Antiscalant for use in ultrafiltration and reverse osmosis processes, and method for its preparation and use
By combining polyepoxysuccinic acid, polyaspartic acid, and composite adhesives, the stability and broad-spectrum properties of scale inhibitors in ultrafiltration and reverse osmosis processes are solved, effectively preventing and reducing various types of scale, and improving the operating efficiency and equipment life of water treatment systems.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- BEIJING WATER-RES ENVIRONMENT TECH CO LTD
- Filing Date
- 2024-12-20
- Publication Date
- 2026-06-23
Smart Images
Figure SMS_1 
Figure SMS_2
Abstract
Description
Technical Field
[0001] This application relates to the technical field of scale inhibitors, specifically to a scale inhibitor for use in ultrafiltration and reverse osmosis processes, its preparation method, and its application. Background Technology
[0002] During ultrafiltration and reverse osmosis, ions such as calcium, magnesium, and iron in the water can form scale, which not only affects membrane permeability and reduces water production efficiency but may also damage the membrane modules. Therefore, to prevent ultrafiltration and reverse osmosis membranes from being fouled by scale accumulated from salt in the water, a suitable amount of scale inhibitor is generally added at the system inlet to protect the membrane.
[0003] Currently, various types of scale inhibitors exist on the market, such as organic, inorganic, and composite scale inhibitors. With technological advancements and increasingly stringent environmental requirements, the research and application of novel green scale inhibitors have become a hot topic. For example, developing phosphorus-free or low-phosphorus scale inhibitors to reduce the risk of eutrophication and using biodegradable materials to minimize environmental impact. However, these new materials still face numerous challenges in practical applications, such as the complexity of production processes, cost issues, and the need for long-term efficacy verification. Ensuring the long-term stability and broad-spectrum scale inhibition properties of scale inhibitors in practical industrial applications is one of the key issues that needs to be addressed in the research and development of scale inhibitor materials. Summary of the Invention
[0004] To address the aforementioned technical problems, this application provides a scale inhibitor for use in ultrafiltration and reverse osmosis processes, its preparation method, and its application.
[0005] This application provides a scale inhibitor for use in ultrafiltration and reverse osmosis processes, specifically comprising the following components in parts by weight:
[0006] 23-28 parts of polyepoxysuccinic acid, 10-13 parts of polyaspartic acid, 6-8 parts of composite adhesive, 1.5-2.5 parts of defoamer, and 1.5-2.5 parts of stabilizer;
[0007] The composite adhesive is obtained by treating a mixture of DY5010 latex powder, ethylene / vinyl acetate copolymer powder and silane coupling agent by activating it in a water bath at 60-70℃ for 3-5 hours.
[0008] The stabilizer is composed of a mixture of zinc stearate and ethylene bis-stearamide in a weight ratio of 9:0.5-5.
[0009] The scale inhibitor prepared by the above technical solution has good scale inhibition performance for CaCO3, CaSO4 and SiO2, thus expanding the applicable scope of the scale inhibitor.
[0010] The carboxyl and amino functional groups in PASP (polyaspartic acid) molecules can chelate with metal ions such as calcium and magnesium in water to form stable soluble complexes, thereby preventing these ions from combining with anions such as carbonate to form insoluble scale. Polyaspartic acid also has good dispersibility, which can disperse the already formed small scale particles in water and prevent them from depositing and agglomerating into large scale.
[0011] Polyepoxysuccinic acid (PESA) can adsorb onto metal surfaces, forming a protective film that prevents scale-forming ions in the water from depositing on the metal surface. Simultaneously, it can also combine with calcium and magnesium ions in the water to form water-soluble complexes, thus preventing scale formation. Furthermore, PESA is a green and environmentally friendly scale inhibitor, biodegradable and harmless to the environment.
[0012] The components in the composite adhesive work synergistically to form a protective film, effectively preventing the combination of metal ions such as calcium and magnesium with anions such as carbonate in the water, thereby preventing scale formation. Simultaneously, it keeps existing microscale particles suspended, preventing their deposition and aggregation. Through specific water bath activation treatment, the stability and dispersibility of the composite adhesive are improved. This allows it to distribute more evenly in water, exerting its scale-inhibiting effect and extending its service life. Furthermore, the composite adhesive provided in this application has thickening and suspending functions, effectively increasing the viscosity of the water and keeping microscale particles suspended, preventing deposition. When used in combination with polyaspartic acid and polyepoxysuccinic acid scale inhibitors, the composite adhesive works synergistically to enhance the overall scale-inhibiting effect.
