Macrocyclic polyamine supramolecular scale removal and prevention agent, preparation method and application

Abstract

The invention provides a macrocyclic polyamine supramolecular scale removal and prevention agent which comprises the following components in percentage by mass based on the total mass of the macrocyclic polyamine supramolecular complex aqueous solution: 4-6% of a solubilizer, 2-3% of a penetrant and the balance of a slow release agent, and the sum of the mass percentage of the solubilizer, the mass percentage of the penetrant and the mass percentage of the slow release agent is 100%. The mass percentage of the macrocyclic polyamine supramolecular complex aqueous solution is 0.5-2%, the macrocyclic polyamine supramolecular complex aqueous solution comprises macrocyclic polyamine, quaternary ammonium salt and water which are mixed according to the mass ratio of 1: (1-1.5): (4-6), the macrocyclic polyamine has a structure shown as a formula (I), and R1, R2, R3 and R4 are independently selected from groups of-H,-CH3,-CH2CH3 and-CH2COOH respectively. According to the macrocyclic polyamine supramolecular descaling and antiscaling agent disclosed by the invention, the descaling rate of barium sulfate can reach 88-95%, and the scale inhibition rate can reach 90-95%.

Description

Technical Field

[0001] The present invention relates to the technical field of oil and gas production engineering in the petroleum industry, and in particular to a macrocyclic polyamine supramolecular descaling and antiscaling agent, a preparation method and application thereof. Background Art

[0002] As oil and gas field development enters the middle and late stages, the application of technologies such as water injection and tertiary oil recovery has made scaling problems inevitable in injection systems, production systems, and surface gathering and transportation systems. Types of oilfield scaling include carbonate scale (CaCO3), sulfate scale (CaSO4, BaSO4, SrSO4), and iron scale, which form mixed scales. Scale is deposited in the wellbore tubing in the form of a thick layer, thereby reducing the diameter of the tubing, causing blockage and fluid obstruction. Severe scaling can lead to pump sticking and rod breakage, posing a threat to safe production operations. Barium strontium scale, in particular, is insoluble in acid, has a hard texture, and is difficult to remove, posing a huge challenge to the later development of the oilfield. Damage caused by barium strontium scale in oilfields is a problem faced by oilfield water flooding, gas flooding, chemical flooding, and other technologies. How to remove and prevent the formation of barium strontium scale is one of the current global problems.

[0003] Barium strontium scale is a hard scale that cannot be effectively dissolved by inorganic acids such as sulfuric acid and hydrochloric acid. Once formed, it is difficult to remove by acidification. Using a chelating agent to form a complex with barium strontium metal ions to avoid precipitation by combining with sulfate ions is a feasible method to inhibit or remove barium strontium scale. Common chelating agents include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, gluconic acid, citric acid, and polyacrylic acid or acrylic acid, maleic acid copolymers, etc. Taking ethylenediaminetetraacetic acid as an example, it works by converting insoluble barium sulfate into barium carbonate or other soluble compounds. However, the stability of the metal ion chelate formed is controlled by the hydrogen ion concentration in the environment, that is, it is very sensitive to pH value, resulting in poor descaling and anti-scaling effect of the chelation method, and it cannot fundamentally solve the scaling problem.

[0004] In recent years, supramolecular chemistry has experienced rapid development, blurring the boundaries between organic chemistry, inorganic chemistry, biochemistry, and materials chemistry, emphasizing supramolecular systems with specific structures and functions. Some atoms in the supramolecular molecule have unsaturated outer orbitals. They continuously search for metal atoms with free outer electrons in solution, borrowing electrons and orbitals from each other to form stable "marriage molecules" beyond molecular boundaries. This is known as supramolecular selective assembly, forming a stable monolayer on the atomic metal surface—a thin, dense supramolecular membrane. This selective supramolecular assembly process vibrates, penetrates, disperses, and cleans various contaminants, dispersing solid particles into molecular or ionic states to form water-soluble polycyclic complexes, ultimately achieving cleaning of pipeline interior surfaces.

