Concentrated water reverse osmosis scale inhibitor and preparation method thereof
By introducing boron and zinc into dendrimer scale inhibitors and condensing with polybutylene succinate prepolymers, the problems of insufficient long-term effect and slow biodegradation of existing scale inhibitors are solved, and higher stability, long-term effect and biodegradability are achieved.
Patent Information
- Application Number
- CN202510398431.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-01
- Publication Date
- 2025-06-27
AI Technical Summary
The existing dendrimer scale inhibitors have insufficient long-term effect on scale inhibition and are slow in biodegradation, which has potential impact on the ecological environment.
The tree-like structure is constructed through the esterification reaction of pentaerythritol and acrylic acid, and boron and zinc are introduced into the tree-like structure to replace the traditional phosphorus elements and reduce potential harm to the environment. Meanwhile, the polybutylene succinate (PBS) segment is attached to the dendrimer by condensation with the polybutylene succinate prepolymer, thereby enhancing the biodegradability of the scale inhibitor.
It enhances the ability of scale inhibitors to inhibit different types of scales, improves their stability and long-term effectiveness in water, promotes their biodegradability, and reduces potential harm to the ecological environment.
Smart Images
Figure CN120209327A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of the preparation of reverse osmosis scale inhibitors, and more particularly to a reverse osmosis scale inhibitor for concentrated water and a preparation method thereof. Background Art
[0002] The reverse osmosis system is a membrane separation technology driven by a pressure difference. In this system, pressure is applied to the raw water by a high-pressure pump, enabling water to overcome the osmotic pressure and pass through the semi-permeable membrane. The semi-permeable membrane can block dissolved salts, colloids, organic matter, bacteria, and other impurities in the water, thus achieving water purification. However, during the reverse osmosis process, as water continuously passes through the membrane, the concentration of these ions gradually increases on the concentrated water side. With the occurrence of concentration polarization, the ion concentration may exceed its saturation solubility, resulting in precipitation and deposition on the surface of the reverse osmosis membrane. To solve this problem, a reverse osmosis scale inhibitor for concentrated water is generally added to the reverse osmosis system to prevent scale formation on the surface of the reverse osmosis membrane.
[0003] Traditional reverse osmosis scale inhibitors for concentrated water are generally divided into the following categories: phosphorus-containing small molecule scale inhibitors, polymer scale inhibitors, and natural dispersants. However, these traditional polymers have the drawbacks of self-winding and self-adhesion. To solve the problems of traditional scale inhibitors, dendritic polymer scale inhibitors have been developed. Their unique dendritic spherical structure provides a scale and fouling resistance effect, and also overcomes the drawbacks of self-winding and self-adhesion of traditional polymers, making them more stable, phosphorus-free, and avoiding problems such as microbial growth and membrane fouling caused by phosphorus components. However, the existing dendritic polymer scale inhibitors have insufficient long-term scale inhibition effect and slow biodegradation rate, which may have a potential impact on the ecological environment.
[0004] Therefore, it is necessary to design a new reverse osmosis scale inhibitor for concentrated water to solve the problems of the existing dendritic polymer scale inhibitors, such as insufficient long-term scale inhibition effect, slow biodegradation rate, and potential impact on the ecological environment. Summary of the Invention
[0005] In view of this, the present invention provides a reverse osmosis scale inhibitor for concentrated water, aiming to solve the problems of the existing dendritic polymer scale inhibitors, such as insufficient long-term scale inhibition effect, slow biodegradation rate, and potential impact on the ecological environment.
[0006] On the one hand, the present invention provides a reverse osmosis scale inhibitor for concentrated water, comprising the following components in parts by mass:
[0007] 8 - 10 parts of pentaerythritol, 10 - 30 parts of acrylic acid, 10 - 30 parts of triallyl borate monomer, 5 - 10 parts of zinc acrylate monomer, 3 - 6 parts of vinylsulfonic acid monomer, and 10 - 30 parts of poly(butylene succinate) prepolymer.
[0008] On the other hand, the present invention also provides a method for preparing a scale inhibitor for reverse osmosis of concentrated water, comprising the following steps:
[0009] Mix pentaerythritol, toluenesulfonic acid catalyst and acrylic acid for the first time, and obtain a first mixture after stirring;
[0010] Dissolve the first mixture in toluene, add triallyl borate monomer and azobisisobutyronitrile initiator, conduct a second mixing, cool to room temperature after stirring, and obtain a second mixture after the first treatment;
[0011] Dissolve the second mixture in toluene, add zinc acrylate monomer and azobisisobutyronitrile initiator, conduct a third mixing, cool to room temperature after stirring, and obtain a third mixture after the first treatment;
[0012] Dissolve the third mixture and vinylsulfonic acid monomer in a toluene solution, add azobisisobutyronitrile initiator, conduct a fourth mixing, and obtain a fourth mixture after the second treatment after the reaction ends;
[0013] Add polybutylene succinate prepolymer and tetrabutyl titanate to the fourth mixture for the fifth mixing, and obtain the scale inhibitor for reverse osmosis of concentrated water after the third treatment after the reaction ends.
