阅读说明：本技术 一种原油三采采出液用磺酸盐型破乳剂及其制备方法 (Sulfonate demulsifier for crude oil three-recovery produced liquid and preparation method thereof ) 是由 崔仕章 郭玉玺 张向红 王黎明 宋新旺 于长禄 侯青怡 吴艳青 于 2020-04-28 设计创作，主要内容包括：本发明提供了一种原油三采采出液用磺酸盐型破乳剂,采用以下方法制备：(1)将起始剂与催化剂投加至反应釜,通入环氧丙烷、环氧乙烷,制得聚醚A；(2)将聚醚A与马来酸酐投加至反应釜内,进行脱水反应制得酯化物B；(3)将酯化物B与磺化剂投加至反应釜进行磺化改性,制得所述磺酸盐破乳剂。本发明提供的原油三采采出液用磺酸盐型破乳剂具有较高的表面活性,很大程度地削弱界面张力,吸附在油水界面,更多的覆盖原有的成膜物质,有效地消除界面张力梯度,使原本的油水界面膜破裂,膜内液体流出聚集,实现油水分离,表现出了显著的破乳性能。(The invention provides a sulfonate demulsifier for crude oil tertiary recovery produced liquid, which is prepared by the following method: (1) adding an initiator and a catalyst into a reaction kettle, and introducing epoxypropane and epoxyethane to prepare polyether A; (2) adding polyether A and maleic anhydride into a reaction kettle, and performing dehydration reaction to obtain an esterified substance B; (3) and adding the esterified substance B and a sulfonating agent into a reaction kettle for sulfonation modification to obtain the sulfonate demulsifier. The sulfonate demulsifier for the crude oil three-recovery produced liquid provided by the invention has higher surface activity, greatly weakens the interfacial tension, adsorbs to an oil-water interface, more covers the original film-forming substances, effectively eliminates the interfacial tension gradient, enables the original oil-water interface film to crack, enables liquid in the film to flow out and gather, realizes oil-water separation, and shows remarkable demulsification performance.)

1. A sulfonate-type demulsifier, wherein the demulsifier has a polymer represented by formula (I):

in formula (I), X is selected from one of the following groups: -Na, -NH₂or-Cl;

in the formula (I), R is selected from one of three structures of formula (1) to formula (3):

structure (1):

wherein: m is m₁+m₂And m is₁＝m₂＝(m/2)，n＝n₁+n₂And n is₁＝n₂＝(n/2)；

Structure (2):

wherein: m is m₁+m₂+m₃+m₄And m is₁＝m₂＝m₃＝m₄＝(m/4)，n＝n₁+n₂+n₃+n₄And n is₁＝n₂＝n₃＝n₄＝(n/4)；

Structure (3):

wherein: m is m₁+m₂And m is₁＝m₂＝(m/2)，n＝n₁+n₂And n is₁＝n₂＝(n/2)；

In the formula R, m is 80-110, n is 30-60, and the molecular weight of the polymer represented by the formula (I) is 6000-9000.

2. The sulfonate demulsifier of claim 1, wherein the polymer has a density of 0.99g/cm³～1.05g/cm³The viscosity is 2000-3000 mPa.s, the flash point is more than 60 ℃, the condensation point is less than-15 ℃, and the RSN value is 13-17.

3. The method of preparing the sulfonate demulsifier of claim 1, comprising:

(1) adding an initiator and a catalyst into a reaction kettle, and introducing epoxypropane and epoxyethane to prepare polyether A; the initiator is selected from one of propylene glycol, diethylenetriamine and tert-butylphenol formaldehyde resin;

(2) adding polyether A and maleic anhydride into a reaction kettle, and performing dehydration reaction to obtain an esterified substance B;

(3) and adding the esterified substance B and a sulfonating agent into a reaction kettle for sulfonation modification to obtain the sulfonate demulsifier.

4. The production method according to claim 3, wherein the mass ratio of the initiator, propylene oxide and ethylene oxide in the step (1) is 1: (50-150): (10-40).

5. The process according to claim 3, wherein the mass ratio of the total mass of propylene oxide and ethylene oxide to the catalyst in step (1) is 1000: (2-7).

6. The method according to claim 3, wherein the catalyst in the step (1) is one selected from the group consisting of potassium hydroxide, sodium hydroxide and potassium methoxide.

7. The production method according to claim 3, wherein the mass ratio of polyether A to maleic anhydride in step (2) is 100: (2-10).

