阅读说明：本技术 一种新型高分子共聚物破乳剂及其制备方法 (Novel high-molecular copolymer demulsifier and preparation method thereof ) 是由 李奎 汤永昌 胡涛 于 2021-09-23 设计创作，主要内容包括：本发明适用于石油开采技术领域,提供了一种新型高分子共聚物破乳剂及其制备方法,包括将丙烯酸丁酯和α-甲基苯乙烯线性二聚体、将苯乙烯和链转移剂α-甲基苯乙烯线性二聚体混合、将N-甲基丙烯酰胺和链转移剂混合、将2-丙烯酰胺-2-甲基丙磺酸和链转移剂混合后备用,接着向丙酮及乳化剂十二烷基磺酸钠依次加入引发剂使其形成稳定胶束体系,然后依次添加之前制备的混合物,通过添加叔丁基过氧化氢、焦亚硫酸钠、对叔丁基邻苯二酚,加工获得共聚物固体,最后通过将共聚物与阳离子有机硅表面活性剂水按照一定比例混合,搅拌获得破乳剂,其具备环境友好、非聚醚类破乳剂、分子量高的特点复配时引入有机硅表面活性剂,破乳速度更快且效果更好。(The invention is suitable for the technical field of oil exploitation, and provides a novel high-molecular copolymer demulsifier and a preparation method thereof, which comprises the steps of mixing butyl acrylate and an alpha-methyl styrene linear dimer, mixing styrene and a chain transfer agent, mixing N-methacrylamide and a chain transfer agent, mixing 2-acrylamide-2-methylpropanesulfonic acid and the chain transfer agent for later use, sequentially adding an initiator into acetone and an emulsifier sodium dodecyl sulfate to form a stable micelle system, sequentially adding the prepared mixture, processing to obtain a copolymer solid by adding tert-butyl hydroperoxide, sodium metabisulfite and p-tert-butyl catechol, finally mixing the copolymer and a cationic organosilicon surfactant water according to a certain proportion, stirring to obtain the demulsifier, the organic silicon demulsifying agent has the characteristics of environmental friendliness, non-polyether demulsifier and high molecular weight, and the organic silicon surfactant is introduced during compounding, so that the demulsification speed is higher and the demulsification effect is better.)

1. A preparation method of a novel high-molecular copolymer demulsifier is characterized by comprising the following steps: the method comprises the following steps:

s1, adding 5-10 parts of hydrophobic monomer butyl acrylate into 0.2-1 part of chain transfer agent alpha-methyl styrene linear dimer, and mixing to obtain a mixture component A for later use; 5-15 parts of hydrophobic monomer styrene and 0.2-1 part of chain transfer agent alpha-methyl styrene linear dimer are mixed to obtain a mixture component B for later use; mixing 1-6 parts of hydrophilic monomer N-methacrylamide and 0.2-1 part of chain transfer agent to obtain a mixture component C for later use; mixing 1-5 parts of 2-acrylamide-2-methylpropanesulfonic acid and 0.2-1 part of chain transfer agent alpha-methyl styrene linear dimer to obtain a mixture component D for later use;

s2, adding a certain amount of water, acetone and an emulsifier sodium dodecyl sulfate into a four-neck flask, stirring and heating the flask in a water bath to dissolve the mixture, heating the mixture to 73-75 ℃, adding 5% of the total amount of an initiator, and adding all the initiators to form a stable micelle system when the temperature is raised to 78-81 ℃;

s3, when the system generates blue light, alternately dripping A, B, C and D components into the flask, finishing dripping within 2.5h, and preserving heat for 1.5h after finishing dripping to further finish the polymerization reaction;

s4, reducing the temperature to 62-65 ℃, respectively adding tert-butyl hydroperoxide, sodium metabisulfite tert-butyl hydroperoxide and sodium metabisulfite twice, wherein the total amount of the tert-butyl hydroperoxide, the sodium metabisulfite tert-butyl hydroperoxide and the sodium metabisulfite is 1-1.5 percent of the total amount of the monomers, and preserving the temperature for 1 hour to further polymerize the unreacted monomers, so as to improve the conversion rate;

s5, adding a chain terminator, wherein the chain terminator accounts for 0.1-2% of the total amount of the monomers, slowly cooling, stopping the reaction after 0.5h, cooling to 35-40 ℃, and adjusting the pH value to 7-8 with ammonia water to obtain a copolymer emulsion;

s6, adding the obtained emulsion into saturated salt water, stirring to demulsify, filtering out solids, fully washing with deionized water to remove unreacted monomers, and then drying in vacuum at 25 ℃ to obtain copolymer solids;

s7, mixing the copolymer with the mass ratio of 30-55%, the cationic organosilicon surfactant with the mass ratio of 5-20% and the water with the mass ratio of 25-60%, stirring for 30-70 minutes at the temperature of 30-70 ℃, cooling to room temperature at the rotation speed of 200-600 rpm, and filtering to remove impurities to obtain the novel high-molecular copolymer demulsifier.