[0014] Further, collect the generated water during the first mixing, and after the end, conduct vacuum distillation on the first mixture.
[0015] Further, the method of vacuum distillation is as follows: start from normal pressure, reduce to 20 mmHg at a speed of 10 - 20 mmHg / min, and the distillation temperature is 80 - 90 °C.
[0016] Further, the stirring speed of the first mixing is 300 - 500 revolutions per minute, the time is 12 - 24 hours, and the temperature is 80 - 100 °C; the stirring speed of the second mixing is 400 - 600 revolutions per minute, the time is 6 - 10 hours, and the temperature is 60 - 80 °C; the stirring speed of the third mixing is 400 - 600 revolutions per minute, the time is 6 - 10 hours, and the temperature is 60 - 80 °C; the stirring speed of the fourth mixing is 400 - 600 revolutions per minute, the time is 4 - 8 hours, and the temperature is 60 - 80 °C; the stirring speed of the fifth mixing is 400 - 600 revolutions per minute, the time is 8 - 16 hours, and the temperature is 120 - 150 °C;.
[0017] Further, the method of the first treatment is as follows: Pour the reaction solution into methanol at 0 - 5°C, stir the methanol solution, filter out the precipitate, wash the precipitate with methanol at 0 - 5°C for 3 - 5 times, then perform secondary washing with n - hexane, also wash for 3 - 5 times, and after washing, dry the precipitate. The drying temperature is 40 - 50°C, the vacuum degree is 0.08 - 0.09 MPa, and the drying time is 12 - 24 hours.
[0018] Further, before the fourth mixing, pre - activate the third mixture: Dry the third mixture in an environment of 60 - 70°C and a vacuum degree of 0.08 - 0.09 MPa for 2 - 3 hours.
[0019] Further, the method of the second treatment is as follows: Centrifuge the reaction solution at a speed of 8000 - 10000 revolutions per minute for 10 - 15 minutes, then filter out the precipitate. Subsequently, first wash the precipitate with acetone for 2 - 3 times, with the amount of each washing solution being 3 - 4 times the volume of the precipitate, then wash with water for 3 - 5 times, with the amount of each time being 4 - 5 times the volume of the precipitate. Finally, dry the precipitate. The drying temperature is 50 - 60°C, the vacuum degree is 0.09 - 0.1 MPa, and the drying time is 12 - 24 hours.
[0020] Further, before the fifth mixing, melt the polybutylene succinate prepolymer at 120 - 130°C and keep it in a molten state under nitrogen protection for 10 - 15 minutes.
[0021] Further, the method of the third treatment is as follows: After cooling the product to room temperature, first drop the product solution into cold petroleum ether at 0 - 5°C, filter to remove impurities, then continue to drop the remaining solution into cold petroleum ether at 0 - 5°C, filter out the precipitate, wash the precipitate with cold petroleum ether at 0 - 5°C for 3 - 5 times, with the amount of each washing solution being 4 - 5 times the volume of the precipitate. Finally, dry the precipitate. The drying conditions are a temperature of 40 - 50°C, a pressure of 8 - 10 MPa, and a drying time of 6 - 8 hours.
[0022] Compared with the prior art, the beneficial effects of the present invention are as follows: Construct a dendritic structure through the esterification reaction of pentaerythritol and acrylic acid, and then introduce boron and zinc elements onto the dendritic structure to replace the traditional phosphorus element, reducing the potential harm to the environment while utilizing the characteristics of its multi - functional groups and high dispersibility to enhance the inhibition ability of the scale inhibitor against different types of scale and improve its stability and long - term effectiveness in water. Then, connect the polybutylene succinate (PBS) chain segment to the dendritic polymer by condensation with the polybutylene succinate prepolymer to improve the biodegradability of the scale inhibitor. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Upon reading the following detailed description of the preferred embodiments, various other advantages and benefits will become apparent to those of ordinary skill in the art. The drawings are only for the purpose of showing the preferred embodiments and are not to be considered as limiting the present invention. Also, throughout the drawings, the same reference numerals are used to denote the same components. In the drawings:
[0024] Figure 1 It is a flowchart of the preparation method of the concentrated water reverse osmosis scale inhibitor provided by the embodiment of the present invention. Specific embodiments
[0025] The exemplary embodiments of the present disclosure will be described in more detail below with reference to the drawings. Although the exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided so that the present disclosure can be more thoroughly understood and the scope of the present disclosure can be fully conveyed to those skilled in the art. It should be noted that, without conflict, the embodiments in the present invention and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the drawings and in combination with the embodiments.