8. The preparation method according to claim 3, wherein the mass ratio of the ester B to the sulfonating agent in the step (3) is 1: (0.3-0.7).

9. The method according to claim 3, wherein the sulfonating agent in the step (3) is selected from chlorosulfonic acid, sulfamic acid and sodium bisulfite.

10. Use of the sulfonate demulsifier of any one of claims 1 to 2 and/or the sulfonate demulsifier obtained by the process of any one of claims 3 to 9 in a crude oil tertiary recovery produced fluid; preferably, the water content of the crude oil tertiary recovery produced liquid is 35%; more preferably, the emulsion breaker is a sulfonate type emulsion breaker: methanol: the water is prepared and used according to the mass ratio of 2:1: 2.

Technical Field

The application relates to the technical field of petrochemical industry, in particular to a sulfonate demulsifier for crude oil tertiary recovery produced liquid and a preparation method thereof.

Background

The crude oil demulsifier is an oil field chemical agent for performing oil-water separation on petroleum produced liquid, and is one of important links in petroleum production and processing processes. The demulsifying principle is that the demulsifier goes deep and adheres to the interface of emulsified liquid drops, replaces the original emulsifier, destroys the surface film, releases the liquid drops coated in the film and makes the liquid drops coalesce, thereby separating the oil phase from the water phase. In the process of oil field exploitation, along with the implementation of oil extraction process technologies such as steam flooding, surfactant, polymer and ternary complex flooding, the water content in the crude oil emulsion is increased, the stability is enhanced, and the demulsification difficulty of the crude oil is increased. The water content of crude oil will gradually rise when crude oil is continuously mined, the oil-water mixed liquid gradually forms a stable oil-water emulsion through an oil nozzle and a gathering and transportation pipeline, and a petroleum outlet enters an oil refinery and is reinjected with sewage, which have related requirements on the residual water content of crude oil and the oil content of sewage. Therefore, it is necessary to demulsify and dewater emulsified crude oil.

Demulsifiers for water-in-oil emulsified crude oil have been developed very early, and three generations of demulsifiers have been developed since the 20 th century. In order to solve the problem of demulsification of W/O type crude oil emulsion in 20 to 30 years in the 20 th century, a first-generation anionic demulsifier which is mainly a low-molecular anionic surfactant such as a sulfate type, a sulfonate type and a carboxylate type is developed; its advantages are low cost, high dosage, low effect and easy influence of electrolyte. Second generation low molecular weight non-ionic demulsifiers, such as Peregal, OP and Tween types, were developed in the 40 to 50 s. Although the demulsifier can resist acid, alkali and salt, the dosage of the demulsifier is large. In the 60 s, third-generation high-molecular-weight nonionic demulsifiers such as Dissolvan4411, SP type, AE type, AP type and the like are developed; its advantages are less consumption, high effect, high specificity and low adaptability.

At present, the demulsifiers studied at home and abroad are mainly nonionic polyoxyethylene polyoxypropylene block polymers from the chemical type. In recent years, special surfactants have been synthesized according to newly developed organic synthesis techniques. The wide application of the organic synthesis technology leads the demulsifier to be rapidly developed in variety and quantity, and the application of means such as compounding and copolymerization leads the application range of the demulsifier to be wider and wider.

Disclosure of Invention

The invention aims to provide a novel demulsifier with high dehydration speed and high dehydration rate, which solves the problem of difficult demulsification of stable crude oil emulsion caused by a crude oil three-recovery technology in the prior art.

In one aspect, the present application provides a sulfonate-type demulsifier that is a polymer represented by formula (I):

in formula (I), X is selected from one of the following groups: -Na, -NH₂or-Cl;

r in the formula (I) is selected from one of three structures of formula (1) to formula (3):

structure (1):

wherein: m is m₁+m₂And m is₁＝m₂＝(m/2)，n＝n₁+n₂And n is₁＝n₂＝(n/2)；

Structure (2):

wherein: m is m₁+m₂+m₃+m₄And m is₁＝m₂＝m₃＝m₄＝(m/4)，n＝n₁+n₂+n₃+n₄And n is₁＝n₂＝n₃＝n₄＝(n/4)；

Structure (3):

wherein: m is m₁+m₂And m is₁＝m₂＝(m/2)，n＝n₁+n₂And n is₁＝n₂＝(n/2)；

In the formula R, m is 80-110, n is 30-60, and the molecular weight of the polymer represented by the formula (I) is 6000-9000.

Further, the polymer had a density of 0.99g/cm³～1.05g/cm³The viscosity is 2000-3000 mPa.s, the flash point is more than 60 ℃, the condensation point is less than-15 ℃, and the RSN value is 13-17.

