Fluorescent tracer-type scale inhibitors, their preparation methods and applications

Abstract

This invention provides a fluorescent tracer-type scale inhibitor, its preparation method, and its application. The fluorescent tracer-type scale inhibitor, by mass percentage, comprises: a first mass percentage of an organophosphonic acid compound, a second mass percentage of an acrylic polymer, a third mass percentage of a fluorescent tracer, and the balance being water. This invention exhibits excellent scale inhibition performance against CaCO3, CaSO4, BaSO4, and SrSO4. By introducing a fluorescent tracer, the scale inhibitor is endowed with unique optical signal characteristics, enabling real-time monitoring of its concentration in water. Through an online monitoring system for reverse osmosis membrane scaling, real-time monitoring and precise control of the scale inhibitor concentration can be achieved, solving the problems of traditional scale inhibitors' inability to be monitored online and the reliance on experience for dosage, leading to over- or under-dosing. Its application in reverse osmosis systems of steel plants has shown significant results, not only ensuring membrane performance stability but also reducing system operating costs.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, and in particular to a fluorescent tracer-type scale inhibitor, its preparation method, and its application. Background Technology

[0002] Reverse osmosis (RO) water treatment is a high-precision filtration technology based on selective semi-permeable membranes. It utilizes pressure differentials to separate dissolved impurities in water and is widely used in drinking water purification and industrial desalination. The RO membrane is the core component of RO technology; whether it is fouled or scaled directly affects the operating efficiency of the RO system. During RO, impurities such as hardness ions, organic matter, and microorganisms in the raw water easily form deposits on the membrane surface on the concentrate side as they pass through the membrane, leading to fouling or scaling. This results in increased transmembrane pressure differential, decreased desalination rate, reduced recovery rate, and in severe cases, even damage to the RO membrane. Therefore, adding antiscalants to the feed water of the RO system has become a common and cost-effective preventative measure in industry to prevent RO membrane scaling and extend membrane lifespan.

[0003] However, traditional scale inhibitors (such as polyacrylic acid and organophosphonic acid), while inhibiting scaling through lattice distortion, have poor scale inhibition performance and lack optical or electrical signals detectable by external instruments, making real-time monitoring of membrane scaling status impossible. Furthermore, current scale inhibitor dosing strategies rely heavily on operator experience, lacking real-time online monitoring methods, which easily leads to over- or under-dosing. Over-dosing results in waste and increased costs; conversely, under-dosing fails to provide effective protection, leading to membrane fouling. Summary of the Invention

[0004] The purpose of this invention is to provide a fluorescent tracer-type scale inhibitor, its preparation method, and its application, in order to solve one or more of the problems existing in the prior art, such as poor scale inhibition performance of scale inhibitors, inability to monitor the scale formation state on the membrane surface in real time, and the dependence of scale inhibitor addition on experience.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solution: a fluorescent tracer-type scale inhibitor, comprising, by mass percentage: a first mass percentage of an organophosphonic acid compound, a second mass percentage of an acrylic polymer, a third mass percentage of a fluorescent tracer, and the balance being water.

[0006] Optionally, the organophosphonic acid compound includes at least one of 2-phosphono-1,2,4-tricarboxylate, hydroxyethylidene diphosphonic acid, and aminotrimethylenephosphonic acid.

[0007] Optionally, the acrylic polymer includes at least one of polyacrylic acid, maleic acid-acrylic acid copolymer, and carboxylate-sulfonate-acrylate.

[0008] Optionally, the fluorescent tracer includes tetrasodium 1,3,6,8-pyrenetetrasulfonate.

[0009] Optionally, the first mass percentage includes 30% to 50%, the second mass percentage includes 25% to 35%, and the third mass percentage includes 0.1% to 1%.

[0010] Optionally, the third mass percentage is 0.1% to 0.5%.

[0011] To achieve the above objectives, the present invention also provides a method for preparing a fluorescent tracer-type scale inhibitor as described in any of the preceding claims, comprising:

[0012] Weigh each component according to its mass percentage;

[0013] The weighed organophosphonic acid compound, acrylic polymer, fluorescent tracer and water are added to a stirred tank and mixed evenly to obtain the fluorescent tracer-type scale inhibitor.

[0014] To achieve the above objectives, the present invention also provides the application of a fluorescent tracer-type scale inhibitor as described in any of the preceding claims in a reverse osmosis system, wherein the fluorescent tracer-type scale inhibitor is added as a membrane scale inhibitor to the inlet of the security filter of the reverse osmosis system.