[0026] On the one hand, in some embodiments of the present application, a concentrated water reverse osmosis scale inhibitor includes the following components in parts by mass:
[0027] Pentaerythritol 8 - 10 parts, acrylic acid 10 - 30 parts, triallyl borate monomer 10 - 30 parts, zinc acrylate monomer 5 - 10 parts, vinylsulfonic acid monomer 3 - 6 parts, and polybutylene succinate prepolymer 10 - 30 parts.
[0028] The components of the concentrated water reverse osmosis scale inhibitor in the present invention preferably include: pentaerythritol 9 - 10 parts, acrylic acid 20 - 30 parts, triallyl borate monomer 20 - 30 parts, zinc acrylate monomer 8 - 10 parts, vinylsulfonic acid monomer 4 - 6 parts, and polybutylene succinate prepolymer 20 - 30 parts.;
[0029] The components of the concentrated water reverse osmosis scale inhibitor in the present invention are further preferably: pentaerythritol 10 parts, acrylic acid 30 parts, triallyl borate monomer 30 parts, zinc acrylate monomer 10 parts, vinylsulfonic acid monomer 6 parts, and polybutylene succinate prepolymer 30 parts.;
[0030] On the other hand, in some embodiments of the present application, a preparation method of a concentrated water reverse osmosis scale inhibitor is provided, including the following steps:
[0031] Mix pentaerythritol, p - toluenesulfonic acid catalyst, and acrylic acid for the first time, and obtain a first mixture after stirring;
[0032] Dissolve the first mixture in toluene, add triallyl borate monomer and azobisisobutyronitrile initiator, conduct a second mixing, cool to room temperature after stirring, and obtain a second mixture through a first treatment;
[0033] Dissolve the second mixture in toluene, add zinc acrylate monomer and azobisisobutyronitrile initiator, conduct a third mixing, cool to room temperature after stirring, and obtain a third mixture after the first treatment;
[0034] Dissolve the third mixture and vinylsulfonic acid monomer in a toluene solution, add azobisisobutyronitrile initiator, conduct a fourth mixing, and obtain a fourth mixture after a second treatment after the reaction ends;
[0035] Add polybutylene succinate prepolymer and tetrabutyl titanate to the fourth mixture, conduct a fifth mixing, and obtain the concentrated water reverse osmosis scale inhibitor after a third treatment after the reaction ends.
[0036] Specifically, when adding the acrylic acid, it should be slowly dropped under nitrogen protection.
[0037] It can be understood that a dendritic structure is constructed through the esterification reaction of pentaerythritol and acrylic acid, and then boron and zinc elements are introduced into the dendritic structure to replace the traditional phosphorus element, reducing the potential harm to the environment while utilizing its multi-functional group and high dispersibility characteristics to enhance the inhibition ability of the scale inhibitor against different types of scale and improve its stability and long-term effectiveness in water. Then, the polybutylene succinate (PBS) chain segment is connected to the dendritic polymer by condensation with the polybutylene succinate prepolymer to improve the biodegradability of the scale inhibitor.
[0038] In some embodiments of the present application, the water generated during the first mixing is collected, and after the end, the first mixture is subjected to vacuum distillation.
[0039] Specifically, an oil-water separator can be used to collect the generated water.
[0040] It can be understood that collecting the water generated during the reaction is equivalent to reducing the concentration of the generated water. According to Le Chatelier's principle, the reaction system will automatically adjust to restore equilibrium, thereby promoting the reaction to proceed in the direction of generating more products (the first-generation dendritic acrylate), thus improving the conversion rate and yield of the reaction.
[0041] In some embodiments of the present application, the method of vacuum distillation is as follows: starting from normal pressure, reducing to 20 mmHg at a rate of 10 - 20 mmHg / min, and the distillation temperature is 80 - 90 °C; preferably, reducing to 20 mmHg at a rate of 10 mmHg / min, and the distillation temperature is 90 °C.
[0042] It is understandable that gradually reducing the system pressure can remove unreacted acrylic acid and the generated water more gently, while avoiding the decomposition of the product due to overheating.
