Preparation method of slow-release scale inhibition material

Abstract

This invention discloses a method for preparing a slow-release scale inhibitor material. The preparation method includes the following steps: Step 1, dissolving divalent zinc salt and polyvinylpyrrolidone in an alcohol solvent to obtain solution A; Step 2, dissolving 2-methylimidazole in an alcohol solvent to obtain solution B; Step 3, adding solution A to solution B and reacting to obtain a metal-organic framework material; Step 4, adding the metal-organic framework material and a solid scale inhibitor to an alcohol solvent, stirring at a preset temperature for a preset time, and then sequentially washing and drying to obtain the slow-release scale inhibitor material. This invention loads the solid scale inhibitor within the pore structure of the metal-organic framework material, enabling the solid scale inhibitor to be released at a continuous rate, thus improving the stability of scale inhibition. Simultaneously, the pore size of the metal-organic framework material can be adjusted, allowing precise control of the slow-release rate of the solid scale inhibitor according to different application scenarios, improving its applicability to various applications.

Description

Technical Field

[0001] This invention belongs to the field of scale inhibitor preparation technology, and specifically relates to a method for preparing a slow-release scale inhibitor material. Background Technology

[0002] Slow-release scale inhibitors are substances that can slowly release active materials to achieve scale prevention. Specifically, they can disperse insoluble inorganic salts in water and prevent or interfere with the scaling of insoluble inorganic salts on pipes and metal surfaces, thereby maintaining the unobstructed flow of pipes and ensuring that equipment has good operating conditions.

[0003] However, existing slow-release scale inhibitors have the following problems:

[0004] (1) Existing slow-release scale inhibitors have unstable release rates during use. When the release rate is too slow, the scale prevention effect is affected, resulting in scale adsorption on the inner wall of the pipeline. When the release rate is too fast, it is easy to cause excessive amounts of scale inhibitor, resulting in waste.

[0005] (2) The release amount of existing slow-release scale inhibitors cannot be precisely controlled, that is, the release amount cannot be adjusted according to the usage scenario, which affects the accuracy of the dosage of slow-release scale inhibitors.

[0006] (3) Existing slow-release scale inhibitors lose their activity after a period of time and cannot continue to inhibit scale, which requires frequent replacement of scale inhibitors, leading to an increase in scale inhibition costs. Summary of the Invention

[0007] To address the aforementioned problems, this invention discloses a method for preparing a slow-release scale inhibitor material, thereby overcoming or at least partially solving the problems.

[0008] To achieve the above objectives, the present invention adopts the following technical solution:

[0009] A method for preparing a slow-release scale inhibitor, the method comprising the following steps:

[0010] Step 1: Dissolve divalent zinc salt and polyvinylpyrrolidone in an alcohol solvent to obtain solution A;

[0011] Step 2: Dissolve 2-methylimidazole in an alcohol solvent to obtain solution B;

[0012] Step 3: Add solution A to solution B to react and obtain a metal-organic framework material;

[0013] Step 4: Add the metal-organic framework material and solid scale inhibitor to an alcohol solvent, stir at a preset temperature for a preset time, and then wash and dry in sequence to obtain a slow-release scale inhibitor material.

[0014] Furthermore, the divalent zinc salt is one or more of zinc acetate, zinc sulfate, zinc nitrate, zinc lactate, and zinc citrate.

[0015] Further, in step 1, the mass ratio of the divalent zinc salt to the polyvinylpyrrolidone is 1:(1-3), and the mass ratio of the divalent zinc salt to the alcohol solvent is 1:(3-10).

[0016] Furthermore, the molar ratio of the divalent zinc salt to the 2-methylimidazole is 1:(1-5);

[0017] In step 2, the mass ratio of 2-methylimidazole to the alcohol solvent is 1:(5-15).

[0018] Furthermore, in step 3, solution A is added to solution B dropwise.

[0019] Furthermore, in step 3, solution A and solution B are stirred and reacted at a temperature of 25℃ to 50℃ for 12h to 24h.