[0015] To achieve the above objectives, the present invention also provides an online monitoring system for reverse osmosis membrane scaling, comprising: an antiscalant dosing device connected to the inlet of a security filter of the reverse osmosis system for adding a fluorescent tracer-type antiscalant as described above to the reverse osmosis system; an online fluorescence monitor connected to the outlet of the security filter for real-time monitoring of the antiscalant concentration at the outlet of the security filter; and a control device having a signal input terminal connected to the online fluorescence monitor and a signal output terminal connected to the antiscalant dosing device; the control device is configured to receive the monitoring signal from the online fluorescence monitor and control the antiscalant dosing device to adjust the dosage of the fluorescent tracer-type antiscalant.

[0016] Optionally, the control device is further configured to control the concentration of the fluorescent tracer scale inhibitor at 3.8 mg / L to 4.2 mg / L.

[0017] Compared with the prior art, the fluorescent tracer-type scale inhibitor, its preparation method, and its application provided by the present invention have the following beneficial effects:

[0018] The fluorescent tracer-type scale inhibitor provided by this invention comprises, by mass percentage: a first mass percentage of an organophosphonic acid compound, a second mass percentage of an acrylic polymer, a third mass percentage of a fluorescent tracer, and the balance being water. Therefore, the fluorescent tracer-type scale inhibitor provided by this invention utilizes the excellent lattice distortion and threshold effect of organophosphonic acid compounds (such as 2-phosphono-1,2,4-tricarboxylate butane) to effectively interfere with the normal growth of microcrystals such as calcium carbonate (CaCO3) and calcium sulfate (CaSO4). Simultaneously, combined with the strong dispersing effect and electrostatic repulsion of acrylic polymers (such as polyacrylic acid and maleic acid-acrylic acid copolymers), it can further prevent the aggregation and deposition of sparingly soluble salts such as barium sulfate (BaSO4) and strontium sulfate (SrSO4). The fluorescent tracer-type scale inhibitor provided by this invention exhibits excellent scale inhibition performance against CaCO3, CaSO4, BaSO4, and SrSO4, solving the problem of insufficient inhibition ability of traditional single scale inhibitors against specific scale types (especially sulfate scale), and significantly improving the broad-spectrum and stable scale inhibition. Furthermore, by introducing a fluorescent tracer, the scale inhibitor is endowed with its own unique optical signal characteristics, enabling the concentration of the scale inhibitor in the water to be monitored in real time, providing a material basis for subsequent precise dosing and prevention of membrane fouling.

[0019] Since the preparation method of the fluorescent tracer-type scale inhibitor provided by this invention, the application of the fluorescent tracer-type scale inhibitor in a reverse osmosis system, and the online monitoring system for reverse osmosis membrane scaling provided by this invention all belong to the same inventive concept as the fluorescent tracer-type scale inhibitor provided by this invention, the preparation method of the fluorescent tracer-type scale inhibitor provided by this invention, the application of the fluorescent tracer-type scale inhibitor in a reverse osmosis system, and the online monitoring system for reverse osmosis membrane scaling provided by this invention at least have all the advantages of the fluorescent tracer-type scale inhibitor provided by this invention. For the advantages of the preparation method of the fluorescent tracer-type scale inhibitor provided by this invention, the application of the fluorescent tracer-type scale inhibitor in a reverse osmosis system, and the online monitoring system for reverse osmosis membrane scaling provided by this invention, please refer to the relevant description of the beneficial effects of the fluorescent tracer-type scale inhibitor provided by this invention, which will not be repeated here. Furthermore, the application of the fluorescent tracer-type scale inhibitor in a reverse osmosis system provided by this invention involves adding the fluorescent tracer-type scale inhibitor as a membrane scale inhibitor to the inlet of the security filter in the reverse osmosis system. This allows the membrane scale inhibitor to be fully mixed with the raw water, and after being buffered by the security filter, it reaches the optimal state for scale inhibition, thereby preventing subsequent scaling of the reverse osmosis membrane. The online monitoring system for reverse osmosis membrane scaling provided by this invention can realize real-time monitoring and precise control of the concentration of the reverse osmosis membrane scale inhibitor, solving the technical problems of traditional scale inhibitors that cannot be monitored online and whose dosage relies on experience, leading to over- or under-dosing. Its application in reverse osmosis systems of steel plants has shown significant results, not only ensuring membrane performance stability but also reducing system operating costs. Attached Figure Description