2. The method for preparing the novel polymer copolymer demulsifier according to claim 1, wherein the method comprises the following steps: the initiator is one or a mixture of azodiisobutyronitrile and azodiisoheptonitrile.

3. The method for preparing the novel polymer copolymer demulsifier according to claim 1, wherein the method comprises the following steps: in step S2, A, B, C was alternately added dropwise to the flask in an amount of 15 drops per second when three components D were added dropwise.

4. The method for preparing the novel polymer copolymer demulsifier according to claim 1, wherein the method comprises the following steps: the chain terminator adopts p-tert-butyl catechol.

5. A novel high-molecular copolymer demulsifier is characterized in that: prepared by the preparation method of any one of the above claims 1 to 4.

Technical Field

The invention belongs to the technical field of oil exploitation, and particularly relates to a novel high-molecular copolymer demulsifier and a preparation method thereof.

Background

A demulsifier is a surfactant that breaks emulsions. Demulsifiers break emulsions primarily by the action of partially displacing the stabilizing membrane. The dehydrating agent is used for dehydrating crude oil and heavy oil to ensure that the water content meets the requirement; can be used in oil well to reduce the viscosity of crude oil and prevent oil well from blocking.

However, the existing demulsifier causes great pollution when in use, and the demulsification speed needs to be improved.

Disclosure of Invention

The invention provides a novel high-molecular copolymer demulsifier and a preparation method thereof, aiming at solving the problems in the prior art.

The invention is realized in this way, a method for preparing novel polymer demulsifier, comprising the following steps:

s1, adding 5-10 parts of hydrophobic monomer butyl acrylate into 0.2-1 part of chain transfer agent alpha-methyl styrene linear dimer, and mixing to obtain a mixture component A for later use; 5-15 parts of hydrophobic monomer styrene and 0.2-1 part of chain transfer agent alpha-methyl styrene linear dimer are mixed to obtain a mixture component B for later use; mixing 1-6 parts of hydrophilic monomer N-methacrylamide and 0.2-1 part of chain transfer agent to obtain a mixture component C for later use; mixing 1-5 parts of 2-acrylamide-2-methylpropanesulfonic acid and 0.2-1 part of chain transfer agent alpha-methyl styrene linear dimer to obtain a mixture component D for later use;

s2, adding a certain amount of water, acetone and an emulsifier sodium dodecyl sulfate into a four-neck flask, stirring and heating the flask in a water bath to dissolve the mixture, heating the mixture to 73-75 ℃, adding 5% of the total amount of an initiator, and adding all the initiators to form a stable micelle system when the temperature is raised to 78-81 ℃;

s3, when the system generates blue light, alternately dripping A, B, C and D components into the flask, finishing dripping within 2.5h, and preserving heat for 1.5h after finishing dripping to further finish the polymerization reaction;

s4, reducing the temperature to 62-65 ℃, respectively adding tert-butyl hydroperoxide, sodium metabisulfite tert-butyl hydroperoxide and sodium metabisulfite twice, wherein the total amount of the tert-butyl hydroperoxide, the sodium metabisulfite tert-butyl hydroperoxide and the sodium metabisulfite is 1-1.5 percent of the total amount of the monomers, and preserving the temperature for 1 hour to further polymerize the unreacted monomers, so as to improve the conversion rate;

s5, adding a chain terminator, wherein the chain terminator accounts for 0.1-2% of the total amount of the monomers, slowly cooling, stopping the reaction after 0.5h, cooling to 35-40 ℃, and adjusting the pH value to 7-8 with ammonia water to obtain a copolymer emulsion;

s5, adding the obtained emulsion into saturated salt water, stirring to demulsify, filtering out solids, fully washing with deionized water to remove unreacted monomers, and then drying in vacuum at 25 ℃ to obtain copolymer solids;

s7, mixing the copolymer with the mass ratio of 30-55%, the cationic organosilicon surfactant with the mass ratio of 5-20% and the water with the mass ratio of 25-60%, stirring for 30-70 minutes at the temperature of 30-70 ℃, cooling to room temperature at the rotation speed of 200-600 rpm, and filtering to remove impurities to obtain the novel high-molecular copolymer demulsifier.

Preferably, the initiator is one or a mixture of two of azobisisobutyronitrile and azobisisoheptonitrile.

Preferably, in step S2, A, B, C and three D components are alternately added dropwise to the flask in an amount of 15 drops per second.

Preferably, p-tert-butylcatechol is used as the chain terminator.

The invention also provides a novel high-molecular copolymer demulsifier prepared by any one of the preparation methods.

