阅读说明：本技术 一种三元复合驱原油破乳剂的制备方法 (Preparation method of ternary combination flooding crude oil demulsifier ) 是由 耿孝恒 郭海莹 贾新磊 毕康杰 韩亚男 杨仲年 商希礼 于 2020-07-27 设计创作，主要内容包括：本申请公开了一种三元复合驱原油破乳剂的制备方法,(1)叔丁基苯酚与三乙烯四胺混合并加热至完全溶解,并滴加甲醛溶液,生成起始剂A；(2)将起始剂A和催化剂投入反应釜中密封,抽真空并通入环氧丙烷,升温并控制压力得到中间产物B；(3)将中间产物B和催化剂投入反应釜中密封,抽真空并通入环氧丙烷,升温并控制压力得到聚醚C；(4)向反应容器中加入聚醚C且将其进行溶解,再加入氯化胆碱,搅拌升温至50～75℃,全部溶解后,滴加TDI,待拔丝长度为3～4cm为滴加结束,得到三元复合驱原油破乳剂。通过此工艺得到的破乳剂具有良好的亲油性能,能够显著提高化学剂的使用效率,表面活性高,破乳速度快,破乳效果好。(The application discloses a preparation method of a ternary combination flooding crude oil demulsifier, which comprises the following steps of (1) mixing tert-butyl phenol and triethylene tetramine, heating until the tert-butyl phenol and the triethylene tetramine are completely dissolved, and dropwise adding a formaldehyde solution to generate an initiator A; (2) putting the initiator A and the catalyst into a reaction kettle, sealing, vacuumizing, introducing propylene oxide, heating and controlling the pressure to obtain an intermediate product B; (3) putting the intermediate product B and a catalyst into a reaction kettle, sealing, vacuumizing, introducing propylene oxide, heating and controlling the pressure to obtain polyether C; (4) and adding polyether C into the reaction container, dissolving, adding choline chloride, stirring, heating to 50-75 ℃, dropwise adding TDI after the polyether C is completely dissolved, and finishing dropwise adding when the wire drawing length is 3-4 cm to obtain the ternary combination flooding crude oil demulsifier. The demulsifier obtained by the process has good oleophylic property, can obviously improve the use efficiency of a chemical agent, and has high surface activity, high demulsification speed and good demulsification effect.)

1. A preparation method of a ternary combination flooding crude oil demulsifier is characterized in that,

(1) synthesis of initiator a: mixing p-tert-butylphenol and triethylene tetramine, heating to 50-55 ℃ for complete dissolution, slowly dropwise adding a formaldehyde solution with the concentration of 37-40% at the temperature of 45-55 ℃, keeping the temperature for 30-40 min, adding a certain amount of xylene solution, then refluxing and dehydrating for 2-2.5 h, heating to recover xylene, and generating an initiator A after the residual substances fully react for 1-2 h; the mass parts of the p-tert-butylphenol, the triethylene tetramine and the formaldehyde solution are 1: (1.9-2): (1-1.1);

(2) synthesis of intermediate B: putting the initiator A and the catalyst into a reaction kettle, sealing, vacuumizing to negative pressure, introducing propylene oxide, heating to 110-130 ℃, controlling the pressure to be 0.19-0.21 MPa, and finishing the reaction when the pressure in the reaction kettle is reduced to the negative pressure to obtain an intermediate product B; wherein the mass ratio of the propylene oxide to the initiator is (99-359): 1;

(3) synthesizing polyether C: putting the intermediate product B and a catalyst into a high-temperature high-pressure reaction kettle, sealing, vacuumizing to negative pressure, introducing ethylene oxide into the reaction kettle, heating to 110-130 ℃, controlling the pressure to be 0.19-0.21 MPa, and finishing the reaction when the pressure in the reaction kettle is reduced to negative pressure to obtain polyether C; wherein the mass ratio of the ethylene oxide to the intermediate product B is 1: (2-3.7);

(4) preparing a ternary combination flooding crude oil demulsifier: and adding polyether C into the reaction container, dissolving, adding choline chloride, stirring, heating to 50-75 ℃, dropwise adding TDI after the polyether C is completely dissolved, and finishing dropwise adding when the wire drawing length is 3-4 cm to obtain the ternary combination flooding crude oil demulsifier.

2. The preparation method according to claim 1, wherein in the step (1), the mass parts of p-tert-butylphenol, triethylene tetramine and formaldehyde solution are 1: 1.95: 1.

3. the production method according to claim 1, characterized in that: in the step (2), the mass ratio of the added propylene oxide to the initiator is (159-259): 1.