[0020] Figure 1 In the dynamic scale inhibition test provided in Embodiment 2 of the present invention, Ca 2+ Graph showing the relationship between concentration and time;

[0021] Figure 2 This is a schematic diagram of a wastewater treatment process in a steel plant according to Embodiment 4 of the present invention;

[0022] The annotations in the attached figures are explained as follows:

[0023] 10-Equalization tank, 11-High-density sedimentation tank, 12-Multi-media filter, 13-Ultrafiltration unit, 14-Ultrafiltration permeate tank;

[0024] 20-Reverse osmosis system, 201-Security filter, 202-High pressure pump, 203-First-stage reverse osmosis unit, 204-Second-stage reverse osmosis unit, 205-Sodium ion exchanger;

[0025] 30 - Online monitoring system; 301 - Scale inhibitor dosing device; 302 - Fluorescence online monitoring instrument. Detailed Implementation

[0026] The fluorescent tracer-type scale inhibitor, its preparation method, and its application, proposed in this invention, will be further described in detail below with reference to the accompanying drawings and specific embodiments. The advantages and features of this invention will become clearer from the following description. It should be noted that the drawings are all in a very simplified form and use non-precise proportions, used only to facilitate and clarify the illustration of the embodiments of this invention. Please refer to the drawings to make the objectives, features, and advantages of this invention more apparent and understandable. It should be understood that the structures, proportions, sizes, etc., depicted in the accompanying drawings are only for the purpose of assisting those skilled in the art in understanding and reading the content disclosed in the specification, and are not intended to limit the implementation conditions of this invention. Any modifications to the structure, changes in proportions, or adjustments to the size, provided that the effects and objectives achieved by this invention are the same or similar, should still fall within the scope of the technical content disclosed in this invention. Specific design features of the invention disclosed herein, including, for example, specific dimensions, orientations, positions, and shapes, will be determined in part by the specific application and usage environment. Furthermore, in the embodiments described below, the same reference numerals are sometimes used across different drawings to denote the same parts or parts having the same function, and repeated descriptions are omitted.

[0027] It should be understood that, unless specifically stated or obvious from the context, as used herein, the term “about” is understood to mean within the normal tolerance range in the field, such as within 2 standard deviations of the mean. “About” can be understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise specified from the context, all numerical values ​​provided herein are modified by the term “about”.

[0028] Example 1

[0029] This embodiment provides a fluorescent tracer-type scale inhibitor. Specifically, the fluorescent tracer-type scale inhibitor comprises, by mass percentage: a first mass percentage of an organophosphonic acid compound, a second mass percentage of an acrylic polymer, a third mass percentage of a fluorescent tracer, and the balance being water.

[0030] Therefore, the fluorescent tracer-type scale inhibitor provided in this embodiment utilizes the excellent lattice distortion and threshold effect of organophosphonic acid compounds (such as 2-phosphono-1,2,4-tricarboxylate butane) to effectively interfere with the normal growth of microcrystals such as calcium carbonate (CaCO3) and calcium sulfate (CaSO4). Simultaneously, combined with the strong dispersing effect and electrostatic repulsion of acrylic polymers (such as polyacrylic acid and maleic acid-acrylic acid copolymers), it can further prevent the aggregation and deposition of sparingly soluble salts such as barium sulfate (BaSO4) and strontium sulfate (SrSO4). The fluorescent tracer-type scale inhibitor provided in this embodiment exhibits excellent scale inhibition performance against CaCO3, CaSO4, BaSO4, and SrSO4, solving the problem of insufficient inhibition ability of traditional single scale inhibitors against specific scale types (especially sulfate scale), and significantly improving the broad-spectrum and stable scale inhibition. Furthermore, by introducing a fluorescent tracer, the scale inhibitor is endowed with unique optical signal characteristics, enabling real-time monitoring of the scale inhibitor concentration in the water, providing a material basis for subsequent precise dosing and prevention of membrane fouling.

[0031] Exemplarily, in some embodiments, the organophosphonic acid compound includes at least one of 2-phosphono-1,2,4-tricarboxylate, hydroxyethylidene diphosphonic acid, and aminotrimethylenephosphonic acid.

[0032] Preferably, in some exemplary embodiments, the organophosphonic acid compound is 2-phosphono-1,2,4-tricarboxylate butane.

[0033] Exemplarily, in some embodiments, the acrylic polymer includes at least one of polyacrylic acid, maleic acid-acrylic acid copolymer, and carboxylate-sulfonate-acrylate.