[0005] For example, patent CN111621278B discloses a method for synthesizing a macrocyclic compound supramolecular scale-dissolving material, comprising the following steps: (1) preparation of a supramolecular inclusion body; adding component A, component B, component C and water to a reaction vessel, wherein the molar ratio of component A to component B is 1:(1-1.3), and the mass ratio of (component A+component B), component C and water is (38-42):(4-6):(40-48), stirring and heating to 60-70°C, reacting for 2-3h, and obtaining a mixture containing a supramolecular inclusion body; wherein component A is a macrocyclic compound including β-cyclodextrin, γ-cyclodextrin, 18-crown-6 ether, calix[6]arene and calix[8]arene; component B is selected from quaternary ammonium salt cationic surfactants and zwitterionic surfactants having 12-18 carbon atoms and containing a hydrophobic tail chain; component C is selected from low molecular weight alcohols; (II) compounding of supramolecular antiscalant: continuing to add 4-6.5wt% of solubilizer, 2-3wt% of complexing agent and 2-3wt% of stripping agent, stirring at room temperature for 2-3h to obtain a compounded supramolecular antiscalant. This patent is based on the formation of supramolecular inclusion bodies synthesized by host and guest, and at the same time adding solubilizers, complexing agents and other auxiliary agents to form antiscalants. It can be used in oil and gas fields and other industrial cleaning and prevention fields in the petroleum industry, and is particularly suitable for the prevention and control of barium strontium scale. The supramolecular antiscalant has a pH value of about 9, is environmentally friendly, and improves the antiscaling efficiency and antiscaling effect.

[0006] In view of the complexity of the composition and compounding of scale removers and scale inhibitors in the prior art, it is an urgent problem to provide a supramolecular scale remover and scale inhibitor with a simple formula and excellent scale remover and scale inhibitor effect. Summary of the Invention

[0007] In order to solve the problems of the prior art, the present invention provides a macrocyclic polyamine supramolecular scale remover and scale inhibitor, which utilizes the supramolecular host-guest recognition function and good structural designability of macrocyclic polyamines to prepare supramolecular scale remover and scale inhibitor, thereby improving the scale removal and scale prevention efficiency of barium strontium scale in the field of oil and gas production engineering technology, and solving the defects of the current supramolecular scale remover and scale inhibitor, such as the complicated preparation process.

[0008] The technical solutions of the present invention are as follows:

[0009] The present invention provides a macrocyclic polyamine supramolecular scale remover and anti-scaling agent, comprising a macrocyclic polyamine supramolecular complex aqueous solution, a solubilizer, a penetrant, and a sustained-release agent. Based on the total mass of the macrocyclic polyamine supramolecular complex aqueous solution, the mass percentage of the solubilizer is 4-6%, the mass percentage of the penetrant is 2-3%, and the mass percentage of the sustained-release agent is 0.5-2%. The macrocyclic polyamine supramolecular complex aqueous solution comprises macrocyclic polyamine, quaternary ammonium salt, and water mixed in a mass ratio of 1:(1-1.5):(4-6).

[0010] The macrocyclic polyamine has the following structure:

[0011]

[0012] Wherein, R1, R2, R3, and R4 are each independently selected from -H, -CH3, -CH2CH3, -CH2COOH, group.

[0013] More preferably, R1, R2, R3, and R4 are each independently -CH2COOH, The O-containing or N-containing group contributes to the formation of a more stable supramolecule.

[0014] Furthermore, the quaternary ammonium salt includes at least one of dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium chloride, and hexadecyldimethylbenzylammonium chloride; further preferably, the quaternary ammonium salt is hexadecyldimethylbenzylammonium chloride.

[0015] The quaternary ammonium salt used in the present invention mainly acts as a surfactant, which helps to peel off scale from the metal surface.

[0016] Furthermore, the solubilizer includes a polyol or a polyol amine, including at least one of glycerol, propylene glycol, ethylene glycol, trimethylolpropane, diethanolamine, triethanolamine, and triisopropanolamine.

[0017] The polyol or polyolamine used in the present invention mainly acts as a solubilizer, which is beneficial for solubilizing the scale wrapped by the macrocyclic polyamine supramolecule in water. Among them, the solubilization of alcohols or amines with a large number of hydroxyl groups is better because hydroxyl groups are solubilizing groups.

[0018] Furthermore, the penetrant is a fatty alcohol polyoxyethylene ether having the following structure:

[0019]

[0020] The straight chain or branched chain R is C6~C 10 , n is 4 to 6; preferably R is a straight chain.

[0021] Furthermore, the sustained-release agent is imidazoline, having the following structure:

[0022]

[0023] Wherein the straight chain or branched chain R is C 11 ~C 17 ; Preferably R is a straight chain.