[0020] Further, in step 4, the mass ratio of the metal-organic framework material to the solid scale inhibitor is 1:(1-5), and the mass ratio of the metal-organic framework material to the alcohol solvent is 1:(15-30).

[0021] Furthermore, the preset temperature is 25℃~50℃, and the preset time is 12h~24h.

[0022] Furthermore, in step 4, the drying temperature is 60℃~80℃, and the drying time is 6h~12h.

[0023] Further, the alcohol solvent is methanol or ethanol; the solid scale inhibitor is a green phosphorus-free scale inhibitor, which is one of polyaspartic acid, polyepoxysuccinic acid and S-carboxyethylthiosuccinic acid.

[0024] The advantages and beneficial effects of this invention are:

[0025] In the preparation method of the slow-release scale inhibitor of the present invention, a solid scale inhibitor is loaded into the porous structure of a metal-organic framework material, enabling the solid scale inhibitor to be released at a continuous rate, achieving sustained release and improving the stability of scale inhibition. Simultaneously, the porosity of the metal-organic framework material can be adjusted, allowing for precise control of the slow-release rate and the amount of solid scale inhibitor it can hold according to different application scenarios, thus improving the applicability of the slow-release scale inhibitor material to various application scenarios. Attached Figure Description

[0026] Various other advantages and benefits will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments. The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings:

[0027] Figure 1 This diagram illustrates the implementation steps of a method for preparing a slow-release scale inhibitor in one embodiment of the present invention. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with specific embodiments and corresponding drawings. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0029] The technical solutions provided by the various embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0030] Combination Figure 1 As shown, one embodiment of the present invention discloses a method for preparing a slow-release scale inhibitor, the method comprising the following steps:

[0031] Step 1: Dissolve divalent zinc salt and polyvinylpyrrolidone in an alcohol solvent to obtain solution A. The divalent zinc salt can be one or more of zinc acetate, zinc sulfate, zinc nitrate, zinc lactate, and zinc citrate.

[0032] Step 2: Dissolve 2-methylimidazole in an alcohol solvent to obtain solution B.

[0033] Step 3: Add solution A to solution B. The resulting fixed product is the metal-organic framework material. For example, in one embodiment of this invention, ZIF-8 material (molecular formula C8H) was obtained. 12 N4Zn).

[0034] Step 4: Add the metal-organic framework material and solid scale inhibitor to the alcohol solvent, stir at a preset temperature for a preset time, and then wash and dry in sequence to obtain the slow-release scale inhibitor material.

[0035] In this embodiment, mechanical stirring or ultrasonic dispersion can be used in steps 1, 2, and 4 to improve dissolution efficiency. Furthermore, the alcohol solvent in steps 1 and 4 is methanol or ethanol. The different solubilities of divalent zinc salts in different alcohol solvents affect the performance of the slow-release scale inhibitor, such as the loading capacity and loading efficiency of solid scale inhibitors on metal-organic framework materials. Simultaneously, the solid scale inhibitor is a green, phosphorus-free scale inhibitor, which enhances environmental protection; specifically, it can be one of polyaspartic acid, polyepoxysuccinic acid, and S-carboxyethylthiosuccinic acid.

[0036] In summary, the method for preparing the slow-release scale inhibitor in this embodiment loads a solid scale inhibitor within the porous structure of a metal-organic framework material, enabling the solid scale inhibitor to be released at a continuous rate, achieving sustained release and improving scale inhibition stability. Furthermore, the porosity of the metal-organic framework material can be adjusted, allowing for precise control of the slow-release rate and capacity of the solid scale inhibitor according to different application scenarios, thus enhancing the applicability of the slow-release scale inhibitor material to various applications.

[0037] Meanwhile, the preparation method of this slow-release scale inhibitor is low-cost and can achieve the technical effect of enhancing commercial and industrial competitiveness.