[0034] Preferably, in some exemplary embodiments, the acrylic polymer is a carboxylate-sulfonate-acrylate.

[0035] Exemplarily, in some embodiments, the fluorescent tracer comprises tetrasodium 1,3,6,8-pyrenetetrasulfonate.

[0036] Furthermore, in some embodiments, the first mass percentage comprises 30% to 50%, the second mass percentage comprises 25% to 35%, and the third mass percentage comprises 0.1% to 1%. Thus, by maintaining appropriate mass percentages for each component, the scale inhibition performance can be improved while ensuring that the fluorescent tracer-type scale inhibitor possesses its own unique optical signal characteristics.

[0037] Preferably, in some exemplary embodiments, the third mass percentage is 0.1% to 0.5%. Thus, by limiting the mass percentage of the fluorescent tracer to 0.1% to 0.5%, production costs can be effectively reduced and interference with scale inhibition performance can be avoided while ensuring the sensitivity and linearity of fluorescence signal detection.

[0038] Example 2

[0039] This embodiment provides a method for preparing a fluorescent tracer-type scale inhibitor, wherein the fluorescent tracer-type scale inhibitor is the fluorescent tracer-type scale inhibitor described in any of the above embodiments. Specifically, the preparation method includes:

[0040] S100: Weigh each component according to its mass percentage;

[0041] S200: The weighed organophosphonic acid compound, acrylic polymer, fluorescent tracer and water are added to a stirred tank and mixed evenly to obtain the fluorescent tracer-type scale inhibitor.

[0042] Since the preparation method of the fluorescent tracer scale inhibitor provided in this embodiment belongs to the same inventive concept as the fluorescent tracer scale inhibitor provided in any of the above embodiments, the preparation method of the fluorescent tracer scale inhibitor provided in this embodiment has at least all the advantages of the fluorescent tracer scale inhibitor provided in the above embodiments. For the advantages of the preparation method of the fluorescent tracer scale inhibitor provided in this embodiment, please refer to the relevant descriptions of the beneficial effects of the fluorescent tracer scale inhibitor provided in the above embodiments, which will not be repeated here.

[0043] To better understand the present invention, the following exemplary description illustrates the process of preparing seven specific examples of fluorescent tracer-type scale inhibitors using the preparation method of the fluorescent tracer-type scale inhibitor provided by the present invention.

[0044] Example 1: Weigh the following components by mass percentage: 50% 2-phosphono-1,2,4-tricarboxylate butane, 35% polyacrylic acid, 0.1% tetrasodium 1,3,6,8-pyrenetetrasulfonic acid, and the balance is water. The sum of the mass percentages of the above components is 100%. Add these weighed components to a stirred tank and mix them evenly to obtain the fluorescent tracer scale inhibitor.

[0045] Example 2: Weigh the following components by mass percentage: 50% hydroxyethylidene diphosphonic acid, 35% carboxylate-sulfonate-acrylate, 0.1% tetrasodium 1,3,6,8-pyrenetetrasulfonic acid, and the balance is water. The sum of the mass percentages of the above components is 100%. Add these weighed components to a stirred tank and mix them evenly to obtain the fluorescent tracer scale inhibitor.

[0046] Example 3: Weigh the following components by mass percentage: 50% aminotrimethylenephosphonic acid, 35% maleic acid-acrylic acid copolymer, 0.1% tetrasodium 1,3,6,8-pyrenetetrasulfonic acid, and the balance is water. The sum of the mass percentages of the above components is 100%. Add these weighed components to a stirred tank and mix them evenly to obtain the fluorescent tracer scale inhibitor.

[0047] Example 4: Weigh the following components by mass percentage: 25% 2-phosphono-1,2,4-tricarboxylate, 25% hydroxyethylidene diphosphonic acid, 25% polyacrylic acid, 0.1% tetrasodium 1,3,6,8-pyrene tetrasulfonate, and the balance is water. The sum of the mass percentages of the above components is 100%. Add these weighed components to a stirred tank and mix them evenly to obtain the fluorescent tracer-type scale inhibitor.

[0048] Example 5: Weigh the following components by mass percentage: 25% 2-phosphono-1,2,4-tricarboxylate butane, 10% hydroxyethylidene diphosphonic acid, 12.5% ​​maleic acid-acrylic acid copolymer, 12.5% ​​carboxylate-sulfonate-acrylate, 0.1% tetrasodium 1,3,6,8-pyrene tetrasulfonate, with the balance being water. The sum of the mass percentages of the above components is 100%. Add these weighed components to a stirred tank and mix thoroughly to obtain the fluorescent tracer-type scale inhibitor.