[0013] The zinc stearate and ethylene bis-stearamide components in the stabilizer interact to form a protective film, effectively preventing scale-forming ions (such as calcium and magnesium ions) in the water from combining to form scale. Simultaneously, it keeps existing microscale particles dispersed, preventing their deposition on equipment or pipe surfaces. The mixture of zinc stearate and ethylene bis-stearamide exhibits good stability, maintaining its scale-inhibiting effect under varying water quality conditions; this allows the scale inhibitor to function effectively in diverse environments, reducing scale formation. The combination of the two components may produce a synergistic effect, enhancing each other's scale-inhibiting effect. This synergy may stem from their chemical reactions or physical interactions, thereby improving overall scale inhibition efficiency.
[0014] In summary, to further improve scale inhibition performance, the scale inhibitor provided in this application, through the combined action of multiple mechanisms such as chelation, dispersion, adsorption, and thickening, can fully leverage the advantages of various scale inhibitors, effectively preventing and reducing the formation and deposition of scale, achieving a better synergistic scale inhibition effect. It exhibits good and sufficient effectiveness against a variety of substances and has a wide range of applications. It not only improves scale inhibition performance but also reduces the amount of a single scale inhibitor used, thereby lowering costs. This is of great significance for maintaining the cleanliness and efficient operation of water treatment systems.
[0015] Preferably, the scale inhibitor specifically comprises the following components in parts by weight: 25 parts of polyepoxysuccinic acid, 12 parts of polyaspartic acid, 7 parts of composite adhesive, 2 parts of defoamer, and 2 parts of stabilizer.
[0016] Preferably, the composite adhesive is obtained by treating a mixture of DY5010 latex powder, ethylene / vinyl acetate copolymer powder and silane coupling agent in a weight ratio of 5-15:5-15:1-3 with water bath activation at 60-70℃ for 3-5 hours.
[0017] Preferably, the composite adhesive is obtained by treating a mixture of DY5010 latex powder, ethylene / vinyl acetate copolymer powder and silane coupling agent in a weight ratio of 10-15:5-10:1-3 with water bath activation at 60-70℃ for 3-5 hours.
[0018] Preferably, the stabilizer is composed of a mixture of zinc stearate and ethylene bis-stearamide in a weight ratio of 9:1-3.
[0019] In some specific embodiments, the weight ratio of zinc stearate to ethylene bis-stearamide in the stabilizer is 9:0.5-1, 9:0.5-2, 9:0.5-3, 9:0.5-4, 9:0.5-5, 9:2-3, 9:2-4, 9:2-5, 9:3-4, 9:3-5, or 9:4-5.
[0020] In one specific implementation, the weight ratio of zinc stearate and ethylene bis-stearamide in the stabilizer can also be 9:0.5, 9:1, 9:2, 9:3, 9:4, or 9:5.
[0021] Experimental analysis shows that by controlling the weight ratio of zinc stearate and ethylene bis-stearamide within the above-mentioned range, this application further improves the performance of the scale inhibitor.
[0022] Preferably, the defoamer is selected from one or more of polydimethylsiloxane and polysiloxane polyether.
[0023] Preferably, in the preparation method of the composite adhesive, the silane coupling agent is selected from one or more of vinyltriethoxysilane, aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, methacryloxypropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, ethylenediaminepropyltriethoxysilane, vinyltriethoxysilane, mercaptopropyltrimeth(eth)oxysilane, and ethylenediaminepropylmethyldimethoxysilane.
[0024] Secondly, this application provides a method for preparing the above-mentioned scale inhibitor, which specifically includes the following steps in sequence:
[0025] Weigh out the corresponding weights of each raw material component, put each raw material and water into a mixing tank, stir for 40-90 minutes, and let stand for 10-15 minutes to obtain the final product.
[0026] Thirdly, this application provides the application of the aforementioned scale inhibitor in wastewater treatment.
