阅读说明：本技术 一种缓释型长效示踪剂及其制备方法 (Slow-release type long-acting tracer and preparation method thereof ) 是由 敖科 曾斌 袁琴 钟萍萍 刘想平 李玉金 于 2021-09-03 设计创作，主要内容包括：本发明公开了一种缓释型长效示踪剂及其制备方法,属于油田示踪技术领域,解决了现有技术中示踪剂制备工艺复杂且普适性不强的问题。本发明包括以下步骤：1.将双酚A型环氧树脂在30～65℃下加热软化30 min；2.向软化后的双酚A型环氧树脂中加入质量分数为10%～50%的示踪剂,常温下搅拌均匀,得到体系A；3.向体系A中依次加入稀释剂、助剂,常温下搅拌均匀,得到体系B；4.向体系B中加入固化剂,常温下充分搅拌均匀后,倒入模具中,在20～120℃下固化2～10 h后,制得缓释型长效示踪剂。本方法制备工艺条件温和、周期短,易成型,通过调节工艺参数,且可以调节示踪剂有效成分的释放速率,以满足不同场合的使用要求,能实现大规模批量生产,具有良好的应用前景。(The invention discloses a slow-release long-acting tracer and a preparation method thereof, belongs to the technical field of oilfield tracing, and solves the problems of complex preparation process and poor universality of the tracer in the prior art. The invention comprises the following steps: 1. heating and softening the bisphenol A type epoxy resin at 30-65 ℃ for 30 min; 2. adding a tracer with the mass fraction of 10-50% into the softened bisphenol A epoxy resin, and uniformly stirring at normal temperature to obtain a system A; 3. sequentially adding a diluent and an auxiliary agent into the system A, and uniformly stirring at normal temperature to obtain a system B; 4. and adding a curing agent into the system B, fully and uniformly stirring at normal temperature, pouring into a mold, and curing at 20-120 ℃ for 2-10 h to obtain the slow-release long-acting tracer. The method has the advantages of mild preparation process conditions, short period and easy molding, can adjust the release rate of the active ingredients of the tracer by adjusting process parameters so as to meet the use requirements of different occasions, can realize large-scale batch production, and has good application prospect.)

1. The slow-release type long-acting tracer is characterized by comprising the following raw materials in percentage by mass: 45-75% of bisphenol A epoxy resin, 10-50% of a tracer, 0.5-4% of a diluent, 0.5-3% of an auxiliary agent and 4-8% of a curing agent.

2. A method for preparing a slow-release long-acting tracer according to claim 1, comprising the steps of:

step 1: heating and softening the bisphenol A type epoxy resin at 30-65 ℃ for 30 min;

step 2: adding a tracer with the mass fraction of 10-50% into the softened bisphenol A epoxy resin, and uniformly stirring at normal temperature to obtain a system A;

and step 3: sequentially adding a thinner and an auxiliary agent into the system A, and uniformly stirring at normal temperature to obtain a system B;

and 4, step 4: and adding a curing agent into the system B, fully and uniformly stirring at normal temperature, pouring into a mold, and curing at 20-120 ℃ for 2-10 h to obtain the slow-release long-acting tracer.

3. The method for preparing a slow-release type long-acting tracer according to claim 2, wherein the bisphenol a type epoxy resin in step 1 is one or more of E-55, E-51, E-44, E-42, E-35, and E-20.

4. The method as claimed in claim 2, wherein the tracer in step 2 is a gas phase tracer, an oil phase tracer or a water phase tracer.

5. The method as claimed in claim 2, wherein the component of the gas phase tracer includes perfluoroalkane, perfluorocycloalkane, perfluoroaromatic hydrocarbon, the perfluoroalkane is one or more selected from perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluoroundecane, perfluorododecane, perfluorotridecane, perfluorotetradecane, perfluoropentadecane, and perfluorohexadecane, the perfluorocycloalkane is one or more selected from perfluorocyclopentane, perfluorocyclohexane, perfluoromethylcyclopentane, and perfluorodimethylcyclohexane, and the perfluoroaromatic hydrocarbon is one or more selected from perfluorobenzene, perfluorotoluene, perfluoronaphthalene, and perfluorobiphenyl.