[0038] Specifically, zeolite imidazolate frameworks (ZIFs) are a type of metal-organic framework (MOF) composed of metal ions or oxides and organic ligands. ZIF-8, a material within the zeolite imidazolate framework (ZIF), is considered an ideal precursor for producing hierarchical porous catalysts due to its controlled porosity, large surface area, and uniform heteroatom decoration. In one embodiment of this invention, the cage-like structure of the ZIF-8 material is adapted to the size of the solid scale inhibitor, and loading and release are achieved through the concentration difference of the scale inhibitor inside and outside the ZIF-8 material. This not only enhances the adsorption capacity of the solid scale inhibitor but also enables its stable release. Furthermore, the carboxyl and hydroxyl groups in the solid scale inhibitor can form electrostatic attraction with the metal atoms in the ZIF-8 material and hydrogen bonds with the nitrogen atoms in the ZIF-8 material. Under the influence of these two forces, the solid scale inhibitor can be stably loaded within the ZIF-8 material, forming a slow-release scale inhibitor.

[0039] Based on this, by combining ZIF-8 material with a solid scale inhibitor, the solid scale inhibitor can be loaded within the ZIF-8 material structure. At the same time, the concentration difference inside and outside the ZIF-8 material is used to release the solid scale inhibitor at a continuous rate, thereby achieving a stable scale prevention effect.

[0040] Furthermore, by combining the porous and framework structures of ZIF-8 material with the properties of the solid scale inhibitor, precise control of the slow-release rate is achieved, enabling the solid scale inhibitor to be released at an appropriate rate, thus improving the stability of the release rate. Compared to traditional chemical cleaning agents, the slow-release scale inhibitor material in this invention can slowly and continuously release the solid scale inhibitor, thereby avoiding pollution caused by excess solid scale inhibitor, reducing environmental impact, and improving the safety of workers.

[0041] Furthermore, the ZIF-8 material loaded with solid scale inhibitor can continuously release the solid scale inhibitor, preventing it from rapidly losing its activity. This enhances the durability of the slow-release scale inhibitor and eliminates the need for frequent replacement of the solid scale inhibitor, thereby reducing maintenance costs.

[0042] Furthermore, in step 1, the mass ratio of divalent zinc salt to polyvinylpyrrolidone is 1:(1-3), and in step 2, the molar ratio of divalent zinc salt to 2-methylimidazole is 1:(1-5). Based on this, by adjusting the mass ratio of divalent zinc salt to polyvinylpyrrolidone and the molar ratio of divalent zinc salt to 2-methylimidazole, the pore structure of the metal-organic framework material can be adjusted. Thus, according to different application scenarios of the slow-release scale inhibitor, the amount of solid scale inhibitor loaded on the metal-organic framework material can be adjusted, thereby achieving the technical effect of improving the flexibility of the application scenarios of the slow-release scale inhibitor.

[0043] In addition, the mass ratio of divalent zinc salt to alcohol solvent in step 1 is 1:(3-10), and the mass ratio of 2-methylimidazole to alcohol solvent in step 2 is 1:(5-15).

[0044] Furthermore, in step 3, solution A is added to solution B dropwise to ensure a complete reaction between them. Further, solutions A and B are mixed and stirred at a temperature of 25°C to 50°C at a stirring speed of 100 to 200 rpm for 12 to 24 hours to improve the reaction efficiency between solutions A and B.

[0045] In steps 3 and 4, the reaction products need to be filtered. The filtered solid products are washed with ethanol and deionized water, for example, three times, and then washed by centrifugation to separate the solid and liquid.

[0046] Specifically, the centrifugation speed is 8000–10000 rpm, and the centrifugation washing time is 10–20 min, so that the solid and liquid are completely separated.

[0047] Furthermore, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0048] Of course, in other embodiments, solid-liquid separation can also be performed manually using a filter screen. In one embodiment of the present invention, centrifugation can improve the completeness of solid-liquid separation and also improve the ease of solid-liquid separation.

[0049] In another embodiment, in step 4, the mass ratio of the metal-organic framework material to the solid scale inhibitor is 1:(1-5), and the mass ratio of the metal-organic framework material to the alcohol solvent is 1:(15-30). The preset temperature is 25°C-50°C, and the preset time is 12-24 hours. Simultaneously, the drying temperature is 60°C-80°C, and the drying time is 6-12 hours. This ensures the stability of the slow-release scale inhibitor while improving the completeness of the drying process, further enhancing the purity of the slow-release scale inhibitor.