[0024] The imidazoline used in the present invention plays a role of slow release. After the macrocyclic polyamine supramolecular descaling and anti-scaling is completed, the imidazoline can be adsorbed on the metal surface to form a protective film to prevent scale from depositing again.

[0025] The present invention also provides a method for preparing the aforementioned macrocyclic polyamine supramolecular descaling and antiscaling agent, comprising the following steps:

[0026] Step (1): macrocyclic polyamine, quaternary ammonium salt and water are charged into a reaction kettle in a mass ratio of 1:(1-1.5):(4-6), heated to 60-80° C. under stirring, and refluxed for 2-4 hours to obtain a supramolecular complex aqueous solution;

[0027] Step (2): adding 4-6w% by weight of a solubilizer and 2-3w% by weight of a penetrant to the supramolecular complex aqueous solution, and stirring at room temperature for 1-2 hours;

[0028] Step (3): continue to add 0.5-2w% of the sustained-release agent to the mixed solution of step (2), stirring at room temperature for 1-2 hours to obtain a macrocyclic polyamine supramolecular descaling and antiscaling agent.

[0029] Furthermore, in step (1), the stirring rate is 100 to 500 rpm.

[0030] The present invention also provides a use of the macrocyclic polyamine supramolecular descaling and antiscaling agent, including but not limited to descaling and antiscaling operations in oilfield gathering and transportation pipelines, wherein the prepared macrocyclic polyamine supramolecular descaling and antiscaling agent is prepared into an aqueous solution with a mass fraction of 15 to 20%, and injected into the pipeline to be treated for soaking treatment.

[0031] The excellent effects of the present invention are as follows:

[0032] (1) The macrocyclic polyamine supramolecular scale remover and scale inhibitor of the present invention has the functions of selective assembly and host-guest recognition. Through the processes of penetration, dispersion, molecular assembly, etc., it can realize the stripping, decomposition and cleaning of insoluble scales such as barium strontium scale and oil scale, and self-assemble into a dense supramolecular film on the metal surface. The supramolecular film has the anti-corrosion and anti-fouling properties similar to those of lotus leaves, achieving the purpose of long-term scale removal and scale prevention.

[0033] (2) The pH value of the macrocyclic polyamine supramolecular descaling and antiscaling agent is between 7 and 8. It has no corrosion to the metal surface and no pollution to the environment, and is environmentally friendly and green.

[0034] (3) The preparation method of the macrocyclic polyamine supramolecular descaling and antiscaling agent of the present invention can be obtained by simple compounding, which is conducive to industrial production operation.

[0035] (4) When applied to oilfield gathering and transportation pipelines, the macrocyclic polyamine supramolecular descaling and antiscaling agent only needs to be prepared into an aqueous solution and added into the system through a pump to achieve online cleaning and reduce operating costs.

[0036] (5) The macrocyclic polyamine supramolecular descaling and antiscaling agent of the present invention can achieve a descaling rate of 88-95% for barium sulfate and a scale inhibition rate of 90-95%. DETAILED DESCRIPTION

[0037] The preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described below, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. Instead, these embodiments are provided to make the present invention more thorough and complete and to fully convey the scope of the present invention to those skilled in the art.

[0038] Example 1

[0039] Example 1 provides a macrocyclic polyamine supramolecular scale remover and anti-scaling agent, comprising a macrocyclic polyamine supramolecular complex aqueous solution, a solubilizer, a penetrant and a sustained-release agent. Based on the total mass of the macrocyclic polyamine supramolecular complex aqueous solution, the mass percentage of the solubilizer is 4%, the mass percentage of the penetrant is 3%, and the mass percentage of the sustained-release agent is 0.5%. The macrocyclic polyamine supramolecular complex aqueous solution is composed of a macrocyclic polyamine, a quaternary ammonium salt and water mixed in a mass ratio of 1:1:4.