4. the production method according to any one of claims 1 to 3, wherein in the step (3), the mass ratio of the ethylene oxide to the intermediate product B is 1: (3-3.7).

5. The production method according to any one of claims 1 to 3, wherein in the step (2), the mass ratio of propylene oxide to the initiator is 199: 1; in the step (3), the mass ratio of the added ethylene oxide to the intermediate product B is 1: 3.

6. the production method according to claim 4, characterized in that: in the steps (2) and (3), the reaction temperature is 120 ℃, and the reading of a pressure gauge in the reaction kettle is controlled to be 0.20 MPa.

7. The process according to claim 1, wherein in the step (2) (3), the catalyst for polyether reaction is potassium hydroxide; wherein the dosage of the catalyst in the step (2) is 0.2 percent of the total mass of the ethylene oxide and the propylene oxide; the dosage of the catalyst added in the step (3) is 0.15 percent of the total mass of the ethylene oxide and the propylene oxide.

8. The process according to claim 7, wherein in the step (2) (3), the gas used in the reactor is nitrogen, and the pressure is reduced to-0.09 MPa.

9. The production method according to claim 1, wherein, in the step (4),

adding polyether C into a reaction container, adding dimethylbenzene as a solvent for dissolving, adding choline chloride into a three-necked bottle, heating to 60 ℃, and completely dissolving the polyether C.

10. The method according to claim 9, wherein in the step (4), the mass ratio of the choline chloride to the polyether is 0.11: 1.

Technical Field

The invention belongs to the technical field of oil exploitation, and particularly relates to a preparation method of a ternary combination flooding crude oil demulsifier.

Background

With the continuous deepening of tertiary oil recovery, the oil recovery is gradually changed from conventional recovery into the recovery of heavy oil and heavy oil or even ultra-heavy oil. Therefore, the crude oil development also puts higher requirements on the commonly used crude oil demulsifiers. The crude oil demulsifier is an indispensable chemical reagent for the current united station and refinery, and the produced liquid tends to be in a more stable state due to the addition of various oil displacement agents in the process of exploitation.

However, as the water content and the proportion of viscous oil of produced fluid in crude oil extraction of various large oil fields are also increasing, many conventional demulsifiers commonly used in the market at present cannot meet the increasing demulsification requirement of crude oil emulsion, and meanwhile, the components of the crude oil produced fluid become more and more complicated due to the application of SAGD (steam assisted gravity drainage) technology and yield increasing measures of the oil fields aiming at the extra-thick oil.

Therefore, the continuous deepening of the dehydration difficulty of the thick oil in the oil field seriously restricts the exploitation and utilization of the thick oil resource in China, and the dehydration technology needs to be advanced along with the continuous improvement of the dehydration difficulty of the thick oil, so that a novel high-efficiency thick oil emulsion demulsifier is necessary to be developed to improve the capacity of the thick oil in China.

Disclosure of Invention

The invention aims to provide a preparation method of a ternary combination flooding crude oil demulsifier, which aims to solve the technical problem of difficulty in dehydration of thickened oil in the prior art.

In order to realize the purpose, the invention adopts the following technical scheme:

a preparation method of a ternary combination flooding crude oil demulsifier,

(1) synthesis of initiator a: mixing p-tert-butylphenol and triethylene tetramine, heating to 50-55 ℃ for complete dissolution, slowly dropwise adding a formaldehyde solution with the concentration of 37-40% at the temperature of 45-55 ℃, keeping the temperature for 30-40 min, adding a certain amount of xylene solution, then refluxing and dehydrating for 2-2.5 h, heating to recover xylene, and generating an initiator A after the residual substances fully react for 1-2 h; the mass parts of the p-tert-butylphenol, the triethylene tetramine and the formaldehyde solution are 1: (1.9-2): (1-1.1);

(2) synthesis of intermediate B: putting the initiator A and the catalyst into a reaction kettle, sealing, vacuumizing to negative pressure, introducing propylene oxide, heating to 110-130 ℃, controlling the pressure to be 0.19-0.21 MPa, and finishing the reaction when the pressure in the reaction kettle is reduced to the negative pressure to obtain an intermediate product B; wherein the mass ratio of the propylene oxide to the initiator is (99-359): 1;

(3) synthesizing polyether C: putting the intermediate product B and a catalyst into a high-temperature high-pressure reaction kettle, sealing, vacuumizing to negative pressure, introducing 0.27-0.5 part of ethylene oxide into the reaction kettle, heating to 110-130 ℃, controlling the pressure to be 0.19-0.21 MPa, and finishing the reaction when the pressure in the reaction kettle is reduced to negative pressure to obtain polyether C; wherein the mass ratio of the ethylene oxide to the intermediate product B is 1: (2-3.7);

(4) preparing a ternary combination flooding crude oil demulsifier: and adding polyether C into the reaction container, dissolving, adding choline chloride, stirring, heating to 50-75 ℃, dropwise adding TDI after the polyether C is completely dissolved, and finishing dropwise adding when the wire drawing length is 3-4 cm to obtain the ternary combination flooding crude oil demulsifier.