[0027] In summary, the technical solution of this application has the following effects:
[0028] This application utilizes a mixture of DY5010 latex powder, ethylene / vinyl acetate copolymer powder, and silane coupling agent, which is activated by water bath at 60-70℃ for 3-5 hours to obtain a composite adhesive. A stabilizer is composed of zinc stearate and ethylene bis-stearamide in a weight ratio of 9:0.5-5. With specific amounts of polyaspartic acid, polyepoxysuccinic acid, and defoamer as raw materials, the prepared scale inhibitor exhibits good scale inhibition performance for CaCO3, CaSO4, and SiO2, thus expanding the applicable range of scale inhibitors.
[0029] This application improves the performance of scale inhibitors by optimizing the preparation method of composite adhesives and the types of stabilizers, thereby leveraging the synergistic effect of each raw material. Detailed Implementation
[0030] The present application will be further described in detail below with reference to embodiments, comparative examples and performance test results. These embodiments should not be construed as limiting the scope of protection claimed in this application.
[0031] DY5010 latex powder and DY5020 adhesive powder were purchased from Guangzhou Yuanye Industrial Co., Ltd.; ethylene / vinyl acetate copolymer powder and ethylene tert-carbonate / vinyl acetate / ethylene copolymer homopolymer powder were purchased from Guangzhou Yuanye Industrial Co., Ltd.; titanate coupling agent was purchased from Henan Jiyuan Kehui Materials Co., Ltd., and the remaining raw materials were all available through commercial purchase.
[0032] Example
[0033] Examples 1-5
[0034] Examples 1-5 provide a scale inhibitor and its preparation method, respectively.
[0035] The difference in the above embodiments is that the dosage of each component in the scale inhibitor is different, as shown in Table 1.
[0036] The preparation method of the scale inhibitor in the above embodiments is as follows:
[0037] Preparation of composite rubber compound: 12g of DY5010 latex powder, 7g of ethylene / vinyl acetate copolymer powder and 2g of methacryloyloxypropyltrimethoxysilane were weighed according to the weight ratio of 12:7:2 and the mixture was activated by water bath at 65℃ for 4h.
[0038] According to Table 1, weigh out the corresponding weights of polyepoxysuccinic acid, polyaspartic acid, composite rubber, defoamer, and stabilizer (composed of zinc stearate and ethylene bis-stearamide in a weight ratio of 9:2). Place each raw material and water in a mixing tank, turn on the stirring rod at 800 rpm, stir for about 60 minutes, and let stand for 12 minutes to obtain the final product.
[0039] Table 1. Dosage of each component in the scale inhibitor in Examples 1-5 and Comparative Examples 1-3
[0040]
[0041] Examples 6-10
[0042] Examples 6-10 provide a scale inhibitor and its preparation method, respectively.
[0043] The difference between the above embodiment and embodiment 2 is that the preparation methods of the composite adhesive are different, as shown below.
[0044] In Example 6: Preparation of composite adhesive: 12g of DY5010 latex powder, 7g of ethylene / vinyl acetate copolymer powder and 2g of silane coupling agent were weighed according to a weight ratio of 1:7:2 and the mixture was activated by water bath at 85°C for 4 hours.
[0045] In Example 7: Preparation of composite adhesive: 12g of DY5010 latex powder, 7g of ethylene / vinyl acetate copolymer powder and 2g of silane coupling agent were weighed according to the weight ratio of 7:12:2 and the mixture was activated by water bath at 65°C for 4 hours.
[0046] In Example 8: Preparation of composite adhesive: 12g of DY5010 latex powder, 7g of ethylene / vinyl acetate copolymer powder and 2g of silane coupling agent were weighed according to the weight ratio of 5:15:2 and the mixture was activated by water bath at 65℃ for 4h.
[0047] In Example 9: Preparation of composite adhesive: 12g of DY5010 latex powder, 7g of ethylene / vinyl acetate copolymer powder and 2g of silane coupling agent were weighed according to a weight ratio of 10:10:2 and the mixture was activated by water bath at 65°C for 4 hours.
[0048] In Example 10: Preparation of composite adhesive: 12g of DY5010 latex powder, 7g of ethylene / vinyl acetate copolymer powder and 2g of silane coupling agent were weighed according to a weight ratio of 15:5:2 and the mixture was activated by water bath at 65°C for 4 hours.
[0049] All other process parameters in the above embodiments are the same as those in Embodiment 2.
[0050] Examples 11-14
[0051] Examples 11-14 provide a scale inhibitor and its preparation method, respectively.
[0052] The difference between the above embodiment and Embodiment 2 is that the types of stabilizers are different, as shown below.