[0043] In some embodiments of the present application, the stirring speed of the first mixing is 300 - 500 revolutions per minute, the time is 12 - 24 hours, and the temperature is 80 - 100 °C; the stirring speed of the second mixing is 400 - 600 revolutions per minute, the time is 6 - 10 hours, and the temperature is 60 - 80 °C; the stirring speed of the third mixing is 400 - 600 revolutions per minute, the time is 6 - 10 hours, and the temperature is 60 - 80 °C; the stirring speed of the fourth mixing is 400 - 600 revolutions per minute, the time is 4 - 8 hours, and the temperature is 60 - 80 °C; the stirring speed of the fifth mixing is 400 - 600 revolutions per minute, the time is 8 - 16 hours, and the temperature is 120 - 150 °C.
[0044] Preferably, the stirring speed of the first mixing is 500 revolutions per minute, the time is 24 hours, and the temperature is 100 °C; the stirring speed of the second mixing is 600 revolutions per minute, the time is 10 hours, and the temperature is 80 °C; the stirring speed of the third mixing is 600 revolutions per minute, the time is 10 hours, and the temperature is 80 °C; the stirring speed of the fourth mixing is 600 revolutions per minute, the time is 8 hours, and the temperature is 80 °C; the stirring speed of the fifth mixing is 600 revolutions per minute, the time is 16 hours, and the temperature is 150 °C.
[0045] In some embodiments of the present application, the method of the first treatment is: pouring the reaction solution into methanol at 0 - 5 °C, stirring the methanol solution, filtering out the precipitate, washing the precipitate with methanol at 0 - 5 °C for 3 - 5 times, then, performing secondary washing with n - hexane, also washing 3 - 5 times, and drying the precipitate after washing, the drying temperature is 40 - 50 °C, the vacuum degree is 0.08 - 0.09 MPa, and the drying time is 12 - 24 hours.
[0046] It is understandable that a low - temperature environment helps to reduce the solubility of the polymer, making it easier to precipitate from the solution. First washing with cold methanol can reduce the dissolution loss of the polymer during washing. At the same time, low temperature helps to maintain the structural stability of the polymer, and secondary washing with n - hexane further removes residual toluene and other organic impurities, improves the purity of the product, and reduces the influence of impurities on subsequent reactions or product performance.
[0047] In some embodiments of the present application, before the fourth mixing, the third mixture is pre - activated: drying the third mixture for 2 - 3 hours in an environment of 60 - 70 °C and a vacuum degree of 0.08 - 0.09 MPa.
[0048] It is understandable that drying the polymer in advance can remove the possibly adsorbed moisture and a small amount of volatile impurities, better expose the surface active groups of the polymer, and is beneficial to the reaction with the vinylsulfonic acid monomer.
[0049] In some embodiments of the present application, the method of the second treatment is: centrifuging the reaction solution at a speed of 8000 - 10000 revolutions per minute for 10 - 15 minutes, then filtering out the precipitate, subsequently washing the precipitate with acetone 2 - 3 times, with the amount of washing liquid each time being 3 - 4 times the volume of the precipitate, then washing with deionized water 3 - 5 times, with the amount each time being 4 - 5 times the volume of the precipitate, and finally drying the precipitate, with the drying temperature being 50 - 60 °C, the vacuum degree being 0.09 - 0.1 MPa, and the drying time being 12 - 24 hours.
[0050] In some embodiments of the present application, before the fifth mixing, the polybutylene succinate prepolymer is melted at 120 - 130 °C and kept in a molten state for 10 - 15 minutes under nitrogen protection.
[0051] It is understandable that melting the polybutylene succinate prepolymer can effectively remove the possible bubbles and moisture therein.
[0052] In some embodiments of the present application, the method of the third treatment is: after cooling the product to room temperature, first dropping the product solution into cold petroleum ether at 0 - 5 °C, filtering to remove impurities, then continuing to drop the remaining solution into cold petroleum ether at 0 - 5 °C, filtering out the precipitate, washing the precipitate with cold petroleum ether at 0 - 5 °C 3 - 5 times, with the amount of washing liquid each time being 4 - 5 times the volume of the precipitate, and finally drying the precipitate, with the drying conditions being a temperature of 40 - 50 °C, a pressure of 8 - 10 MPa, and a drying time of 6 - 8 hours.