Preferably, in the step (1), the mass parts of the p-tert-butylphenol, the triethylene tetramine and the formaldehyde solution are 1: 1.95: 1.

preferably, in the step (2), the mass ratio of the added propylene oxide to the initiator is (159-259): 1.

preferably, in the step (3), the mass ratio of the added ethylene oxide to the intermediate product B is 1: (3-3.7).

Preferably, in the step (2), the mass ratio of the added propylene oxide to the initiator is 199: 1; in the step (3), the mass ratio of the added ethylene oxide to the intermediate product B is 1: 3.

preferably, in the steps (2) and (3), the reaction temperature is 120 ℃, and the reading of a pressure gauge in the reaction kettle is controlled to be 0.20 MPa.

Preferably, in the step (2) (3), the catalyst for polyether reaction is potassium hydroxide; wherein the dosage of the catalyst in the step (2) is 0.2 percent of the total mass of the ethylene oxide and the propylene oxide; the dosage of the catalyst added in the step (3) is 0.15 percent of the total mass of the ethylene oxide and the propylene oxide.

Preferably, in the steps (2) and (3), the gas used in the reaction kettle is nitrogen, and the pressure is vacuumized to-0.09 MPa.

Preferably, in the step (4), polyether C is added into the reaction vessel, xylene is added as a solvent for dissolution, choline chloride is added into the three-necked flask, the temperature is raised to 60 ℃, and the polyether C is completely dissolved.

Preferably, in the step (4), the mass ratio of the choline chloride to the polyether is 0.11: 1.

compared with the prior art, the invention has the advantages and positive effects that:

according to the invention, a polymer synthesized by tert-butylphenol, triethylene tetramine and formaldehyde is used as an initiator A, on the basis of the initiator A, firstly, the initiator A and propylene oxide are used for obtaining an intermediate product B, then, the intermediate product B and ethylene oxide are further reacted under an alkaline environment to obtain polyether C, and finally, the polyether C is reacted with choline chloride and toluene diisocyanate to obtain the ternary complex flooding crude oil demulsifier. Meanwhile, the ternary composite oil displacement technology has the advantages of high efficiency and low cost of the alkali displacement technology and the advantages of high efficiency and efficiency of polymer displacement. The demulsifier obtained by the process has good oleophylic property, can obviously improve the service efficiency of a chemical agent, has high surface activity, high demulsification speed and good demulsification effect, and has more obvious demulsification effect compared with other demulsifiers. Solves the technical problem of difficult dehydration of the thickened oil in the prior art.

Drawings

FIG. 1 is a graph showing the demulsification effect of samples 1-6 of the present invention on ASP flooding crude oil at 1h from left to right;

FIG. 2 is a graph showing the demulsification effect of samples 7 to 12 of the present invention on ASP flooding crude oil at 1h from left to right;

FIG. 3 is a graph showing the demulsification effect of the ASP flooding crude oil at 2h for samples 1-6 of the present invention from left to right;

FIG. 4 is a graph showing the demulsification effect of samples 7-12 of the present invention on ASP flooding crude oil at 2h from left to right;

FIG. 5 is a graph showing the demulsification effect of the ASP flooding crude oil at 5h for samples 1-6 of the present invention from left to right;

FIG. 6 is a graph showing the demulsification effect of samples 7-12 of the present invention on ASP flooding crude oil at 5h from left to right.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

According to the invention, a polymer synthesized from tert-butylphenol, triethylene tetramine and formaldehyde is used as an initiator A, on the basis of the initiator A, the intermediate B is firstly obtained by reacting with propylene oxide, then the intermediate B is further reacted with ethylene oxide under an alkaline environment to obtain polyether C, and finally the polyether C is reacted with choline chloride and toluene diisocyanate to obtain the ternary complex flooding crude oil demulsifier. Solves the technical problem of difficult dehydration of the thickened oil in the prior art.

The present invention is further described below in conjunction with specific examples so that those skilled in the art may better understand the present invention and can practice it.