阅读说明：本技术 一种活性超分子溶垢剂合成方法及其应用 (Synthesis method and application of active supermolecule scale dissolver ) 是由 虞建业 王彪 包敏新 于 2020-06-03 设计创作，主要内容包括：本发明公开了一种活性超分子溶垢剂合成方法,包括向反应容器中加入有机胺、双卤代烷、相转移剂、溶剂以及pH调节剂,以摩尔比计,有机胺：双卤代烷：相转移剂＝(2.2-2.3)：1：(0.03-0.07)；有机胺、双卤代烷、相转移剂质量之和与溶剂的质量比为＝1:(1-1.2)；加入pH调节剂调节反应体系的pH值至9-9.5；升温至85℃～90℃,搅拌反应22h～24h后,得到活性超分子溶垢剂。本发明适用于溶解清除油田集输管线钡锶垢,水驱、气驱、化学驱注采层钡锶垢以及碳酸钙垢,提高了钡锶垢等难溶垢溶垢率,降低一般强碱性溶垢剂对设备的腐蚀,降低了残液处理成本及对环境伤害,提高了综合效益。(The invention discloses a method for synthesizing an active supermolecule scale dissolver, which comprises the steps of adding organic amine, bihalogenated alkane, a phase transfer agent, a solvent and a pH regulator into a reaction vessel, wherein the molar ratio of the organic amine: bis-alkyl halides: phase transfer agent ═ (2.2-2.3): 1: (0.03-0.07); the mass ratio of the sum of the mass of the organic amine, the bihalogenated alkane and the phase transfer agent to the solvent is 1 (1-1.2); adding a pH regulator to regulate the pH value of the reaction system to 9-9.5; heating to 85-90 ℃, and stirring for reaction for 22-24 h to obtain the active supermolecule scale dissolver. The invention is suitable for dissolving and removing barium and strontium scales, water drive, gas drive, chemical drive injection and extraction layer barium and strontium scales and calcium carbonate scales of oil field gathering and transportation pipelines, improves the scale dissolving rate of insoluble scales such as the barium and strontium scales, reduces the corrosion of a general strong-alkaline scale dissolver to equipment, reduces the treatment cost of residual liquid and the damage to the environment, and improves the comprehensive benefit.)

1. A method for synthesizing an active supramolecular scale dissolver is characterized by comprising the following steps:

adding an organic amine, a bis-haloalkane, a phase transfer agent, a solvent and a pH regulator into a reaction vessel, wherein the molar ratio of the organic amine: bis-alkyl halides: phase transfer agent ═ (2.2-2.3): 1: (0.03-0.07); the mass ratio of the sum of the mass of the organic amine, the bihalogenated alkane and the phase transfer agent to the solvent is 1 (1-1.2); adding a pH regulator to regulate the pH value of the reaction system to 9-9.5; heating to 85-90 ℃, and stirring for reaction for 22-24 h to obtain the active supermolecule scale dissolver.

2. The method of synthesis of claim 1, wherein the organic amine comprises sodium ethylenediaminetetraacetate, sodium diethylenetriaminepentaacetate, and heptasodium diethylenetriaminepentamethylenephosphonic acid.

3. The method of claim 1, wherein the bis-haloalkanes comprise 1, 6-dichlorohexane, 1, 8-dichlorooctane, 1, 10-dichlorodecane, and 1, 10-dibromodecane.

4. The synthetic method of claim 1 wherein the phase transfer agent comprises tetrabutylammonium bromide, 12 alkyl dimethyl ammonium chloride and 12 alkyl dimethyl betaine.

5. The method of synthesis of claims 1-4, wherein the pH adjusting agent comprises EDTA and Na₂EDTA。

6. The synthesis method according to claim 1, wherein the molar ratio of the organic amine: bis-alkyl halides: phase transfer agent 2: 1: 0.05.

7. active supramolecular detergent prepared by the synthesis method of any one of claims 1-6.

8. Use of the reactive supramolecular detergent of claim 6 for descaling in oil field wellbores and perforations.

9. The use of claim 8, wherein the active supramolecular scale dissolver aqueous solution with the mass concentration of 10-15% is prepared, injected from the oil casing annulus, and extracted after the well is closed for 72 hours.

