|
| 王晓娜: "杂环碱季铵盐的结构与缓蚀性能的关系", 中国优秀硕士学位论文全文数据库 工程科技I辑, pages 20 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115228437A (en) * | 2022-08-18 | 2022-10-25 | 四川轻化工大学 | Surface modification method for making surface of activated carbon positive |
| CN115228437B (en) * | 2022-08-18 | 2023-10-31 | 四川轻化工大学 | Surface modification method for making active carbon surface positive |
| CN118388059A (en) * | 2024-06-26 | 2024-07-26 | 西安水创新材料科技有限公司 | Solid slightly-soluble controllable release scale inhibitor and preparation method thereof |
| CN118388059B (en) * | 2024-06-26 | 2024-09-20 | 西安水创新材料科技有限公司 | Solid slightly-soluble controllable release scale inhibitor and preparation method thereof |
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