[0040] The preparation method is as follows:

[0041] (1) macrocyclic polyamine, quaternary ammonium salt (dodecyldimethylbenzyl ammonium chloride) and water are charged into a reaction kettle in a mass ratio of 1:1:4, heated to 60° C. under stirring, and refluxed for 4 hours to obtain a supramolecular complex aqueous solution;

[0042] (2) adding 4w% of a solubilizer (ethylene glycol) and 3w% of a penetrant (fatty alcohol polyoxyethylene ether) to the supramolecular complex aqueous solution and stirring at room temperature for 2 hours;

[0043] (3) adding 0.5w% of a slow-release agent (imidazoline) and stirring at room temperature for 2 hours to obtain a macrocyclic polyamine supramolecular descaling and antiscaling agent;

[0044] The structures of the macrocyclic polyamine, fatty alcohol polyoxyethylene ether and imidazoline used are as follows:

[0045]

[0046] Example 2

[0047] Example 2 provides a macrocyclic polyamine supramolecular scale remover and scale inhibitor, comprising a macrocyclic polyamine supramolecular complex aqueous solution, a solubilizer, a penetrant and a sustained-release agent. Based on the total mass of the macrocyclic polyamine supramolecular complex aqueous solution, the mass percentage of the solubilizer is 6%, the mass percentage of the penetrant is 2%, and the mass percentage of the sustained-release agent is 2%. The macrocyclic polyamine supramolecular complex aqueous solution is composed of a macrocyclic polyamine, a quaternary ammonium salt and water mixed in a mass ratio of 1:1.5:6.

[0048] The preparation method is as follows:

[0049] (1) macrocyclic polyamine, quaternary ammonium salt (octadecyltrimethylammonium chloride) and water are charged into a reaction kettle in a mass ratio of 1:1.5:6, heated to 80° C. under stirring, and refluxed for 2 hours to obtain a supramolecular complex aqueous solution;

[0050] (2) adding 6w% of a solubilizer (triisopropanolamine) and 2w% of a penetrant (fatty alcohol polyoxyethylene ether) to the supramolecular complex aqueous solution and stirring at room temperature for 1 hour;

[0051] (3) Continue to add 2w% of slow-release agent (imidazoline) and stir at room temperature for 1 hour to obtain macrocyclic polyamine supramolecular descaling and antiscaling agent 2;

[0052] The structures of the macrocyclic polyamine, fatty alcohol polyoxyethylene ether and imidazoline used are as follows:

[0053]

[0054] Example 3

[0055] Example 3 provides a macrocyclic polyamine supramolecular scale remover and scale inhibitor, comprising a macrocyclic polyamine supramolecular complex aqueous solution, a solubilizer, a penetrant and a sustained-release agent. Based on the total mass of the macrocyclic polyamine supramolecular complex aqueous solution, the mass percentage of the solubilizer is 5%, the mass percentage of the penetrant is 2.5%, and the mass percentage of the sustained-release agent is 1.8%. The macrocyclic polyamine supramolecular complex aqueous solution is composed of macrocyclic polyamine, quaternary ammonium salt and water mixed in a mass ratio of 1:1.2:5.

[0056] The preparation method is as follows:

[0057] (1) macrocyclic polyamine, quaternary ammonium salt (hexadecyldimethylbenzyl ammonium chloride) and water were charged into a reaction kettle in a mass ratio of 1:1.2:5, heated to 70° C. under stirring, and refluxed for 2.5 hours to obtain a supramolecular complex aqueous solution;

[0058] (2) adding 5w% of a solubilizer (glycerol) and 2.5w% of a penetrant (fatty alcohol polyoxyethylene ether) to the supramolecular complex aqueous solution and stirring at room temperature for 1.5 hours;

[0059] (3) adding 1.8w% of a slow-release agent (imidazoline) and stirring at room temperature for 1.5 hours to obtain a macrocyclic polyamine supramolecular descaling and antiscaling agent;

[0060] The structures of the macrocyclic polyamine, fatty alcohol polyoxyethylene ether and imidazoline used are as follows:

[0061]

[0062] Example 4

[0063] Example 4 provides a macrocyclic polyamine supramolecular scale remover and anti-scaling agent, which comprises a macrocyclic polyamine supramolecular complex aqueous solution, a solubilizer, a penetrant and a sustained-release agent. Based on the total mass of the macrocyclic polyamine supramolecular complex aqueous solution, the mass percentage of the solubilizer is 4.5%, the mass percentage of the penetrant is 2.5%, and the mass percentage of the sustained-release agent is 1.8%. The macrocyclic polyamine supramolecular complex aqueous solution is composed of a macrocyclic polyamine, a quaternary ammonium salt and water mixed in a mass ratio of 1:1.2:4.5.