[0053] Example 1
[0054] S1. Mix 8 parts of pentaerythritol and 0.1 part of p - toluenesulfonic acid catalyst, and drop 10 parts of acrylic acid under nitrogen protection, stir and react at a constant temperature of 80 °C at a speed of 300 revolutions per minute for 12 hours. During the reaction, collect the generated water through an oil - water separator. After the reaction, remove the unreacted acrylic acid and a small amount of moisture by vacuum distillation. When performing vacuum distillation, start from normal pressure and reduce the pressure to the final pressure of 20 mmHg at a speed of 20 mmHg / min, and control the distillation temperature at 80 °C to obtain the first mixture.
[0055] S2. Dissolve the first mixture in 50 parts of toluene, add 10 parts of triallyl borate monomer and 0.1 part of azobisisobutyronitrile initiator, and stir and react at a speed of 400 revolutions per minute at 60 °C for 6 hours. After the reaction is completed, cool to room temperature, pour the reaction solution into methanol at 0 - 5 °C, stir the methanol solution, filter out the precipitate, wash it 3 times with cold methanol at 0 - 5 °C, then perform secondary washing with n - hexane, also wash 3 times. After washing, dry the precipitate. The drying temperature is 40 °C, the vacuum degree is 0.08 MPa, and the drying time is 12 hours to obtain the second mixture.
[0056] S3. Dissolve the second mixture in 100 parts of toluene, add 5 parts of zinc acrylate monomer and 0.1 part of azobisisobutyronitrile initiator, and stir and react at a speed of 400 revolutions per minute at 60 °C for 6 hours. After the reaction is completed, cool to room temperature, pour the reaction solution into methanol at 0 - 5 °C, stir the methanol solution, filter out the precipitate, wash it 3 times with cold methanol at 0 - 5 °C, then perform secondary washing with n - hexane, also wash 3 times. After washing, dry the precipitate. The drying temperature is 40 °C, the vacuum degree is 0.08 MPa, and the drying time is 12 hours to obtain the third mixture.
[0057] S4. Dry the third mixture in an environment of 60 °C and a vacuum degree of 0.08 MPa for 2 hours, then add it together with 3 parts of vinylsulfonic acid monomer to 100 parts of toluene solution. Subsequently, add 0.1 part of azobisisobutyronitrile initiator, and stir at a speed of 400 revolutions per minute at 60 °C for 4 hours. After the reaction ends, first centrifuge the reaction solution (rotation speed is 8000 revolutions per minute) for 10 minutes, then filter out the precipitate. Subsequently, wash the precipitate with acetone 2 times, with the amount of each washing solution being 3 times the volume of the precipitate, and then wash it 3 times with water, with the amount of each use being 4 times the volume of the precipitate. Finally, dry the precipitate. The drying temperature is 50 °C, the vacuum degree is 0.09 MPa, and the drying time is 12 hours to obtain the fourth mixture.
[0058] S5. Melt 10 parts of polybutylene succinate prepolymer at 120 °C and keep it in a molten state for 10 minutes under nitrogen protection. Then add it to the fourth mixture, add 0.5 part of tetrabutyl titanate, and stir at a speed of 400 revolutions per minute at 120 °C for 8 hours. After the reaction ends, cool the product to room temperature, and then drop the product solution into a small amount of cold petroleum ether (0 - 5 °C) to precipitate out some impurities and oligomers, and filter them out. Then, continue to drop the remaining solution into a large amount of cold petroleum ether to precipitate the target product. After filtration, wash the precipitate with cold petroleum ether 3 times, with the amount of each washing solution being 4 times the volume of the precipitate. Finally, dry the washed precipitate. The drying conditions are a temperature of 40 °C, a pressure of 8 MPa, and a drying time of 6 hours to obtain the concentrated water reverse osmosis scale inhibitor.
[0059] Example 2
[0060] S1. Mix 9 parts of pentaerythritol and 0.2 part of p-toluenesulfonic acid catalyst, and dropwise add 20 parts of acrylic acid under nitrogen protection. Stir the reaction at a constant temperature of 100 °C at a speed of 500 revolutions per minute for 24 hours. During the reaction process, collect the generated water through an oil-water separator. After the reaction, remove the unreacted acrylic acid and a small amount of water by vacuum distillation. When performing vacuum distillation, start from normal pressure and reduce the pressure to the final pressure of 20 mmHg at a speed of 10 mmHg / min, and control the distillation temperature at 90 °C to obtain the first mixture.
[0061] S2. Dissolve the first mixture in 75 parts of toluene, add 20 parts of triallyl borate monomer and 0.2 part of azobisisobutyronitrile initiator, and stir the reaction at 80 °C at a speed of 600 revolutions per minute for 10 hours. After the reaction, cool to room temperature, pour the reaction solution into methanol at 0 - 5 °C, stir the methanol solution, filter out the precipitate, wash it 5 times with cold methanol at 0 - 5 °C, then perform secondary washing with n-hexane, also wash 5 times. After washing, dry the precipitate at a drying temperature of 50 °C, a vacuum degree of 0.09 MPa, and a drying time of 24 hours to obtain the second mixture.