6. The method as claimed in claim 2, wherein the component of the oil phase tracer comprises one or more of methyl perfluoroalkanoate and perfluoroalkyl ethyl acrylate, the methyl perfluoroalkanoate is one or more of methyl perfluoroformate, methyl perfluoroacetate, methyl perfluoropropionate, methyl perfluorobutyrate, methyl perfluorovalerate, methyl perfluorohexanoate, methyl perfluoroheptanoate, methyl perfluorooctanoate, methyl perfluorononanoate, methyl perfluorodecanoate, methyl perfluoroundecanoate, methyl perfluorododecanoate, methyl perfluorotridecanoate, methyl perfluorotetradecanoate, methyl perfluoropentadecanoate and methyl perfluorohexadecanoate, and the perfluoroalkyl ethyl acrylate is perfluoromethylethylacrylate, perfluoroethaneethylacrylate, perfluoropropaneethylacrylate, perfluorobutaneylethylacrylate, perfluorobutaneethylacrylate, perfluorohexadecanoate, perfluoroethaneethylacrylate, perfluorobutaneethylacrylate, perfluorohexadecanoate, One or more of perfluoropentyl ethyl acrylate, perfluorohexyl ethyl acrylate, perfluoroheptane ethyl acrylate, perfluorooctyl ethyl acrylate, perfluorononyl ethyl acrylate, perfluorodecyl ethyl acrylate, perfluoroundecyl ethyl acrylate, and perfluorododecyl ethyl acrylate.

7. The method as claimed in claim 2, wherein the component of the aqueous phase tracer includes one or more of sodium perfluoroalkyl sulfonate selected from the group consisting of sodium perfluorobutyl sulfonate, sodium perfluoropentyl sulfonate, sodium perfluorohexyl sulfonate, sodium perfluoroheptyl sulfonate, sodium perfluorooctyl sulfonate, sodium perfluorononyl sulfonate, sodium perfluorodecyl sulfonate, sodium perfluoroundecyl sulfonate, sodium perfluorododecyl sulfonate, sodium perfluoronaphthalene sulfonate, sodium perfluorobutyl naphthalene sulfonate and sodium perfluorodibutyl naphthalene sulfonate, and the sodium perfluoroalkyl carboxylate is selected from the group consisting of sodium perfluorobutyl carboxylate, sodium perfluoropentyl carboxylate, sodium perfluorohexyl carboxylate, sodium perfluoroheptyl carboxylate, sodium perfluorooctyl carboxylate, sodium perfluorononyl carboxylate, sodium perfluorodecyl carboxylate, sodium perfluoroundecyl carboxylate, sodium perfluorooctyl carboxylate, sodium perfluorodecyl carboxylate, sodium dodecyl carboxylate, sodium perfluorodecyl carboxylate, sodium dodecyl sulfonate, sodium dodecyl sodium sulfonate, sodium dodecyl sodium sulfonate, sodium dodecyl sodium sulfonate, sodium dodecyl sodium sulfonate, sodium sulfate, sodium dodecyl sodium sulfate, sodium dodecyl sodium sulfate, sodium salt, sodium sulfate, sodium salt, sodium sulfate, sodium salt, or the like, or the, One or more of sodium perfluorododecyl carboxylate.

8. The method as claimed in claim 2, wherein the diluent in step 3 is one of dibutyl phthalate, dioctyl phthalate, triethyl phosphate, tricresyl phosphate, triacetin, and nonylphenol.

9. The method for preparing a slow-release type long-acting tracer according to claim 2, wherein the auxiliary agent in step 3 is one of pyridine, triethylamine, triethanolamine, DMP-30, ethylenethiourea, 2-ethyl-4-methylimidazole, and fatty amine.

10. The method as claimed in claim 2, wherein the curing agent in step 4 is one of diethylenetriamine, triethanolamine, tetraethylenepentamine, m-phenylenediamine, m-xylylenediamine, maleic anhydride, phthalic anhydride, 200 polyamide, 203 polyamide, 300 polyamide, 400 polyamide, 600 polyamide, 650 polyamide, 651 polyamide, and methylhexahydrophthalic anhydride.

Technical Field

The invention belongs to the technical field of oilfield tracing, and particularly relates to a solid slow-release type long-acting tracer and a preparation method thereof.

Background

The production profile tracing test of the oil and gas well is to inject tracer solution into each section of fracturing fluid in the whole process during the fracturing period of the oil and gas well, track and research the production dynamics of each fracturing section in a mode of detecting the response of the tracer by well mouth sampling in the subsequent production stage, effectively measure the production profile data of the oil and gas well from the monitored concentration and output curve of each section of the tracer, and further provide technical basis for deepening reservoir recognition and evaluating the process measure effect.