The sulfonate demulsifier provided by the application introduces nonpolar groups, increases the contact area with an oil-water interface film, replaces natural active substances in the crude oil interface film, has higher surface activity, can weaken the interface tension to a great extent when being applied to crude oil three-extraction produced liquid, adsorbs on the oil-water interface, covers more original film-forming substances, effectively eliminates the interface tension gradient, enables the original oil-water interface film to be broken, enables the liquid in the film to flow out and gather, and effectively realizes oil-water separation.

On the other hand, the application also provides a method for preparing the sulfonate demulsifier, which comprises the following steps:

(1) adding an initiator and a catalyst into a reaction kettle, and introducing epoxypropane and epoxyethane to prepare polyether A; the initiator is selected from one of propylene glycol, diethylenetriamine and tert-butylphenol formaldehyde resin;

(2) adding polyether A and maleic anhydride into a reaction kettle, and performing dehydration reaction to obtain an esterified substance B;

(3) and adding the esterified substance B and a sulfonating agent into a reaction kettle for sulfonation modification to obtain the sulfonate demulsifier.

Preferably, the preparation method can specifically adopt the following steps:

(1) synthesis of polyether intermediate polyether A:

adding an initiator and a catalyst into a reaction kettle, dehydrating at high temperature, and slowly introducing propylene oxide and ethylene oxide at a certain temperature to obtain polyether intermediate polyether A;

(2) synthesis of ester intermediate ester B:

adding polyether A and maleic anhydride into a reaction kettle, and dehydrating at high temperature and in vacuum for 3 hours until no water is removed to obtain an esterified substance intermediate esterified substance B;

(3) synthesis of a sulfonate demulsifier dry agent C:

and adding the esterified substance B and a sulfonating agent into a reaction kettle, performing high-temperature sulfonation modification, and preserving the heat for a period of time to obtain a sulfonate demulsifier dry agent C.

Wherein, the initiator in the step (1) is selected from propylene glycol, diethylenetriamine and tert-butyl phenol formaldehyde resin.

Further, in the step (1), the reaction mass ratio of the initiator to the propylene oxide to the ethylene oxide is 1: (50-150): (10-40), preferably 1: (60-100): (15-30).

Further, the mass ratio of the total mass of the propylene oxide and the ethylene oxide to the reaction mass of the catalyst in the step (1) is 1000: (2-7).

Further, the catalyst in step (1) is selected from one of potassium hydroxide, sodium hydroxide and potassium methoxide.

Further, the catalyst is prepared by mixing a solute hydrogen oxidant and solvent water, wherein the solute is selected from one of potassium hydroxide, sodium hydroxide and potassium methoxide, and the solvent is selected from one of deionized water, methanol and ethanol. The solute is preferably potassium hydroxide, and the solvent is preferably deionized water. The mass ratio of the solute to the solvent is 1: (1-10), preferably, the mass ratio of the solute to the solvent is 1: 3.

further, in the step (2), the reaction mass ratio of the polyether A to the maleic anhydride is 100: (2-10).

Further, the mass ratio of the esterification product B to the sulfonating agent in the step (3) is 1: (0.3-0.7).

Further, maleic anhydride is preferable in the step (2).

Further, the sulfonating agent in the step (3) is selected from ClSO₃H (chlorosulfonic acid), H₂NSO₃H (sulfamic acid), NaHSO₃(sodium bisulfite).

Further, the above method uses an electrically heated reaction vessel and/or polymerization vessel.

In a more preferred embodiment, the above preparation method specifically comprises the steps of:

(1) polyether intermediate polyether A synthesis:

cleaning and drying a stainless steel reaction kettle, pumping an initiator and a catalyst into the dry and clean reaction kettle, heating to 100-120 ℃, stirring for 30min until the state is uniform, starting a vacuum pump at 100-120 ℃ to perform high-temperature vacuum dehydration for 2h until no water is removed, then slowly adding epoxypropane at 120-125 ℃, controlling the temperature to 120-125 ℃ in the reaction process, performing heat preservation reaction for 1h after the feeding is finished, heating to 125-130 ℃, slowly adding ethylene oxide, controlling the temperature to 125-130 ℃ in the reaction process, performing heat preservation reaction for 2h after the feeding is finished, cooling, measuring and discharging after sampling and inspection are qualified to obtain the polyether A.