[0050] Example 1

[0051] Step 1: Add 2g (11mmol) of zinc acetate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0052] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0053] In this embodiment, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc acetate to 2-methylimidazole is 1:1. The mass ratio of zinc acetate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0054] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0055] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0056] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0057] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 2g of polyaspartic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0058] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the centrifugation time was 10 min.

[0059] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:1, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0060] Example 2

[0061] Step 1: Add 2g (12mmol) of zinc sulfate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0062] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0063] In this embodiment, the mass ratio of zinc sulfate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc sulfate to 2-methylimidazole is 12:11. The mass ratio of zinc sulfate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0064] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0065] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0066] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0067] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 2g of polyaspartic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0068] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the washing time was 10 min.

[0069] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:1, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0070] Example 3

[0071] Step 1: Add 2g (11mmol) of zinc nitrate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0072] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0073] In this embodiment, the mass ratio of zinc nitrate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc nitrate to 2-methylimidazole is 1:1. The mass ratio of zinc nitrate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0074] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0075] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0076] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0077] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 2g of polyaspartic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0078] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the washing time was 10 min.

[0079] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:1, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0080] Example 4

[0081] Step 1: Add 2g (9mmol) of zinc lactate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0082] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0083] In this embodiment, the mass ratio of zinc lactate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc lactate to 2-methylimidazole is 9:11. The mass ratio of zinc lactate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0084] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0085] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0086] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0087] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 2g of polyaspartic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0088] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the centrifugation time was 10 min.

[0089] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:1, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0090] Example 5

[0091] Step 1: Add 2g (3mmol) of zinc citrate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0092] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0093] In this embodiment, the mass ratio of zinc citrate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc citrate to 2-methylimidazole is 3:11. The mass ratio of zinc citrate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0094] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0095] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0096] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0097] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 2g of polyaspartic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0098] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the centrifugation time was 10 min.

[0099] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:1, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0100] Example 6

[0101] Step 1: Add 2g (11mmol) of zinc acetate and 4g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0102] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0103] In this embodiment, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:2, and the molar ratio of zinc acetate to 2-methylimidazole is 1:1. The mass ratio of zinc acetate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0104] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0105] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0106] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0107] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 2g of polyaspartic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0108] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the centrifugation time was 10 min.

[0109] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:1, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0110] Example 7

[0111] Step 1: Add 2g (11mmol) of zinc acetate and 6g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0112] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0113] In this embodiment, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:3, and the molar ratio of zinc acetate to 2-methylimidazole is 1:1. The mass ratio of zinc acetate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0114] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0115] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0116] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0117] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 2g of polyaspartic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0118] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the centrifugation time was 10 min.

[0119] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:1, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0120] Example 8

[0121] Step 1: Add 2g (11mmol) of zinc acetate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0122] Step 2: Add 1.06g (13mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0123] In this embodiment, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc acetate to 2-methylimidazole is 11:13. The mass ratio of zinc acetate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 10.6:79.

[0124] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0125] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0126] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0127] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 2g of polyaspartic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0128] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the centrifugation time was 10 min.

[0129] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:1, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0130] Example 9

[0131] Step 1: Add 2g (11mmol) of zinc acetate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0132] Step 2: Add 1.23g (15mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0133] In this embodiment, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc acetate to 2-methylimidazole is 11:15. The mass ratio of zinc acetate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 12.3:79.

[0134] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0135] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0136] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0137] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 2g of polyaspartic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0138] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the centrifugation time was 10 min.

[0139] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:1, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0140] Example 10

[0141] Step 1: Add 2g (11mmol) of zinc acetate and 2g of polyvinylpyrrolidone to 10mL of methanol and stir until completely dissolved to form solution A.

[0142] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of methanol and stir until completely dissolved to form solution B.

[0143] In this embodiment, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc acetate to 2-methylimidazole is 1:1. The mass ratio of zinc acetate to methanol is 1:4, and the mass ratio of 2-methylimidazole to methanol is 9:79.