10. Use according to claim 9, characterized in that the concentration of the aqueous solution of active supramolecular detergent is 12 wt%.

Technical Field

The invention relates to the technical field of oil extraction and gas production engineering in the petroleum industry, in particular to a synthetic method of an active supermolecule scale dissolver and application thereof.

Background

The oil field development enters the middle and later stages, and the application of technologies such as water injection, tertiary oil recovery and the like causes the serious scaling problem of the oil field. The oilfield fouling type is carbonate scale (CaC 0)₃) Sulfate scale (CaS 0)₄、BaS0₄、SrS0₄) And iron scale, etc., and form mixed scales with each other. Scaling can occur in strata, mineshafts, equipment, ground systems and the like, so that oil gas pores and channels are blocked, the permeability is reduced, the oil gas yield is reduced, the energy consumption is increased, under-scale corrosion is generated, the normal production of an oil field is seriously influenced, the production efficiency is reduced, even a water injection well is scrapped, particularly, barium strontium scale is insoluble in acid, the texture is hard and difficult to remove, and great challenge is brought to later development of the oil field.

The main causes of barium sulfate scale formation are chemical incompatibility and thermodynamic instability. Chemical incompatibility is the leading cause of barium sulfate scale formation and when injected into water contains significant amounts of Ba²⁺Then, with the formation water S0₄ ²⁺BaS0 is easily generated by meeting₄And (4) scale formation. Since barium sulfate has a very low solubility product and produces a precipitate faster than other types of scales. The scale formation caused by thermodynamic instability is caused by the change of the influence factors such as temperature, pressure, pH, salt content and the like, and the original BaSO is broken₄Dissolving equilibrium in water to cause precipitation of precipitate. The barium and strontium scale damage of the oil field is a problem faced by water flooding, gas flooding and chemical flooding of the oil field, and how to remove the formed barium and strontium scale is still one of the worldwide problems.

In the middle of the last 80 th century, the Dunlin and Brent oil fields in the sea area of the North sea of Shell Esso company firstly use EDTA (ethylene diamine tetraacetic acid) scale remover to carry out chemical removal operation of barium (strontium) sulfate scale in a well for more than 40 times in a squeezing mode, after closing the well for 24 hours, the production capacity of a few oil wells is slightly improved, but the scale remover achieves greater success on a well which is closed for 3 weeks, but when the EDTA is used for removing the barium sulfate scale, the scale remover cannot achieve the purpose of removing the scale within acceptable well closing time. However, recovery of production by re-perforation of partially barium (strontium) scale deposited wells has all been successful, only half of the wells can be recovered to pre-treatment levels. In addition, scale formation has never been found in the wellbore during workover operations, and sulfate in the injected water has been deposited in the pores of the formation as barium sulfate before reaching the bottom of the well. Under the condition of poor chemical descaling effect or high cost, Shell Esso company adopts a method of extruding and injecting a scale inhibitor into oriented stratum to control scaling, and the used scale inhibitor is mainly phosphate or a compound thereof, and the extrusion cycle is generally 4 months. The AKZO company uses AMAGARD 462 to chelate the scale remover, and the thermal cycle process removes the barium sulfate scale in the pipeline, the active ingredients of the scale remover decrease at a rate of about 1% per hour, and the removed scale contains 75% barium sulfate and 20% strontium sulfate.

The addition of the polymer barium sulfate and strontium scale inhibitor is 20mg/L-200mg/L, the scale prevention rate is more than 80% at the temperature of 70 ℃, but the polymer barium sulfate and strontium scale inhibitor has the defects of large dosage, scale prevention effect only on barium sulfate and strontium sulfate scales with low ion concentration, low scale prevention effect on barium sulfate and strontium sulfate scales with high ion concentration and poor scale dissolution performance on barium sulfate and strontium scales in actual use.

The domestic companies such as Heima successively develop composite complexing agents, barium and strontium scales are dissolved through complexing, the composite complexing agents and metal ions are mainly adopted to generate complexes, and a plurality of complexing rings are usually formed. The complex complexing agent can be simultaneously mixed with a plurality of metal ions such as Ca²⁺、Mg²⁺、Fe³⁺、Fe²⁺、Ba²⁺And Sr²⁺The plasma generates a complexing effect to generate a stable complex with higher solubility, prevents the particles from being combined with corresponding acid radicals and from generating precipitates, thereby effectively preventing secondary precipitates after the scale of the blocking remover is dissolved from blocking capillary and throat of oil field stratums. Complex complexing agentThe oxygen atoms in the polar groups of the molecules of the alkali have unshared electron pairs and can be used as adsorption centers to adsorb metal ions to form five-membered or six-membered cyclic compounds.