[0053] In Example 11: The stabilizer is composed of zinc stearate and ethylene bis-stearamide in a weight ratio of 9:0.5.
[0054] In Example 12: The stabilizer is composed of a mixture of zinc stearate and ethylene bis-stearamide in a weight ratio of 9:5.
[0055] In Example 13: The stabilizer is composed of a mixture of zinc stearate and ethylene bis-stearamide in a weight ratio of 9:1.
[0056] In Example 14: The stabilizer is composed of a mixture of zinc stearate and ethylene bis-stearamide in a weight ratio of 9:3.
[0057] All other process parameters in the above embodiments are the same as those in Embodiment 2.
[0058] Comparative Example
[0059] Comparative Examples 1-3
[0060] Comparative Examples 1-3 each provide a scale inhibitor and its preparation method.
[0061] The difference between the above comparative example and Example 2 is that the amount of each component in the scale inhibitor is different, as shown in Table 1.
[0062] All other process parameters in the above comparative examples are the same as those in Example 2.
[0063] Comparative Examples 4-7
[0064] Comparative Examples 4-7 each provide a scale inhibitor and its preparation method.
[0065] The differences between the above comparative example and Example 2 are as follows.
[0066] In Comparative Example 4: Preparation of composite rubber compound: 12g of DY5020 latex powder, 7g of ethylene tert-carbonate / vinyl acetate / ethylene copolymer powder and 2g of silane coupling agent were weighed according to the weight ratio of 12:7:2 and the mixture was activated by water bath at 65℃ for 4h.
[0067] In Comparative Example 5: Preparation of composite rubber compound: 19g of DY5020 latex powder and 2g of silane coupling agent were weighed and the mixture was activated by water bath at 65℃ for 4h.
[0068] In Comparative Example 6: the stabilizer was composed of a mixture of zinc stearate and polyethylene wax in a weight ratio of 9:2.
[0069] In Comparative Example 7: the stabilizer was zinc stearate.
[0070] All other process parameters in the above comparative examples are the same as those in Example 2.
[0071] Performance testing
[0072] (1) Scale inhibition rate test:
[0073] The scale inhibition rate of CaCO3 was determined according to GB / T 16632-2008 "Determination of Scale Inhibition Performance of Water Treatment Agents - Calcium Carbonate Deposition Method": CaCO3 was prepared using deionized water. 2+ The mass concentration is 260 mg / L, HCO3 - A solution with a mass concentration of 760 mg / L was prepared, and the pH was adjusted to 9.0 with sodium hydroxide. The solution was then placed in a constant temperature water bath at 60℃ for 10 hours, cooled, filtered through a 0.22 μm microporous filter, and the Ca content was determined by EDTA. 2+ Concentration, and perform a blank test at the same time.
[0074] According to standard QSY126-2014 "Requirements for Corrosion and Scale Inhibitors for Oilfield Water Treatment", the scale inhibition performance of CaSO4 was tested: CaSO4 was prepared using deionized water. 2+ The mass concentration is 260 mg / L, SO4 2- A solution with a mass concentration of 760 mg / L was prepared, and the pH was adjusted to 9.0 with sodium hydroxide. The solution was then placed in a constant temperature water bath at 60℃ for 10 hours, cooled, filtered through a 0.22 μm microporous filter, and the Ca content was determined by EDTA. 2+ Concentration, and perform a blank test at the same time.
[0075] The scale-inhibiting performance of silica scale inhibitors was determined according to standard GB / T 16633-1996 "Determination of silica content in industrial circulating cooling water - spectrophotometric method", namely the silicomolybdenum blue spectrophotometric method: a Na2SiO3 solution with a mass concentration of 500 mg / L (concentration as SiO2) was prepared with deionized water, 50 mg / L of scale inhibitor was added, the pH of the solution was adjusted to 7.0, and then the solution was placed in a constant temperature water bath at 40℃ for 8 hours. After cooling, the solution was filtered through a 0.22 μm microporous filter, and the SiO2 content in the water sample was determined by the silicomolybdenum blue spectrophotometric method. A blank test was also performed.
[0076] Test results are shown in Table 2.