[0062] S3. Dissolve the second mixture in 125 parts of toluene, add 8 parts of zinc acrylate monomer and 0.2 part of azobisisobutyronitrile initiator, and stir the reaction at 80 °C at a speed of 600 revolutions per minute for 10 hours. After the reaction, cool to room temperature, pour the reaction solution into methanol at 0 - 5 °C, stir the methanol solution, filter out the precipitate, wash it 5 times with cold methanol at 0 - 5 °C, then perform secondary washing with n-hexane, also wash 5 times. After washing, dry the precipitate at a drying temperature of 50 °C, a vacuum degree of 0.09 MPa, and a drying time of 24 hours to obtain the third mixture.
[0063] S4. After drying the third mixture in an environment of 70 °C and a vacuum degree of 0.09 MPa for 3 hours, add it together with 4 parts of vinylsulfonic acid monomer to 125 parts of toluene solution, then add 0.2 part of azobisisobutyronitrile initiator, and stir at 80 °C at a speed of 600 revolutions per minute for 8 hours. After the reaction, first centrifuge the reaction solution (rotation speed: 10000 revolutions per minute) for 15 minutes, then filter out the precipitate. First, wash the precipitate 3 times with acetone, with the amount of each washing solution being 4 times the volume of the precipitate, then wash it 5 times with water, with the amount of each time being 5 times the volume of the precipitate. Finally, dry the precipitate at a drying temperature of 50 °C, a vacuum degree of 0.09 MPa, and a drying time of 12 hours to obtain the fourth mixture.
[0064] S5. Melt 20 parts of the polybutylene succinate prepolymer at 130 °C and keep it in the molten state for 15 minutes under nitrogen protection. Then add it to the fourth mixture, and further add 0.8 part of tetrabutyl titanate. Stir at a speed of 600 revolutions per minute at 150 °C for 16 hours. After completion, cool the product to room temperature and then drop the product solution into a small amount of cold petroleum ether (0 - 5 °C) to precipitate out some impurities and oligomers, and filter them out. Then, continue to drop the remaining solution into a large amount of cold petroleum ether to precipitate the target product. After filtration, wash the precipitate with cold petroleum ether 5 times, with the amount of washing liquid being 5 times the volume of the precipitate each time. Finally, dry the washed precipitate under the drying conditions of a temperature of 50 °C, a pressure of 10 MPa, and a drying time of 8 hours to obtain the concentrated water reverse osmosis scale inhibitor.
[0065] Example 3
[0066] S1. Mix 10 parts of pentaerythritol and 0.3 part of p-toluenesulfonic acid catalyst, and drop 30 parts of acrylic acid under nitrogen protection. Stir and react at a constant temperature of 100 °C at a speed of 500 revolutions per minute for 24 hours. During the reaction, collect the generated water through an oil-water separator. After the reaction is completed, remove the unreacted acrylic acid and a small amount of water by vacuum distillation. When performing vacuum distillation, start from normal pressure and reduce the pressure to the final pressure of 20 mmHg at a speed of 10 mmHg / min, and control the distillation temperature at 90 °C to obtain the first mixture.
[0067] S2. Dissolve the first mixture in 100 parts of toluene, add 30 parts of triallyl borate monomer and 0.3 part of azobisisobutyronitrile initiator, and stir and react at 80 °C at a speed of 600 revolutions per minute for 10 hours. After the reaction is completed, cool to room temperature, pour the reaction solution into methanol at 0 - 5 °C, stir the methanol solution, filter out the precipitate, wash it 5 times with cold methanol at 0 - 5 °C, and then perform secondary washing with n-hexane, also washing 5 times. After washing, dry the precipitate at a drying temperature of 50 °C, a vacuum degree of 0.09 MPa, and a drying time of 24 hours to obtain the second mixture.
[0068] S3. Dissolve the second mixture in 150 parts of toluene, add 10 parts of zinc acrylate monomer and 0.3 part of azobisisobutyronitrile initiator, and stir and react at 80 °C at a speed of 600 revolutions per minute for 10 hours. After the reaction is completed, cool to room temperature, pour the reaction solution into methanol at 0 - 5 °C, stir the methanol solution, filter out the precipitate, wash it 5 times with cold methanol at 0 - 5 °C, and then perform secondary washing with n-hexane, also washing 5 times. After washing, dry the precipitate at a drying temperature of 50 °C, a vacuum degree of 0.09 MPa, and a drying time of 24 hours to obtain the third mixture.