The production profile tracer testing technology has high requirement on the effective monitoring period of the tracer, the conventional liquid tracer has poor timeliness, the monitoring period is difficult to be improved by increasing the injection amount of the tracer, and the monitoring period can only be provided for 2-3 months generally, so that the development of the slow-release and long-acting solid tracer is necessary. Generally, an oilfield tracer and a high molecular substance are mixed and solidified to prepare a solid tracer block, the solid tracer block is installed at different positions of a horizontal-section well completion unit, and a production profile is explained or a water outlet point is judged by monitoring the production conditions of different tracers. The method has the greatest advantage that only the medicament needs to be installed on the completion string, and the string does not need to be used in the whole testing process. The solid tracer has slow release performance, can be used for monitoring a horizontal section for a long time, and has great guiding value for making a production rule and follow-up measures of the horizontal well.

The slow-release tracer system developed at present has limited types and the controllable release difficulty of the tracer is higher. Therefore, the development of the solid tracer with long-acting slow-release effect has wide application prospect.

Chinese patent document CN111911139A (CN 202010820161.0) discloses a tracing slow-release system for water exploration of oil and gas wells and a preparation method thereof. The tracer slow release system comprises a tracer slow release medium with the mass fraction of 10-40%, a tracer with the mass fraction of 5-15%, a framework material with the mass fraction of 50-80%, a solubilizer with the mass fraction of 1-3% and a hydrophilic modifier with the mass fraction of 2-5%. The tracing slow-release system can control the release rate of the trace elements under the condition of stratum water containing by adjusting the component proportion in the system. However, the preparation method and the molding technique of the sustained-release system are complicated, which is not favorable for practical production.

Chinese patent document CN109469481A (CN201811591800. X) discloses a preparation method of a spherical chemical combination tracer with the diameter of 1-1.2 cm. Each group of slow-release solid tracers comprises water-soluble solid tracers and oil-soluble solid tracers. The two types of solid tracers both take epoxy resin 506 and maleic anhydride as basic components, the water-soluble tracer is a fluorobenzoic acid compound, and the oil-soluble tracer is a fluorobenzoic acid ester compound. The invention can increase the uniformity of the interface between the solid tracer and oil and water and improve the effective concentration of the tracer in the system. However, the chemical combination tracer is cured to be spherical and is matched with water-soluble and oil-soluble solid tracers for use, so that the cured tracer is single in form, and the spherical tracer has high requirements on a fixed mold.

Bisphenol A epoxy resin is prepared by reacting bisphenol A with epichlorohydrin. Because the raw material sources of the resin are wide and the cost is low, the bisphenol A type epoxy resin has wide application and large yield, and accounts for more than 85 percent of the total yield of the epoxy resin. The bisphenol A epoxy resin is used as a slow release medium of the solid tracer, so that the universality of the solid tracer is improved. The invention provides a slow-release medium taking bisphenol A type epoxy resin as a solid tracer, which is capable of preparing three types of solid tracers of an oil phase, a gas phase and a water phase by adjusting the component proportion and the curing process conditions, and being capable of being cured into tracers with different shapes.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a slow-release long-acting tracer and a preparation method thereof, and aims to provide a slow-release long-acting tracer which comprises the following components in parts by weight: the preparation process is simplified, the preparation period is shortened, and the release rate of the effective components of the tracer is adjusted by adjusting the process parameters so as to meet the use requirements of different occasions.

The technical scheme adopted by the invention is as follows:

a slow-release type long-acting tracer comprises the following raw materials in percentage by mass: 45-75% of bisphenol A epoxy resin, 10-50% of a tracer, 0.5-4% of a diluent, 0.5-3% of an auxiliary agent and 4-8% of a curing agent.

A preparation method of a slow-release type long-acting tracer comprises the following steps:

step 1: heating and softening the bisphenol A type epoxy resin at 30-65 ℃ for 30 min;

step 2: adding a tracer with the mass fraction of 10-50% into the softened bisphenol A epoxy resin, and uniformly stirring at normal temperature to obtain a system A;

and step 3: sequentially adding a diluent and an auxiliary agent into the system A, and uniformly stirring at normal temperature to obtain a system B;

and 4, step 4: and adding a curing agent into the system B, fully and uniformly stirring at normal temperature, pouring into a mold, and curing at 20-120 ℃ for 2-10 h to obtain the slow-release long-acting tracer.

Preferably, the bisphenol A type epoxy resin in the step 1 is one or more of E-55, E-51, E-44, E-42, E-35 and E-20.

Preferably, the tracer in step 2 is a gas phase tracer, an oil phase tracer or a water phase tracer.