In 1978, the complete concept of "supramolecular chemistry" was first proposed by french scientist j.m. lelin (rayne), who pointed out that "supramolecular chemistry exists based on covalent bonds, and on molecular assemblies and molecular bonds". Supramolecular chemistry generally refers to the combination of two or more molecules, joined by intermolecular interactions, into complex, organized aggregates that retain some integrity, giving them a defined microstructure and macroscopic properties, the intermolecular relationships being the same as atoms forming molecules through covalent bonds. Molecular recognition is due to a specific, exclusive interaction between different molecules, which satisfies both the spatial requirements between the molecules that bind to each other and the matching of various secondary bonding forces between the molecules. In supramolecules, a particular portion of an acceptor molecule has certain groups, which are suitable for binding with groups of another substrate molecule, and when the acceptor molecule meets the substrate molecule, the acceptor molecule and the substrate molecule are mutually selected to form a secondary bond, or the acceptor molecule forms a structure suitable for a hole reserved by the substrate molecule through the secondary bond according to the size of the substrate molecule, so the essence of molecular recognition is the optimal condition for forming the secondary bond between the acceptor and the substrate molecule, and the two parties are mutually selected to be combined together, so that the system tends to be stable. The conventional scale dissolvers generally realize the scale dissolving effect through chelating reaction, but have limitations and unsatisfactory effect, and only can relieve the problem which cannot be solved fundamentally. When the molecular recognition and the chemical bond combination of the supermolecule scale dissolver are carried out, the original scale on the surface of equipment can be repelled and removed, and the cleaning function of thoroughly removing the scale is achieved.

At present, scale dissolution through a chelating reaction can only relieve scale formation, and a scale layer cannot be fundamentally removed. The pH value of the scale dissolving liquid prepared by dissolving barium and strontium scales by complex complexation is 11-13, the pH value is high, the residual liquid needs to be treated by acid liquor, and the treatment cost is high. Even some complex complexing agents have larger biological toxicity and cause damage to constructors and environment. The Bola type surfactant is different from the traditional surfactant consisting of a hydrophilic group and a hydrophobic chain, the special structure of the Bola type surfactant determines that the Bola type surfactant not only has the function of the traditional surfactant, but also has the capability of forming a stable monolayer lipid membrane and vesicle, unique surface performance and aggregation and self-assembly behaviors, when the Bola compound forms spherical micelles, the folding conformation can be adopted in the micelles, rod-shaped micelles can also be formed, a large number of cation and anion groups exist, the capabilities of complexing barium and strontium scales are realized, and no precipitate is generated due to the cation content, so that the application prospect of the amphiphilic Bola compound in the field of oil field scale prevention is displayed. The research and development of the supermolecule barium-strontium scale dissolver with high scale dissolving efficiency and environmental friendliness is the main direction of the technical development.

CN 105949395A discloses a molecular cluster material of supramolecular polymer and a preparation method thereof, which takes polystyrene microspheres as a substrate, and active groups containing a large amount of carboxyl or sulfonic groups are grafted on the surfaces of the polystyrene microspheres to synthesize the molecular cluster material. The preparation method is simple, low in cost, low in energy consumption, environment-friendly, pollution-free, efficient and stable in product, large in descaling amount and strong in oxidation resistance, but a multi-step synthesis process is adopted, and the requirements on synthesis conditions are strict.

Disclosure of Invention

The invention aims to provide an active supermolecule scale dissolver for barium and strontium scales, which improves the scale dissolving speed under a static condition, increases the scale dissolving rate, and solves the technical problems that a strong alkaline scale dissolver seriously corrodes equipment, has high acid-base neutralization cost for residual liquid treatment, has great environmental harm to heterocyclic complexing agents and the like.