[0064] The preparation method is as follows:

[0065] (1) macrocyclic polyamine, quaternary ammonium salt (hexadecyltrimethylammonium chloride) and water were charged into a reaction kettle in a mass ratio of 1:1.2:4.5, heated to 80° C. under stirring, and refluxed for 2.5 hours to obtain a supramolecular complex aqueous solution;

[0066] (2) adding 4.5w% of a solubilizer (propylene glycol) and 2.5w% of a penetrant (fatty alcohol polyoxyethylene ether) to the supramolecular complex aqueous solution and stirring at room temperature for 1 hour;

[0067] (3) 1.8w% of a sustained-release agent (imidazoline) was added and stirred at room temperature for 1 hour to obtain a macrocyclic polyamine supramolecular descaling and antiscaling agent 4;

[0068] The structures of the macrocyclic polyamine, fatty alcohol polyoxyethylene ether and imidazoline used are as follows:

[0069]

[0070] Example 5

[0071] Example 5 provides a macrocyclic polyamine supramolecular scale remover and scale inhibitor, comprising a macrocyclic polyamine supramolecular complex aqueous solution, a solubilizer, a penetrant and a sustained-release agent. Based on the total mass of the macrocyclic polyamine supramolecular complex aqueous solution, the mass percentage of the solubilizer is 4.8%, the mass percentage of the penetrant is 2.5%, and the mass percentage of the sustained-release agent is 1.5%. The macrocyclic polyamine supramolecular complex aqueous solution is composed of a macrocyclic polyamine, a quaternary ammonium salt and water mixed in a mass ratio of 1:1.5:5.5.

[0072] The preparation method is as follows:

[0073] (1) macrocyclic polyamine, quaternary ammonium salt (dodecyltrimethylammonium chloride) and water are charged into a reaction kettle in a mass ratio of 1:1.5:5.5, heated to 80° C. under stirring, and refluxed for 2.5 hours to obtain a supramolecular complex aqueous solution;

[0074] (2) adding 4.8w% of a solubilizer (diethanolamine) and 2.5w% of a penetrant (fatty alcohol polyoxyethylene ether) to the supramolecular complex aqueous solution and stirring at room temperature for 1 hour;

[0075] (3) adding 1.5w% of a slow-release agent (imidazoline) and stirring at room temperature for 1 hour to obtain a macrocyclic polyamine supramolecular descaling and antiscaling agent;

[0076] The structures of the macrocyclic polyamine, fatty alcohol polyoxyethylene ether and imidazoline used are as follows:

[0077]

[0078] Example 6

[0079] Example 6 provides a macrocyclic polyamine supramolecular scale remover and scale inhibitor, comprising a macrocyclic polyamine supramolecular complex aqueous solution, a solubilizer, a penetrant and a sustained-release agent. Based on the total mass of the macrocyclic polyamine supramolecular complex aqueous solution, the mass percentage of the solubilizer is 4.5%, the mass percentage of the penetrant is 2.5%, and the mass percentage of the sustained-release agent is 1.8%. The macrocyclic polyamine supramolecular complex aqueous solution is composed of a macrocyclic polyamine, a quaternary ammonium salt and water mixed in a mass ratio of 1:1.4:5.

[0080] The preparation method is as follows:

[0081] (1) macrocyclic polyamine, quaternary ammonium salt (tetradecyldimethylbenzyl ammonium chloride) and water are charged into a reaction kettle in a mass ratio of 1:1.4:5, heated to 70° C. under stirring, and refluxed for 2.5 hours to obtain a supramolecular complex aqueous solution;

[0082] (2) adding 4.5w% of a solubilizer (trimethylolpropane) and 2.5w% of a penetrant (fatty alcohol polyoxyethylene ether) to the supramolecular complex aqueous solution and stirring at room temperature for 1.5 hours;

[0083] (3) 1.8w% of a sustained-release agent (imidazoline) was added and stirred at room temperature for 1.5 hours to obtain a macrocyclic polyamine supramolecular descaling and antiscaling agent 6;

[0084] The structures of the macrocyclic polyamine, fatty alcohol polyoxyethylene ether and imidazoline used are as follows:

[0085]

[0086] Example 7

[0087] Example 7 provides a macrocyclic polyamine supramolecular scale remover and scale inhibitor, comprising a macrocyclic polyamine supramolecular complex aqueous solution, a solubilizer, a penetrant and a sustained-release agent. Based on the total mass of the macrocyclic polyamine supramolecular complex aqueous solution, the mass percentage of the solubilizer is 4.8%, the mass percentage of the penetrant is 2.5%, and the mass percentage of the sustained-release agent is 1.8%. The macrocyclic polyamine supramolecular complex aqueous solution is composed of a macrocyclic polyamine, a quaternary ammonium salt and water mixed in a mass ratio of 1:1.4:5.