[0049] Example 6: Weigh the following components by mass percentage: 20% 2-phosphono-1,2,4-tricarboxylate butane, 25% aminotrimethylenephosphonic acid, 12.5% ​​carboxylate-sulfonate-acrylate, 12.5% ​​polyacrylic acid, 0.2% tetrasodium 1,3,6,8-pyrenetetrasulfonate, with the balance being water. The sum of the mass percentages of the above components is 100%. Add these weighed components to a stirred tank and mix them evenly to obtain the fluorescent tracer-type scale inhibitor.

[0050] Example 7: Weigh the following components by mass percentage: 20% aminotrimethylenephosphonic acid, 20% hydroxyethylidene diphosphonic acid, 20% polyacrylic acid, 15% maleic acid-acrylic acid copolymer, 0.1% tetrasodium 1,3,6,8-pyrene tetrasulfonate, and the balance is water. The sum of the mass percentages of the above components is 100%. Add these weighed components to a stirred tank and mix them evenly to obtain the fluorescent tracer-type scale inhibitor.

[0051] Furthermore, to verify the scale inhibition performance of the fluorescent tracer-type scale inhibitor provided by this invention, the primary reverse osmosis feed water of a steel plant's water treatment center was used as test water after pretreatment simulating on-site operating conditions (specific water quality indicators are shown in Table 1). The fluorescent tracer-type scale inhibitor obtained in Examples 1-7 above was used as the reverse osmosis scale inhibitor, and the dosage concentration of the reverse osmosis scale inhibitor was 4 mg / L. The scale inhibition performance was tested using the static scale inhibition method. The Ca in the primary reverse osmosis feed water... 2+ The concentration is approximately 120 mg / L, HCO3 - The concentration was approximately 140 mg / L, pH=8, and temperature was 25℃. Assuming a recovery rate of 75%, the water quality of the selected test water and its corresponding concentrate is shown in Table 1.

[0052] Table 1: Water quality of test water and corresponding concentrate water quality

[0053]

[0054] The scale inhibition effect of the fluorescent tracer-type scale inhibitors obtained in Examples 1-7 above on calcium carbonate was evaluated according to GB / T 16632-2019 "Determination of Scale Inhibition Performance of Water Treatment Agents - Calcium Carbonate Deposition Method". The test results are shown in Table 2.

[0055] Table 2: Scale Inhibition Test Results

[0056]

[0057] The above static scale inhibition test shows that the fluorescent tracer-type scale inhibitor provided by this invention has good scale inhibition performance for calcium carbonate. This is because the fluorescent tracer-type scale inhibitor provided by this invention increases the solubility of calcium carbonate crystals through complexation solubilization, lattice distortion, and dispersion adsorption properties, thereby achieving good scale inhibition performance for calcium carbonate and a high scale inhibition rate.

[0058] In addition to using the static scale inhibition method for scale inhibition performance testing, the dynamic scale inhibition test using the full circulation method can also be used to evaluate the scale inhibition performance of the fluorescent tracer-type scale inhibitor provided by this invention as a reverse osmosis scale inhibitor. The full circulation method is a commonly used method for evaluating the scale inhibition performance of scale inhibitors for reverse osmosis membranes. During reverse osmosis equipment operation, all freshwater and concentrate are returned to the raw water to keep the raw water composition constant. The scale inhibition performance of the scale inhibitor is evaluated by comparing changes in calcium ion concentration and conductivity.

[0059] The following example uses the fluorescent tracer-type scale inhibitors obtained in Examples 1-7 as reverse osmosis scale inhibitors, with a dosage concentration of 4 mg / L. A dynamic scale inhibition test was conducted using the full circulation method, controlling the recovery rate of the reverse osmosis equipment at 75%, maintaining the raw water temperature at 25℃~30℃, and adjusting the pH to 8.0 with hydrochloric acid. The equipment operating cycle was 144 hours, and a blank control experiment was performed. For details, please refer to... Figure 1 , Figure 1 In the dynamic scale inhibition test provided in this embodiment, Ca 2+ Graph showing the relationship between concentration and time.

[0060] The above dynamic scale inhibition test shows that by adding the fluorescent tracer-type scale inhibitor provided by the present invention as a reverse osmosis scale inhibitor, scaling problems of membrane modules can be avoided under the condition that the recovery rate of the reverse osmosis equipment is 75%.