[0069] S4. After drying the third mixture in an environment of 70°C and a vacuum degree of 0.09 MPa for 3 hours, it is added together with 4 parts of vinylsulfonic acid monomer into 150 parts of toluene solution. Subsequently, 0.3 part of azobisisobutyronitrile initiator is added. Stirring is carried out at a speed of 600 revolutions per minute at 80°C for 8 hours. After completion, the reaction solution is first centrifuged (at a rotation speed of 10,000 revolutions per minute) for 15 minutes, then the precipitate is filtered out. Subsequently, the precipitate is washed with acetone 3 times, with the amount of washing liquid used each time being 4 times the volume of the precipitate, and then washed with water 5 times, with the amount used each time being 5 times the volume of the precipitate. Finally, the precipitate is dried, with the drying temperature being 50°C, the vacuum degree being 0.09 MPa, and the drying time being 12 hours to obtain the fourth mixture.
[0070] S5. 30 parts of polybutylene succinate prepolymer is melted at 130°C and kept in a molten state for 15 minutes under nitrogen protection. Subsequently, it is added to the fourth mixture, and 1 part of tetrabutyl titanate is added. Stirring is carried out at a speed of 600 revolutions per minute at 150°C for 16 hours. After completion, the product is cooled to room temperature, and then the product solution is dropped into a small amount of cold petroleum ether (0 - 5°C) to precipitate out some impurities and oligomers, which are filtered off. Then, the remaining solution is continuously dropped into a large amount of cold petroleum ether to precipitate the target product. After filtration, the precipitate is washed with cold petroleum ether 5 times, with the amount of washing liquid used each time being 5 times the volume of the precipitate. Finally, the washed precipitate is dried under the drying conditions of a temperature of 50°C, a pressure of 10 MPa, and a drying time of 8 hours to obtain the concentrated water reverse osmosis scale inhibitor.
[0071] Those skilled in the art should understand that the embodiments of the present application can be provided as methods, systems, or computer program products. Therefore, the present application can adopt the form of a complete hardware embodiment, a complete software embodiment, or an embodiment combining software and hardware aspects. Moreover, the present application can adopt the form of a computer program product implemented on one or more computer-usable storage media (including but not limited to disk storage, CD-ROM, optical storage, etc.) containing computer-usable program code.
[0072] The present application is described with reference to the flowcharts and / or block diagrams of methods, devices (systems), and computer program products according to the embodiments of the present application. It should be understood that each process and / or block in the flowcharts and / or block diagrams can be implemented by computer program instructions, and the combination of processes and / or blocks in the flowcharts and / or block diagrams can also be implemented by computer program instructions. These computer program instructions can be provided to the processors of general-purpose computers, special-purpose computers, embedded processors, or other programmable data processing devices to generate a machine, so that the instructions executed by the processors of the computer or other programmable data processing devices generate for implementing in the process Figure 1 a process or multiple processes and / or blocks Figure 1means for the functions specified in one or more boxes.
[0073] These computer program instructions can also be stored in a computer-readable memory that can direct a computer or other programmable data processing device to work in a specific manner, so that the instructions stored in the computer-readable memory produce a manufactured article including an instruction device, and the instruction device implements the functions specified in one Figure 1 process or multiple processes and / or boxes Figure 1 or the functions specified in multiple boxes.
[0074] These computer program instructions can also be loaded onto a computer or other programmable data processing device, so that a series of operation steps are executed on the computer or other programmable device to generate a computer-implemented process. Therefore, the instructions executed on the computer or other programmable device provide steps for implementing the functions specified in one Figure 1 process or multiple processes and / or boxes Figure 1 or the functions specified in multiple boxes.
[0075] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: the specific implementation manners of the present invention can still be modified or equivalently replaced, and any modification or equivalent replacement that does not depart from the spirit and scope of the present invention shall be covered by the protection scope of the claims of the present invention.
Claims
1. A concentrated water reverse osmosis scale inhibitor, characterized in that: The composition includes the following components in parts by weight: 8-10 parts of pentaerythritol, 10-30 parts of acrylic acid, 10-30 parts of triallyl borate monomer, 5-10 parts of zinc acrylate monomer, 3-6 parts of vinyl sulfonic acid monomer and 10-30 parts of polybutylene succinate prepolymer.