[0088] The preparation method is as follows:

[0089] (1) macrocyclic polyamine, quaternary ammonium salt (tetradecyltrimethylammonium chloride) and water are charged into a reaction kettle in a mass ratio of 1:1.2:5, heated to 70° C. under stirring, and refluxed for 2.5 hours to obtain a supramolecular complex aqueous solution;

[0090] (2) adding 4.8w% of a solubilizer (triethanolamine) and 2.5w% of a penetrant (fatty alcohol polyoxyethylene ether) to the supramolecular complex aqueous solution and stirring at room temperature for 1.5 hours;

[0091] (3) 1.8w% of a sustained-release agent (imidazoline) was added and stirred at room temperature for 1.5 hours to obtain a macrocyclic polyamine supramolecular descaling and antiscaling agent 7.

[0092] The structures of the macrocyclic polyamine, fatty alcohol polyoxyethylene ether and imidazoline used are as follows:

[0093]

[0094]

[0095] Test Case

[0096] The macrocyclic polyamine supramolecular descaling and antiscaling agent obtained in Examples 1 to 7 was prepared into an aqueous solution with a mass fraction of 15 to 20%, and a barium sulfate scale sample was added and treated at 50° C. for 48 hours, as shown in Table 1 below.

[0097] Table 1 Test results of the descaling rate and scale inhibition rate of the macrocyclic polyamine supramolecular descaling and antiscaling agent of Examples 1-7

[0098] Descaling and antiscaling agent No. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Mass fraction, % 15 20 18 15 20 16 18 Descaling rate, % 88.2 91.2 90.0 89.7 91.5 90.0 90.8 Scale inhibition rate, % 91.2 92.4 90.8 91.2 90.8 91.4 91.1

[0099] In Table 1, the descaling rate and antiscaling rate are tested according to the following industry standards:

[0100] The descaling rate is implemented in accordance with the Technical Requirements for Chemical Descaling Agents for Oilfield Technical Systems (Q / SY148-2007). The experimental steps are as follows:

[0101] ① Select and clean several conical flasks and separatory funnels, fold and mark the filter paper to be used, place the scale sample and filter paper in an oven (102℃) and dry for 2 hours, and weigh the filter paper as M0;

[0102] ② Weigh the dried scale sample for scale dissolution experiment (under the specified experimental temperature, scale sample mass M, macrocyclic polyamine supramolecular scale remover and anti-scaling agent dosage, dilute to 100mL with deionized water, and heat in a constant temperature water bath for 24h), and perform filtration experiment operation;

[0103] ③ Place the filter paper with scale sample after filtration in an oven (102℃) and dry it for 6 hours. Weigh its weight as M1 and calculate its descaling rate.

[0104] ④Calculation formula for descaling rate:

[0105]

[0106] The scale inhibition rate is determined according to the static anti-scaling method specified in the "Evaluation Method for Performance of Oilfield Anti-scaling Agents" (SY-T5673-1993). The static anti-scaling method is an important means of evaluating scale inhibition performance. Its principle is to prepare a certain volume and concentration of Ba 2+ Metal cation solution, add an equivalent amount of SO4 2- Add a certain concentration of anti-scaling agent solution to the scale-forming anion solution, keep the temperature constant for a certain time under certain temperature and pH conditions, and allow the BaSO4 scale to completely precipitate. After the solution is cooled to room temperature, filter it and measure the Ba 2+ concentration.