[0061] Example 3

[0062] This embodiment provides an application of a fluorescent tracer-type scale inhibitor in a reverse osmosis system, wherein the fluorescent tracer-type scale inhibitor is the fluorescent tracer-type scale inhibitor described in any of the above embodiments. Specifically, the fluorescent tracer-type scale inhibitor is added as a membrane scale inhibitor to the inlet of the security filter of the reverse osmosis system.

[0063] Therefore, the application of the fluorescent tracer-type scale inhibitor in the reverse osmosis system provided in this embodiment, by adding the fluorescent tracer-type scale inhibitor as a membrane scale inhibitor to the inlet of the security filter of the reverse osmosis system, allows the membrane scale inhibitor to be fully mixed with the raw water, and after being buffered by the security filter, it can achieve the optimal state of scale inhibition, thereby preventing subsequent reverse osmosis membrane scaling.

[0064] Example 4

[0065] This embodiment provides an online monitoring system for reverse osmosis membrane fouling. For details, please refer to [link to documentation]. Figure 2 , Figure 2 This is a schematic diagram of a wastewater treatment process in a steel plant, as provided in this embodiment. Figure 2As can be seen, the online monitoring system 30 includes: an antiscalant dosing device 301, which is connected to the inlet of the security filter 201 of the reverse osmosis system 20, for adding the fluorescent tracer-type antiscalant described in any of the above embodiments to the reverse osmosis system 20; a fluorescent online monitor 302, which is connected to the outlet of the security filter 201, for real-time monitoring of the antiscalant concentration at the outlet of the security filter 201; and a control device (not shown in the figure), whose signal input terminal is connected to the fluorescent online monitor 302 and whose signal output terminal is connected to the antiscalant dosing device 301; the control device is configured to: receive the monitoring signal from the fluorescent online monitor 302 and control the antiscalant dosing device 301 to adjust the dosage of the fluorescent tracer-type antiscalant.

[0066] Since the reverse osmosis membrane scaling online monitoring system provided in this embodiment belongs to the same inventive concept as the fluorescent tracer-type scale inhibitor provided in any of the above embodiments, the reverse osmosis membrane scaling online monitoring system provided in this embodiment has at least all the advantages of the fluorescent tracer-type scale inhibitors provided in the above embodiments. For details regarding the advantages of the reverse osmosis membrane scaling online monitoring system provided in this embodiment, please refer to the relevant descriptions of the beneficial effects of the fluorescent tracer-type scale inhibitors provided in the above embodiments; these will not be repeated here. Furthermore, the reverse osmosis membrane scaling online monitoring system provided in this embodiment can achieve real-time monitoring and precise control of the reverse osmosis membrane scale inhibitor concentration, solving the technical problems of traditional scale inhibitors being unable to be monitored online and relying on experience for dosage, leading to over- or under-dosing. Its application in steel plant reverse osmosis systems has significant effects, not only ensuring membrane performance stability but also reducing system operating costs.

[0067] Furthermore, the control device is configured to control the concentration of the fluorescent tracer-type scale inhibitor within the range of 3.8 mg / L to 4.2 mg / L. This solves the problem of large fluctuations in the concentration of membrane scale inhibitors in traditional solutions, ensuring the scale inhibition effect of the reverse osmosis membrane while effectively saving scale inhibitors and thus reducing system operating costs.