[0144] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0145] The filtered solid product was then washed three times with anhydrous methanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0146] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0147] Step 4: First, take 2g of ZIF-8 material obtained in step 3 and 2g of polyaspartic acid and add them to 50mL of methanol. Stir at 25℃ for 12h and then filter the product.

[0148] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the centrifugation time was 10 min.

[0149] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:1, and the mass ratio of ZIF-8 material to methanol is 1:19.

[0150] Example 11

[0151] Step 1: Add 2g (11mmol) of zinc acetate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0152] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0153] In this embodiment, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc acetate to 2-methylimidazole is 1:1. The mass ratio of zinc acetate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0154] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0155] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0156] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0157] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 4g of polyaspartic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0158] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the washing time was 10 min.

[0159] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:2, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0160] Example 12

[0161] Step 1: Add 2g (11mmol) of zinc acetate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0162] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0163] In this embodiment, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc acetate to 2-methylimidazole is 1:1. The mass ratio of zinc acetate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0164] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0165] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0166] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0167] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 6g of polyaspartic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0168] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the washing time was 10 min.

[0169] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:3, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0170] Example 13

[0171] Step 1: Add 2g (11mmol) of zinc acetate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0172] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0173] In this embodiment, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc acetate to 2-methylimidazole is 1:1. The mass ratio of zinc acetate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0174] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0175] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0176] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0177] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 8g of polyaspartic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0178] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the centrifugation time was 10 min.

[0179] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:4, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0180] Example 14

[0181] Step 1: Add 2g (11mmol) of zinc acetate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0182] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0183] In this embodiment, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc acetate to 2-methylimidazole is 1:1. The mass ratio of zinc acetate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0184] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0185] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0186] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0187] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 10g of polyaspartic acid and add it to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0188] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the washing time was 10 min.

[0189] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:5, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0190] Example 15

[0191] Step 1: Add 2g (11mmol) of zinc acetate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0192] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0193] In this embodiment, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc acetate to 2-methylimidazole is 1:1. The mass ratio of zinc acetate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0194] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0195] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0196] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0197] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 2g of polyaspartic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0198] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the centrifugation time was 10 min.

[0199] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 18 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:1, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0200] Example 16

[0201] Step 1: Add 2g (11mmol) of zinc acetate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0202] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0203] In this embodiment, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc acetate to 2-methylimidazole is 1:1. The mass ratio of zinc acetate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0204] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0205] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0206] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0207] Step 4: First, take 2g of the ZIF-8 material obtained in step 3 and 2g of polyaspartic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0208] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the washing time was 10 min.

[0209] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 24 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyaspartic acid is 1:1, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0210] Example 17

[0211] Step 1: Add 2g (11mmol) of zinc acetate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0212] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0213] In this embodiment, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc acetate to 2-methylimidazole is 1:1. The mass ratio of zinc acetate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0214] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0215] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0216] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0217] Step 4: First, take 2g of ZIF-8 material obtained in step 3 and 2g of polyepoxysuccinic acid and add it to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0218] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the centrifugation time was 10 min.

[0219] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to polyepoxysuccinic acid is 1:1, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0220] Example 18

[0221] Step 1: Add 2g (11mmol) of zinc acetate and 2g of polyvinylpyrrolidone to 10mL of ethanol and stir until completely dissolved to form solution A.

[0222] Step 2: Add 0.9g (11mmol) of 2-methylimidazole to 10mL of ethanol and stir until completely dissolved to form solution B.

[0223] In this embodiment, the mass ratio of zinc acetate to polyvinylpyrrolidone is 1:1, and the molar ratio of zinc acetate to 2-methylimidazole is 1:1. The mass ratio of zinc acetate to ethanol is 1:4, and the mass ratio of 2-methylimidazole to ethanol is 9:79.

[0224] Step 3: First, add solution A to solution B dropwise, stir and mix at 25°C, and after reacting for 12 hours, filter the reaction product.

[0225] The filtered solid product was then washed three times with anhydrous ethanol and deionized water. The centrifugation washing was performed at a speed of 8000 rpm for 10 minutes.