[0107] ① Prepare aqueous solutions of barium chloride, strontium chloride, sodium sulfate, and macrocyclic polyamine supramolecular descaling and antiscaling agent of the required concentrations, and calculate the theoretical amount of barium sulfate / strontium precipitation M1 of the prepared aqueous solution mixture;

[0108] ② Take 50mL of mixed aqueous solution of barium chloride and strontium chloride and 50mL of sodium sulfate aqueous solution and place them in 100mL narrow-necked bottles respectively, and add 10mL of macrocyclic polyamine supramolecular descaling and antiscaling agent aqueous solution to each of the two bottles of solution;

[0109] ③ Preheat the two bottles of solution at the required experimental temperature for 30 minutes;

[0110] ④ Mix the preheated solutions and keep them at the preheated temperature for more than 16 hours;

[0111] ⑤ Filter the resulting solution using filter paper and a suction filter, then dry the precipitate for more than 30 minutes and weigh it to obtain the actual precipitate amount M2;

[0112] ⑥Calculate the scale inhibition rate S by the following formula:

[0113]

[0114] The above description is merely a preferred embodiment of the present invention and does not constitute any other form of limitation to the present invention. Any modification or equivalent variation based on the technical essence of the present invention shall still fall within the scope of protection claimed by the present invention.

Claims

1. A macrocyclic polyamine supramolecular descaling and antiscaling agent, characterized in that: The invention comprises a macrocyclic polyamine supramolecular complex aqueous solution, a solubilizer, a penetrant and a sustained-release agent. Based on the total mass of the macrocyclic polyamine supramolecular complex aqueous solution, the mass percentage of the solubilizer is 4-6%, the mass percentage of the penetrant is 2-3%, and the mass percentage of the sustained-release agent is 0.5-2%. The macrocyclic polyamine supramolecular complex aqueous solution comprises macrocyclic polyamine, quaternary ammonium salt and water mixed in a mass ratio of 1:(1-1.5):(4-6). The macrocyclic polyamine has the following structure: Wherein, R1, R2, R3, and R4 are each independently selected from -H, -CH3, -CH2CH3, -CH2COOH, group.

2. The macrocyclic polyamine supramolecular descaling and antiscaling agent according to claim 1, characterized in that R1, R2, R3, and R4 are each independently -CH2COOH, O- or N-containing groups.

3. The macrocyclic polyamine supramolecular descaling and antiscaling agent according to claim 1 or 2, characterized in that The quaternary ammonium salt includes at least one of dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium chloride, and hexadecyldimethylbenzylammonium chloride.

4. The macrocyclic polyamine supramolecular descaling and antiscaling agent according to claim 1 or 2, characterized in that The solubilizer includes a polyol or a polyol amine, including at least one of glycerol, propylene glycol, ethylene glycol, trimethylolpropane, diethanolamine, triethanolamine, and triisopropanolamine.

5. The macrocyclic polyamine supramolecular descaling and antiscaling agent according to claim 1 or 2, characterized in that: The penetrant is a fatty alcohol polyoxyethylene ether having the following formula (II): Among them, the straight chain or branched chain R is C6~C 10 , n is 4 to 6.

6. The macrocyclic polyamine supramolecular descaling and antiscaling agent according to claim 1 or 2, characterized in that: The sustained-release agent is imidazoline, having the following structure: Among them, the straight chain or branched chain R is C 11 ~C 17 .

7. A method for preparing the macrocyclic polyamine supramolecular descaling and antiscaling agent according to any one of claims 1 to 6, characterized in that: The steps include: Step (1): macrocyclic polyamine, quaternary ammonium salt and water are charged into a reaction kettle in a mass ratio of 1:(1-1.5):(4-6), heated to 60-80° C. under stirring, and refluxed for 2-4 hours to obtain a supramolecular complex aqueous solution; Step (2): adding 4-6w% by weight of a solubilizer and 2-3w% by weight of a penetrant to the supramolecular complex aqueous solution, and stirring at room temperature for 1-2 hours; Step (3): continue to add 0.5-2w% of the sustained-release agent to the mixed solution of step (2), stirring at room temperature for 1-2 hours to obtain a macrocyclic polyamine supramolecular descaling and antiscaling agent.

8. The method for preparing the macrocyclic polyamine supramolecular descaling and antiscaling agent according to claim 7, wherein: In step (1), the stirring rate is 100 to 500 rpm.

9. Use of the macrocyclic polyamine supramolecular descaling and antiscaling agent according to any one of claims 1 to 6, characterized in that: Including but not limited to descaling and antiscaling operations on oilfield gathering and transportation pipelines, the prepared macrocyclic polyamine supramolecular descaling and antiscaling agent is prepared into an aqueous solution with a mass fraction of 15-20%, and injected into the pipeline to be treated for soaking treatment.

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