(2) Synthesis of ester intermediate ester B

Cleaning and drying a stainless steel reaction kettle, pumping polyether A into the dry and clean reaction kettle, adding maleic anhydride, heating to 90 ℃, stirring for 30min until the state is uniform, slowly heating to 170-175 ℃, keeping the temperature, reacting and dehydrating for 2h until no water is removed, starting a vacuum pump, dehydrating for 1h under the condition of 170-175 ℃ in vacuum until no water is removed, cooling, sampling, checking to be qualified, metering and discharging to obtain an esterified substance B.

(3) Synthesis of sulfonate demulsifier and drying agent C

Cleaning and drying a stainless steel reaction kettle, pumping an esterified substance B and a sulfonating agent into the dry and clean reaction kettle, heating to 50-60 ℃, stirring for 30min until the state is uniform, slowly heating to 120-135 ℃, carrying out heat preservation reaction for 5h, cooling, measuring and discharging after sampling and inspection are qualified, and thus obtaining the sulfonate demulsifier C.

The synthetic route for synthesizing the sulfonate demulsifier by adopting the synthetic method is as follows:

(1) synthesis of polyether intermediate polyether A:

polyether intermediate a-1 (propylene glycol as initiator):

wherein: m is m₁+m₂，m₁＝m₂＝(m/2)

n＝n₁+n₂，n₁＝n₂＝(n/2)

Polyether intermediate a-2 (diethylenetriamine as initiator):

wherein: m is m₁+m₂+m₃+m₄，m₁＝m₂＝m₃＝m₄＝(m/4)

n＝n₁+n₂+n₃+n₄And n is₁＝n₂＝n₃＝n₄＝(n/4)

Polyether intermediate a-3 (tert-butylphenol formaldehyde resin as initiator):

wherein: m is m₁+m₂，m₁＝m₂＝(m/2)

n＝n₁+n₂，n₁＝n₂＝(n/2)

(2) Synthesis of ester intermediate ester B:

wherein: r has the following three structures:

structure (1):

structure (2):

structure (3):

(3) synthesis of a sulfonate demulsifier dry agent C:

wherein: r has the following three structures:

structure (1):

structure (2):

structure (3):

x has the following structure:

-Na or-NH₂or-Cl

On the other hand, the application also provides the application of the sulfonate demulsifier and/or the sulfonate demulsifier prepared by the method in the crude oil tertiary recovery produced fluid.

Preferably, the water content of the crude oil tertiary recovery produced liquid is 35%, and more preferably, the dehydration temperature is 45 ℃.

More preferably, the sulfonate demulsifier, when used to treat a crude oil tertiary recovery produced fluid, is treated with a sulfonate demulsifier: methanol: the water is prepared and used according to the mass ratio of 2:1: 2. Under the using conditions, the absolute dehydration rate of the sulfonate demulsifier at 50ppm can reach 92.9 percent, and the absolute dehydration rate at 100ppm can reach 96.4 percent.

The following beneficial effects can be brought through the application:

the sulfonate demulsifier for the crude oil tertiary recovery produced liquid provided by the invention has the advantages of simple preparation method, easily available raw materials, easy industrial production, higher surface activity, high dehydration speed, clear removed water quality and uniform oil-water interface, can weaken the interfacial tension to a great extent, adsorb the interfacial tension on the oil-water interface, cover more original film-forming substances, effectively eliminate the interfacial tension gradient, crack the original oil-water interfacial film, flow and gather the liquid in the film, realize oil-water separation and show remarkable demulsification performance, and experiments show that the dehydration rate of the crude oil tertiary recovery produced liquid reaches 92.9% when the chemical concentration of the demulsifier is 50ppm under specific use conditions, and the dehydration rate reaches 96.4% when the chemical concentration is 100 ppm.

Detailed Description

In order to more clearly explain the overall concept of the present application, the following detailed description is given by way of example. In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present application. It will be apparent, however, to one skilled in the art, that the present application may be practiced without one or more of these specific details. In other instances, well-known features of the art have not been described in order to avoid obscuring the present application.

Reagents in the following examples, if not specifically indicated, were: propylene glycol (CAS:57-55-6), diethylenetriamine (CAS: 111-40-0), tert-butylphenol formaldehyde resin (CAS: 65733-76-8), maleic anhydride (CAS: 108-31-6), sodium bisulfite (CAS: 7631-90-5), sulfamic acid (CAS:7790-94-5), chlorosulfonic acid (CAS: 5329-14-6) are commercially available; both ethylene oxide and propylene oxide were taken from commercial samples. The purity of the reagents is analytical purity.