[0077] Table 2 Performance test results of scale inhibitors in Examples 1-14 and Comparative Examples 1-7
[0078]
[0079] Based on the test results in Table 2 and by comparing the test results of the examples and comparative examples, it can be seen that the composite adhesive obtained by this application is prepared by using a mixture of DY5010 latex powder, ethylene / vinyl acetate copolymer powder and silane coupling agent and activating it in a water bath at 60-70℃ for 3-5 hours. The stabilizer is composed of zinc stearate and ethylene bis-stearamide mixed in a weight ratio of 9:0.5-5. With specific amounts of polyaspartic acid, polyepoxysuccinic acid and defoamer as raw materials, the scale inhibitor prepared has good scale inhibition performance for CaCO3, CaSO4 and SiO2, thus expanding the applicable scope of the scale inhibitor.
[0080] No composite adhesive was added in Comparative Example 1, no stabilizer was added in Comparative Example 2, the amounts of each raw material component were mismatched in Comparative Example 3, the preparation methods of the composite adhesive were mismatched in Comparative Examples 4 and 5, the stabilizer in Comparative Example 6 was composed of zinc stearate and polyethylene wax in a weight ratio of 9:2, and the stabilizer in Comparative Example 7 was zinc stearate. The scale inhibitors prepared in the above comparative examples had poor performance.
[0081] By comparing the test results of Examples 2 and 6-10, it can be seen that the present application obtains a composite material by treating a mixture of DY5010 latex powder, ethylene / vinyl acetate copolymer powder and silane coupling agent in a weight ratio of 5-15:5-15:1-3 with water bath activation at 60-70℃ for 3-5 hours, which further improves the performance of the scale inhibitor.
[0082] By comparing the test results of Examples 2 and 11-14, it can be seen that the present application further improves the performance of the scale inhibitor by using a stabilizer composed of zinc stearate and ethylene bis-stearamide in a weight ratio of 9:1-3.
[0083] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.
Claims
1. A scale inhibitor for use in ultrafiltration and reverse osmosis processes, characterized in that, Specifically, it includes the following components in parts by weight: 23-28 parts of polyepoxysuccinic acid, 10-13 parts of polyaspartic acid, 6-8 parts of composite adhesive, 1.5-2.5 parts of defoamer, and 1.5-2.5 parts of stabilizer; The composite adhesive is obtained by treating a mixture of DY5010 latex powder, ethylene / vinyl acetate copolymer powder and silane coupling agent by activating it in a water bath at 60-70℃ for 3-5 hours. The stabilizer is composed of a mixture of zinc stearate and ethylene bis-stearamide in a weight ratio of 9:0.5-5.
2. The scale inhibitor according to claim 1, characterized in that, The scale inhibitor specifically comprises the following components in parts by weight: 25 parts polyepoxysuccinic acid, 12 parts polyaspartic acid, 7 parts composite adhesive, 2 parts defoamer, and 2 parts stabilizer.
3. The scale inhibitor according to claim 2, characterized in that, The composite adhesive is obtained by treating a mixture of DY5010 latex powder, ethylene / vinyl acetate copolymer powder and silane coupling agent in a weight ratio of 5-15:5-15:1-3 with water bath activation at 60-70℃ for 3-5 hours.
4. The scale inhibitor according to claim 1, characterized in that, The composite adhesive is obtained by treating a mixture of DY5010 latex powder, ethylene / vinyl acetate copolymer powder and silane coupling agent in a weight ratio of 10-15:5-10:1-3 with water bath activation at 60-70℃ for 3-5 hours.
5. The scale inhibitor according to claim 1, characterized in that, The stabilizer is composed of a mixture of zinc stearate and ethylene bis-stearamide in a weight ratio of 9:1-3.
6. The scale inhibitor according to claim 5, characterized in that, The defoamer is selected from one or more of polydimethylsiloxane and polysiloxane polyether.
7. The scale inhibitor according to claim 1, characterized in that, In the preparation method of the composite adhesive, the silane coupling agent is selected from one or more of vinyltriethoxysilane, aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, methacryloxypropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, ethylenediaminepropyltriethoxysilane, vinyltriethoxysilane, mercaptopropyltrimeth(eth)oxysilane, and ethylenediaminepropylmethyldimethoxysilane.
8. The method for preparing the scale inhibitor according to any one of claims 1-7, characterized in that, Specifically, the following steps are performed sequentially: Weigh out the corresponding weights of each raw material component, put each raw material and water into a mixing tank, stir for 40-90 minutes, and let stand for 10-15 minutes to obtain the final product.
9. The application of the scale inhibitor as described in any one of claims 1-7 in wastewater treatment.