[0226] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material.

[0227] Step 4: First, take 2g of ZIF-8 material obtained in step 3 and 2g of S-carboxyethyl thiosuccinic acid and add them to 50mL of ethanol. Stir at 25℃ for 12h and then filter the product.

[0228] Then, it was washed three times with deionized water by centrifugation, and then three times with anhydrous ethanol by centrifugation. The centrifugation speed for the washing was 8000 rpm, and the centrifugation time was 10 min.

[0229] Finally, the solid obtained after centrifugation was dried in a vacuum oven at 60°C for 6 hours to obtain ZIF-8 material with a fixed solid scale inhibitor load, i.e., a slow-release scale inhibitor material. In this embodiment, the mass ratio of ZIF-8 material to S-carboxyethyl thiosuccinic acid is 1:1, and the mass ratio of ZIF-8 material to ethanol is 1:19.

[0230] The above description is merely a specific embodiment of the present invention. Under the teachings of the present invention, those skilled in the art can make other improvements or modifications based on the above embodiments. Those skilled in the art should understand that the above specific description is only to better explain the purpose of the present invention, and the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing a slow release scale inhibiting material, characterized by, The preparation method includes the following steps: Step 1: Dissolve divalent zinc salt and polyvinylpyrrolidone in an alcohol solvent to obtain solution A; Step 2: Dissolve 2-methylimidazole in an alcohol solvent to obtain solution B; Step 3: Add solution A to solution B to react and obtain a metal-organic framework material; Step 4: Add the metal-organic framework material and solid scale inhibitor to an alcohol solvent, stir at a preset temperature for a preset time, and then wash and dry in sequence to obtain a slow-release scale inhibitor material; The mass ratio of the divalent zinc salt to polyvinylpyrrolidone is 1:(1-3), and the molar ratio of the divalent zinc salt to 2-methylimidazole is 1:(1-5). By adjusting the mass ratio of the divalent zinc salt to polyvinylpyrrolidone and the molar ratio of the divalent zinc salt to 2-methylimidazole, the porosity structure of the metal-organic framework material can be adjusted.

2. The method of claim 1, wherein the slow release scale inhibiting material is prepared by the steps of: The divalent zinc salt is one or more of zinc acetate, zinc sulfate, zinc nitrate, zinc lactate, and zinc citrate.

3. The method for preparing the slow-release scale inhibitor material according to claim 1, characterized in that, In step 1, the mass ratio of the divalent zinc salt to the alcohol solvent is 1:(3~10).

4. The method for preparing the slow-release scale inhibitor material according to claim 1, characterized in that, In step 2, the mass ratio of 2-methylimidazole to the alcohol solvent is 1:(5~15).

5. The method for preparing the slow-release scale inhibitor material according to claim 1, characterized in that, In step 3, solution A is added to solution B dropwise.

6. The method for preparing the slow-release scale inhibitor according to claim 1, characterized in that, In step 3, solution A and solution B are stirred and reacted at a temperature of 25℃ to 50℃ for 12 h to 24 h.

7. The method for preparing the slow-release scale inhibitor material according to claim 1, characterized in that, In step 4, the mass ratio of the metal-organic framework material to the solid scale inhibitor is 1:(1~5), and the mass ratio of the metal-organic framework material to the alcohol solvent is 1:(15~30).

8. The method for preparing the slow-release scale inhibitor material according to claim 1, characterized in that, The preset temperature is 25℃ ~ 50℃, and the preset time is 12 h ~ 24 h.

9. The method for preparing the slow-release scale inhibitor material according to claim 1, characterized in that, In step 4, the drying temperature is 60 ℃ ~ 80 ℃, and the drying time is 6 h ~ 12 h.

10. The method for preparing the slow-release scale inhibitor material according to any one of claims 1-9, characterized in that, The alcohol solvent is methanol or ethanol; the solid scale inhibitor is a green phosphorus-free scale inhibitor, which is one of polyaspartic acid, polyepoxysuccinic acid and S-carboxyethyl thiosuccinic acid.

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