Preferably, the component of the gas phase tracer includes perfluoroalkane, perfluorocycloalkane, and perfluoroaromatic hydrocarbon, the perfluoroalkane is one or more of perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluoroundecane, perfluorododecane, perfluorotridecane, perfluorotetradecane, perfluoropentadecane, and perfluorohexadecane, the perfluorocycloalkane is one or more of perfluorocyclopentane, perfluorocyclohexane, perfluoromethylcyclopentane, and perfluorodimethylcyclohexane, and the perfluoroaromatic hydrocarbon is one or more of perfluorobenzene, perfluorotoluene, perfluoronaphthalene, and perfluorobiphenyl.

Preferably, the components of the oil phase tracer include methyl perfluoroalkanoate and perfluoroalkyl ethyl acrylate, the methyl perfluoroalkanoate is one or more of methyl perfluoroformate, methyl perfluoroacetate, methyl perfluoropropionate, methyl perfluorobutyrate, methyl perfluorovalerate, methyl perfluorohexanoate, methyl perfluoroheptanoate, methyl perfluorooctanoate, methyl perfluorononanoate, methyl perfluorodecanoate, methyl perfluoroundecanoate, methyl perfluorododecanoate, methyl perfluorotridecanoate, methyl perfluorotetradecanoate, methyl perfluoropentadecanoate, methyl perfluorohexadecanoate, and the perfluoroalkyl ethyl acrylate is perfluoromethyl ethyl acrylate, perfluoroethane ethyl acrylate, perfluoropropyl ethyl acrylate, perfluorobutane ethyl acrylate, perfluoropentane ethyl acrylate, perfluorohexane ethyl acrylate, perfluoroheptane ethyl acrylate, perfluorodecane methyl propionate, perfluoroheptane ethyl acrylate, perfluorodecane ethyl acrylate, and water, perfluorodecane ethyl acrylate, water-ethyl acrylate, water, perfluorodecane ethyl acrylate, water-ethyl acrylate, perfluorodecane water-ethyl acrylate, one or more of perfluorooctyl ethyl acrylate, perfluorononyl ethyl acrylate, perfluorodecyl ethyl acrylate, perfluoroundecyl ethyl acrylate, and perfluorododecyl ethyl acrylate.

Preferably, the components of the aqueous phase tracer include perfluoroalkyl sodium sulfonate or perfluoroalkyl sodium carboxylate, the perfluoroalkyl sodium sulfonate is one or more of perfluorobutyl sodium sulfonate, perfluoropentyl sodium sulfonate, perfluorohexyl sodium sulfonate, perfluoroheptyl sodium sulfonate, perfluorooctyl sodium sulfonate, perfluorononyl sodium sulfonate, perfluorodecyl sodium sulfonate, perfluoroundecyl sodium sulfonate, perfluorododecyl sodium sulfonate, perfluoronaphthalene sodium sulfonate, perfluorobutyl naphthalene sodium sulfonate, and perfluorodibutyl naphthalene sodium sulfonate, and the perfluoroalkyl sodium carboxylate is one or more of perfluorobutyl sodium carboxylate, perfluoropentyl sodium carboxylate, perfluorohexyl sodium carboxylate, perfluoroheptyl sodium carboxylate, perfluorooctyl sodium carboxylate, perfluorononyl sodium carboxylate, perfluorodecyl sodium carboxylate, perfluoroundecyl sodium carboxylate, and perfluorododecyl sodium carboxylate.

Preferably, the diluent in step 3 is one of dibutyl phthalate, dioctyl phthalate, triethyl phosphate, tricresyl phosphate, triacetin and nonylphenol.

Preferably, the auxiliary agent in step 3 is one of pyridine, triethylamine, triethanolamine, DMP-30, ethylenethiourea, 2-ethyl-4-methylimidazole and fatty amine.

Preferably, the curing agent in step 4 is one of diethylenetriamine, triethanolamine, tetraethylenepentamine, m-phenylenediamine, m-xylylenediamine, maleic anhydride, phthalic anhydride, 200 polyamide, 203 polyamide, 300 polyamide, 400 polyamide, 600 polyamide, 650 polyamide, 651 polyamide and methylhexahydrophthalic anhydride.

A slow-release long-acting tracer is prepared by the preparation method.

In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:

1. according to the preparation method provided by the invention, bisphenol A epoxy resin is used as a slow release medium of the solid tracer, and the oil phase, the gas phase and the water phase solid tracer can be prepared by preferably selecting the epoxy resin, the curing agent and the auxiliary agent which are compatible with the tracer and adjusting the proportion of each component and the curing process conditions;

2. according to the preparation method provided by the invention, the effective release rate of the solid tracer can be controlled by adjusting the proportion of the components of the system and the curing process conditions, so that the long-acting slow release effect is realized;

3. the preparation method of the solid tracer can be used for preparing the solid tracer in various shapes such as strips, plates, blocks, beams and the like, and is favorable for being matched with different fixing devices to meet the requirements of different production fields;

4. the preparation method of the solid tracer provided by the invention has the advantages of cheap raw materials, mild process conditions, low equipment requirements, short preparation period, simplicity in operation and low production cost, and is suitable for large-scale production.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application are described clearly and completely, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all the embodiments. Thus, the following detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present application without making any creative effort, shall fall within the protection scope of the present application.