[0068] For example, please continue to see Figure 2 ,like Figure 2 As shown, in some embodiments, in the wastewater treatment process of a steel plant, the production wastewater is first treated sequentially through an equalization tank 10, a high-density sedimentation tank 11, a multi-media filter 12, and an ultrafiltration unit 13, and then the ultrafiltration permeate is stored in an ultrafiltration permeate tank 14; wherein, the ultrafiltration unit 13 includes a permeate flow rate of 168m³. 3Four ultrafiltration units with a per-hour capacity of 120 m³ / h are then used. The ultrafiltration permeate is then transported to the subsequent reverse osmosis system 20. The reverse osmosis system 20 includes, in sequence, a security filter 201, a high-pressure pump 202, a primary reverse osmosis unit 203, and a secondary reverse osmosis unit 204. A sodium ion exchanger 205, filled with sodium ion exchange resin, is connected to the outlet of the primary reverse osmosis unit 203. The primary reverse osmosis unit 203 comprises four units (A, B, C, and D) with a permeate capacity of 120 m³ / h. 3 The first-stage reverse osmosis unit has a per-hour capacity of 105 m³ / h, and the second-stage reverse osmosis unit 204 includes a per-water production capacity of 105 m³ / h. 3 Two sets of secondary reverse osmosis units with a capacity of 120 m³ / h each, wherein the sodium ion exchanger 205 has a water production capacity of 120 m³ / h. 3 The system operates at a rate of / h, and is equipped with two groups. Ultimately, soft water is obtained through the sodium ion exchanger 205, and demineralized water is obtained through the secondary reverse osmosis unit 204. As the treated water volume changes, the four primary reverse osmosis units (A, B, C, and D) in the primary reverse osmosis unit 203 are switched on and off at any time. In traditional solutions, the addition of membrane antiscalant relies on the operator's experience. To solve this problem and maintain the stability of the antiscalant concentration, this invention connects the reverse osmosis system 20 to a reverse osmosis membrane scaling online monitoring system 30. The online monitoring system 30 includes an antiscalant dosing device 301 connected to the inlet of the security filter 201, a fluorescence online monitoring instrument 302 connected to the outlet of the security filter 201, and a control device (such as a PLC controller). The antiscalant dosing device 301 is used to add the fluorescence tracer-type antiscalant provided by this invention to the reverse osmosis system 20; the fluorescence online monitoring instrument 302 is used to monitor the antiscalant concentration at the outlet of the security filter 201 in real time. The signal input terminal of the PLC controller is connected to the fluorescence online monitoring instrument 302, and the signal output terminal is connected to the dosing controller (not shown in the figure) in the scale inhibitor dosing device 301, thereby forming a PID closed-loop control unit for fluorescence parameters. When the intensity of the monitoring signal received by the PLC controller is lower than a preset threshold, the scale inhibitor dosing device 301 is automatically triggered to open, and the dosing amount of the scale inhibitor dosing device 301 is dynamically adjusted according to the scale inhibitor residue amount fed back by the fluorescence online monitoring instrument 302 in real time. The following uses the dosing of the fluorescent tracer-type scale inhibitor prepared in Example 4 of Embodiment 2 of the present invention into the scale inhibitor dosing device 301 as an example, with a dosing concentration range of 3.8 mg / L to 4.2 mg / L, to illustrate the performance indicators of the first-stage reverse osmosis membranes in the four groups of first-stage reverse osmosis units A, B, C, and D in the first-stage reverse osmosis unit 203. The specific membrane performance data are shown in Table 3.

[0069] Table 3: Performance data of primary reverse osmosis membranes from January to March 2025

[0070]

[0071] As can be seen from Table 3, the performance indicators of the first-stage reverse osmosis membrane (such as pressure difference, desalination rate, and recovery rate) are quite stable.

[0072] In summary, the fluorescent tracer-type scale inhibitor, its preparation method, and its application provided by this invention have the following advantages: The fluorescent tracer-type scale inhibitor provided by this invention, by mass percentage, comprises: a first mass percentage of an organophosphonic acid compound, a second mass percentage of an acrylic polymer, a third mass percentage of a fluorescent tracer, and the balance being water. Therefore, the fluorescent tracer-type scale inhibitor provided by this invention utilizes the excellent lattice distortion and threshold effect of organophosphonic acid compounds (such as 2-phosphono-1,2,4-tricarboxylate butane, etc.) to effectively interfere with the normal growth of microcrystals such as calcium carbonate (CaCO3) and calcium sulfate (CaSO4); simultaneously, combined with the strong dispersing effect and electrostatic repulsion of acrylic polymers (such as polyacrylic acid, maleic acid-acrylic acid copolymer, etc.), it can further prevent the aggregation and deposition of sparingly soluble salts such as barium sulfate (BaSO4) and strontium sulfate (SrSO4). The fluorescent tracer-type scale inhibitor provided by this invention exhibits excellent scale inhibition performance against CaCO3, CaSO4, BaSO4, and SrSO4, solving the problem of insufficient inhibition ability of traditional single scale inhibitors against specific scale types (especially sulfate scale), and significantly improving the broad-spectrum and stable scale inhibition. Furthermore, by introducing a fluorescent tracer, the scale inhibitor is endowed with unique optical signal characteristics, enabling real-time monitoring of its concentration in water, providing a material basis for subsequent precise dosing and prevention of membrane fouling.