The technical scheme provided by the invention is as follows:

a method for synthesizing an active supramolecular scale dissolver comprises the following steps:

adding an organic amine, a bis-haloalkane, a phase transfer agent, a solvent and a pH regulator into a reaction vessel, wherein the molar ratio of the organic amine: bis-alkyl halides: phase transfer agent ═ (2.2-2.3): 1: (0.03-0.07); the mass ratio of the sum of the mass of the organic amine, the bihalogenated alkane and the phase transfer agent to the solvent is 1 (1-1.2); adding a pH regulator to regulate the pH value of the reaction system to 9-9.5; heating to 85-90 ℃, and stirring for reaction for 22-24 h to obtain the active supermolecule scale dissolver.

Preferably, the organic amine includes sodium ethylenediaminetetraacetate, sodium diethylenetriaminepentaacetate, and heptasodium diethylenetriaminepentamethylenephosphonate.

Preferably, the bis-haloalkanes include 1, 6-dichlorohexane, 1, 8-dichlorooctane, 1, 10-dichlorodecane and 1, 10-dibromodecane.

Preferably, the phase transfer agent comprises tetrabutylammonium bromide, 12 alkyl dimethyl ammonium chloride and 12 alkyl dimethyl betaine.

Preferably, the pH adjusting agent comprises EDTA and Na₂EDTA。

Preferably, the molar ratio of organic amine: bis-alkyl halides: phase transfer agent 2: 1: 0.05.

as another object of the present invention, the present invention also provides the active supramolecular detergent prepared by the above synthesis method.

As another object of the invention, the invention also provides the application of the supramolecular scale dissolver in descaling in oil field wellbores and perforations.

Preferably, preparing an active supermolecule scale dissolver aqueous solution with the mass concentration of 10-15%, injecting from the oil sleeve annulus, closing the well and extracting after 72 hours.

The invention has the beneficial effects that: the active supermolecule scale dissolver prepared by the invention is suitable for dissolving and removing barium and strontium scales of oil field gathering and transportation pipelines, water-driven, gas-driven and chemical-driven injection and extraction layers of barium and strontium scales, is suitable for dissolving and removing pollution blockage of barite slurry weighting agents, is also suitable for removing calcium carbonate scales, improves the scale dissolving rate of difficult scale dissolving such as barium and strontium scales, and the scale dissolving rate is more than 90%. Reduce the corrosion of the common strong alkaline detergent to equipment, reduce the treatment cost of residual liquid and the harm to the environment, and improve the comprehensive benefit.

Detailed Description

The technical solutions and advantages of the present invention will be explained and explained in more detail with reference to the detailed embodiments of the specification. It should be understood that the contents presented in the description and the detailed description are only for more clearly illustrating the technical solution and the advantages thereof, and do not limit the protection scope of the present invention. On the basis of the disclosure of the specification, a person skilled in the art can modify the technical solution according to various reasonable changes, and the modified technical solution is included in the protection scope of the invention as long as the person does not depart from the spirit of the invention.

A method for synthesizing an active supramolecular scale dissolver comprises the following steps:

adding an organic amine, a bis-haloalkane, a phase transfer agent, a solvent and a pH regulator into a reaction vessel, wherein the molar ratio of the organic amine: bis-alkyl halides: phase transfer agent ═ (2.2-2.3): 1: (0.03-0.07); the mass ratio of the sum of the mass of the organic amine, the bihalogenated alkane and the phase transfer agent to the solvent is 1 (1-1.2); adding a pH regulator to regulate the pH value of the reaction system to 9-9.5; heating to 85-90 ℃, and stirring for reaction for 22-24 h to obtain the active supermolecule scale dissolver.

The organic amine comprises sodium ethylene diamine tetracetate, sodium diethylenetriamine pentaacetate and heptasodium diethylenetriamine penta (methylene phosphonic acid).

The double halogenated alkyl comprises 1, 6-dichlorohexane, 1, 8-dichlorooctane, 1, 10-dichloro decane and 1, 10-dibromo decane.

The phase transfer agent includes tetrabutylammonium bromide, 12 alkyl dimethyl ammonium chloride and 12 alkyl dimethyl betaine.

The pH regulator comprises EDTA and Na₂EDTA。

The reaction principle of the invention is as follows:

the synthetic product has the general formula

R₁: at least 2 carboxylate or phosphate functions contained in the organic baseAnd (4) clustering.

X is chlorine atom or bromine atom.

n:3-12。