Example 1:

a preparation method of a slow-release type long-acting tracer comprises the following steps:

step 1: heating and softening 75 g of E-55 and 25 g of E-42 type epoxy resin at 60 ℃ for 30 min;

step 2: adding 30 mass percent of perfluoro methyl caprylate into the softened epoxy resin, and uniformly stirring at normal temperature to obtain a system A;

and step 3: sequentially adding 10 g of dioctyl phthalate and 1 g of triethylamine into the system A, and uniformly stirring at normal temperature to obtain a system B;

and 4, step 4: and adding 50 g of methyl hexahydrophthalic anhydride into the system B, fully and uniformly stirring at normal temperature, pouring into a mould, and curing at 80 ℃ for 2 h to obtain the slow-release solid oil phase tracer.

Example 2:

step 1: heating and softening 100 g of E-44 type epoxy resin at 40 ℃ for 30 min;

step 2: adding 35% of perfluoromethylcyclopentane by mass into the softened epoxy resin, and uniformly stirring at normal temperature to obtain a system A;

and step 3: sequentially adding 5 g of dibutyl phthalate and 2 g of DMP-30 into the system A, and uniformly stirring at normal temperature to obtain a system B;

and 4, step 4: and adding 650 g of polyamide into the system B, fully and uniformly stirring at normal temperature, pouring into a mould, and curing at 65 ℃ for 4 hours to obtain the slow-release solid gas phase tracer.

Example 3:

(1) heating and softening 50 g of E-44 and 50 g of E-51 type epoxy resin at 30 ℃ for 30 min;

(2) adding 20 mass percent of sodium perfluoroundecyl sulfonate into the softened epoxy resin, and uniformly stirring at normal temperature to obtain a system A;

(3) sequentially adding 5 g of dibutyl phthalate and 2 g of triethylamine into the system A, and uniformly stirring at normal temperature to obtain a system B;

(4) and adding 20 g of triethanolamine into the system B, fully and uniformly stirring at normal temperature, pouring into a mold, and curing at 100 ℃ for 2 hours to obtain the slow-release solid water phase tracer.

Example 4:

(1) heating and softening 65 g of E-55 and 35 g of E-20 type epoxy resin at 65 ℃ for 30 min;

(2) adding 40% of perfluoropropyl ethyl acrylate by mass into the softened epoxy resin, and uniformly stirring at normal temperature to obtain a system A;

(3) sequentially adding 5 g of triacetin and 5 g of nonyl phenol into the system A, and uniformly stirring at normal temperature to obtain a system B;

(4) and adding 15 g of tetraethylenepentamine into the system B, fully and uniformly stirring at normal temperature, pouring into a mould, and curing at 80 ℃ for 3 h to obtain the slow-release solid oil phase tracer.

Example 5:

(1) heating and softening 45 g of E-51 and 55 g of E-35 type epoxy resin at 60 ℃ for 30 min;

(2) adding perfluorotetradecane with the mass fraction of 25% into the softened epoxy resin, and uniformly stirring at normal temperature to obtain a system A;

(3) sequentially adding 3 g of triethyl phosphate and 5 g of fatty amine into the system A, and uniformly stirring at normal temperature to obtain a system B;

(4) and adding 40 g of 400 polyamide into the system B, fully and uniformly stirring at normal temperature, pouring into a mould, and curing at 65 ℃ for 3 h to obtain the slow-release solid gas phase tracer.

Example 6:

(1) heating and softening 60 g of E-44 and 40 g of E-35 type epoxy resin at 60 ℃ for 30 min;

(2) adding 30 mass percent of sodium perfluorooctyl carboxylate into the softened epoxy resin, and uniformly stirring at normal temperature to obtain a system A;

(3) sequentially adding 3 g of tricresyl phosphate and 2 g of triethanolamine into the system A, and uniformly stirring at normal temperature to obtain a system B;

(4) and adding 20 g of m-phenylenediamine into the system B, fully and uniformly stirring at normal temperature, pouring into a mold, and curing at 85 ℃ for 4 h to obtain the slow-release solid aqueous phase tracer.

The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.