[0073] Since the preparation method of the fluorescent tracer-type scale inhibitor provided by this invention, the application of the fluorescent tracer-type scale inhibitor in a reverse osmosis system, and the online monitoring system for reverse osmosis membrane scaling provided by this invention all belong to the same inventive concept as the fluorescent tracer-type scale inhibitor provided by this invention, the preparation method of the fluorescent tracer-type scale inhibitor provided by this invention, the application of the fluorescent tracer-type scale inhibitor in a reverse osmosis system, and the online monitoring system for reverse osmosis membrane scaling provided by this invention at least have all the advantages of the fluorescent tracer-type scale inhibitor provided by this invention. For the advantages of the preparation method of the fluorescent tracer-type scale inhibitor provided by this invention, the application of the fluorescent tracer-type scale inhibitor in a reverse osmosis system, and the online monitoring system for reverse osmosis membrane scaling provided by this invention, please refer to the relevant description of the beneficial effects of the fluorescent tracer-type scale inhibitor provided by this invention, which will not be repeated here. Furthermore, the application of the fluorescent tracer-type scale inhibitor in a reverse osmosis system provided by this invention involves adding the fluorescent tracer-type scale inhibitor as a membrane scale inhibitor to the inlet of the security filter in the reverse osmosis system. This allows the membrane scale inhibitor to be fully mixed with the raw water, and after being buffered by the security filter, it reaches the optimal state for scale inhibition, thereby preventing subsequent scaling of the reverse osmosis membrane. The online monitoring system for reverse osmosis membrane scaling provided by this invention can realize real-time monitoring and precise control of the concentration of the reverse osmosis membrane scale inhibitor, solving the technical problems of traditional scale inhibitors that cannot be monitored online and whose dosage relies on experience, leading to over- or under-dosing. Its application in reverse osmosis systems of steel plants has shown significant results, not only ensuring membrane performance stability but also reducing system operating costs.

[0074] 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 it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A fluorescent tracer-type scale inhibitor, characterized in that, By mass percentage, it comprises: a first mass percentage of an organophosphonic acid compound, a second mass percentage of an acrylic polymer, a third mass percentage of a fluorescent tracer, and the balance being water.

2. The fluorescent tracer-type scale inhibitor as described in claim 1, characterized in that, The organophosphonic acid compounds include at least one of 2-phosphono-1,2,4-tricarboxylate, hydroxyethylidene diphosphonic acid, and aminotrimethylene phosphonic acid.

3. The fluorescent tracer-type scale inhibitor as described in claim 1, characterized in that, The acrylic polymers include at least one of polyacrylic acid, maleic acid-acrylic acid copolymer, and carboxylate-sulfonate-acrylate.

4. The fluorescent tracer-type scale inhibitor as described in claim 1, characterized in that, The fluorescent tracer comprises tetrasodium 1,3,6,8-pyrenetetrasulfonate.

5. The fluorescent tracer-type scale inhibitor as described in claim 1, characterized in that, The first mass percentage includes 30% to 50%, the second mass percentage includes 25% to 35%, and the third mass percentage includes 0.1% to 1%.

6. The fluorescent tracer-type scale inhibitor as described in claim 5, characterized in that, The third mass percentage is 0.1% to 0.5%.

7. A method for preparing a fluorescent tracer-type scale inhibitor as described in any one of claims 1 to 6, characterized in that, include: Weigh each component according to its mass percentage; The weighed organophosphonic acid compound, acrylic polymer, fluorescent tracer and water are added to a stirred tank and mixed evenly to obtain the fluorescent tracer-type scale inhibitor.

8. The application of a fluorescent tracer-type scale inhibitor as described in any one of claims 1 to 6 in a reverse osmosis system, characterized in that, The fluorescent tracer-type scale inhibitor is added as a membrane scale inhibitor to the inlet of the security filter of the reverse osmosis system.

9. An online monitoring system for reverse osmosis membrane scaling, characterized in that, include: A scale inhibitor dosing device, connected to the inlet of the security filter of the reverse osmosis system, is used to add the fluorescent tracer-type scale inhibitor as described in any one of claims 1 to 6 to the reverse osmosis system; An online fluorescence monitor is connected to the outlet of the security filter to monitor the scale inhibitor concentration at the outlet of the security filter in real time. A control device, whose signal input terminal is connected to the online fluorescence monitor and whose signal output terminal is connected to the scale inhibitor dosing device; the control device is configured to: receive the monitoring signal from the online fluorescence monitor and control the scale inhibitor dosing device to adjust the dosage of the fluorescent tracer-type scale inhibitor.

10. The online monitoring system for reverse osmosis membrane scaling as described in claim 9, characterized in that, The control device is further configured to control the concentration of the fluorescent tracer scale inhibitor at 3.8 mg / L to 4.2 mg / L.

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