2. A method for preparing a concentrated water reverse osmosis scale inhibitor, characterized in that: The following steps are involved: The pentaerythritol, toluenesulfonic acid catalyst and acrylic acid are first mixed and stirred to obtain a first mixture; Dissolving the first mixture in toluene, adding triallyl borate monomer and azobisisobutyronitrile initiator, performing a second mixing, stirring and cooling to room temperature, and performing a first treatment to obtain a second mixture; The second mixture is dissolved in toluene, and zinc acrylate monomer and azobisisobutyronitrile initiator are added to perform a third mixing, and the mixture is stirred and cooled to room temperature, and the third mixture is obtained after the first treatment; The third mixture and the vinyl sulfonic acid monomer are dissolved in a toluene solution, an azobisisobutyronitrile initiator is added, and a fourth mixture is performed. After the reaction is completed, a second treatment is performed to obtain a fourth mixture; Polybutylene succinate prepolymer and tetrabutyl titanate are added to the fourth mixture, and a fifth mixing is performed. After the reaction is completed, the concentrated water reverse osmosis antiscalant is obtained by a third treatment.
3. The method for preparing the concentrated water reverse osmosis antiscalant according to claim 2, characterized in that: The generated water is collected during the first mixing and stirring, and after completion, the first mixture is subjected to reduced pressure distillation.
4. The method for preparing a concentrated water reverse osmosis antiscalant according to claim 3, characterized in that: The reduced pressure distillation method is: starting from normal pressure, reducing the pressure to 20 mmHg at a speed of 10-20 mmHg / min, and the distillation temperature is 80-90°C.
5. The method for preparing the concentrated water reverse osmosis antiscalant according to claim 2, characterized in that: The stirring speed of the first mixing is 300-500 rpm, the time is 12-24 hours, and the temperature is 80-100°C; the stirring speed of the second mixing is 400-600 rpm, the time is 6-10 hours, and the temperature is 60-80°C; the stirring speed of the third mixing is 400-600 rpm, the time is 6-10 hours, and the temperature is 60-80°C; the stirring speed of the fourth mixing is 400-600 rpm, the time is 4-8 hours, and the temperature is 60-80°C; the stirring speed of the fifth mixing is 400-600 rpm, the time is 8-16 hours, and the temperature is 120-150°C.
6. The method for preparing the concentrated water reverse osmosis antiscalant according to claim 2, characterized in that: The first treatment method is: pouring the reaction solution into methanol at 0-5°C, stirring the methanol solution, filtering out the precipitate, washing the precipitate with methanol at 0-5°C for 3-5 times, and then washing it twice with n-hexane, also washing it 3-5 times, and drying the precipitate after washing, the drying temperature is 40-50°C, the vacuum degree is 0.08-0.09MPa, and the drying time is 12-24 hours.
7. The method for preparing a concentrated water reverse osmosis antiscalant according to claim 2, characterized in that: Before the fourth mixing, the third mixture is pre-activated: the third mixture is dried for 2-3 hours at 60-70° C. and a vacuum degree of 0.08-0.09 MPa.
8. The method for preparing the concentrated water reverse osmosis antiscalant according to claim 2, characterized in that: The second treatment method is: centrifuge the reaction solution at a speed of 8000-10000 rpm for 10-15 minutes, then filter out the precipitate, then wash the precipitate with acetone 2-3 times, each time using 3-4 times the volume of the precipitate, then wash with water 3-5 times, each time using 4-5 times the volume of the precipitate, finally, dry the precipitate, the drying temperature is 50-60°C, the vacuum degree is 0.09-0.1MPa, and the drying time is 12-24 hours.
9. The method for preparing a concentrated water reverse osmosis antiscalant according to claim 2, characterized in that: Before the fifth mixing, the polybutylene succinate prepolymer is melted at 120-130° C. and kept in a molten state for 10-15 minutes under nitrogen protection.
10. The method for preparing the concentrated water reverse osmosis antiscalant according to claim 2, characterized in that: The third treatment method is: after the product is cooled to room temperature, the product solution is first added dropwise to cold petroleum ether at 0-5°C, and impurities are filtered out. Then, the remaining solution is continued to be added dropwise to cold petroleum ether at 0-5°C, and the precipitate is filtered out. The precipitate is washed 3-5 times with cold petroleum ether at 0-5°C, and the amount of washing liquid used each time is 4-5 times the volume of the precipitate. Finally, the precipitate is dried, and the drying conditions are a temperature of 40-50°C, a pressure of 8-10MPa, and a drying time of 6-8 hours.
Citation Information
Cited By
Anti-scaling agent for water with high calcium and magnesium content and preparation method of anti-scaling agent
CN122166940A