Compared with the prior art, the invention has the beneficial effects that: the novel high-molecular copolymer demulsifier and the preparation method thereof have the advantages of low preparation cost, environment friendliness, non-polyether demulsifier, and high molecular weight, and the organic silicon surfactant is introduced when the prepared high-molecular copolymer demulsifier is compounded, so that the demulsification speed is higher and the demulsification effect is better.

Drawings

FIG. 1 is a schematic diagram of the structural formula of a novel polymer demulsifier of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Example 1

The embodiment provides a technical scheme: a novel high-molecular copolymer demulsifier and a preparation method thereof, wherein the demulsifier is prepared by adopting the following preparation method, and comprises the following steps:

s1, 6.5 parts of butyl acrylate is added to 0.3 part of chain transfer agent AMSD, and the mixture (marked as component A) is mixed for standby. A mixture of 8 parts of styrene and 0.3 part of the chain transfer agent AMSD (denoted as component B), a mixture of 3 parts of N- (3-dimethylaminopropyl) methacrylamide and 0.3 part of the chain transfer agent AMSD (denoted as component C), and a mixture of 2.5 parts of AMPS and 0.3 part of the chain transfer agent AMSD (denoted as component D) were prepared for use. The chain transfer agent AMSD is alpha-methyl styrene linear dimer. AMPS is 2-acrylamide-2-methylpropanesulfonic acid.

S2: adding a certain amount of water, acetone and 0.32 part of emulsifier sodium dodecyl sulfate into a four-neck flask, stirring and heating the flask in a water bath to dissolve the mixture, heating the mixture to 73-75 ℃, adding an initiator azobisisobutyronitrile accounting for 5% of the total amount of the initiator, and adding all the initiator azobisisobutyronitrile when the temperature is raised to 78-81 ℃ to form a stable micelle system.

S3: when the system in the second step generates blue light, A, B, C and D are alternately dripped into the flask by a starvation type dripping method, and after dripping is finished for 2.5 hours, the mixture is uniformly dripped, wherein the dripping amount is 15 drops per second. After the completion of the dropwise addition, the polymerization reaction was further completed by keeping the temperature for 1.5 hours.

S4: and reducing the temperature to 62-65 ℃, respectively adding 0.12 part of tert-butyl hydroperoxide and 0.08 part of sodium metabisulfite twice, and preserving the temperature for 1 hour to further polymerize the unreacted monomers.

S5: and adding 0.02 part of p-tert-butyl catechol, slowly cooling, stopping the reaction after 0.5h, cooling to 35-40 ℃, and adjusting the pH value to 7-8 by using ammonia water to obtain the copolymer emulsion.

S6: adding the emulsion obtained in the step S5 into saturated saline water, stirring to break the emulsion, filtering out solids, fully washing with deionized water to remove unreacted monomers, and then drying at 25 ℃ to obtain a copolymer solid.

S7: and (3) mixing the copolymer obtained in the step S6 with dodecyl trimethyl ammonium chloride and water according to the weight ratio of 55: 5: 40 at 35 deg.c, stirring for 40 min at 400rpm, cooling to room temperature, filtering to remove impurities, and obtaining a novel polymer demulsifier with a molecular formula shown in fig. 1.

Example 2

The embodiment provides a technical scheme: a novel high-molecular copolymer demulsifier and a preparation method thereof, wherein the demulsifier is prepared by adopting the following preparation method, and comprises the following steps:

s1: 5 parts of butyl acrylate are added to 0.25 part of the chain transfer agent AMSD and the mixture (designated as component A) is ready for use after mixing. 10 parts of styrene and 0.3 part of chain transfer agent AMSD (noted as component B), a mixture of 3.5 parts of N- (3-dimethylaminopropyl) methacrylamide and 0.3 part of chain transfer agent AMSD (noted as component C) and a mixture of 1.5 parts of AMPS and 0.25 part of chain transfer agent AMSD (noted as component D) are mixed for later use. The chain transfer agent AMSD is alpha-methyl styrene linear dimer. AMPS is 2-acrylamide-2-methylpropanesulfonic acid.

S2: adding a certain amount of water, 0.15 part of acetone and 0.32 part of emulsifier sodium dodecyl sulfate into a four-neck flask, stirring and heating the flask in a water bath kettle to dissolve the mixture, heating the flask to 73-75 ℃, adding an initiator azobisisobutyronitrile accounting for 5 percent of the total amount of the initiator, and adding all the initiators (the total addition amount is 0.1 part) when the temperature is raised to 78-81 ℃ to form a stable micelle system.

S3: when the system generates blue light, A, B, C and D components are alternately dripped into the flask by a starvation type dripping method, and after dripping is finished within 2.5 hours, uniform dripping is required, and the dripping amount can be considered to be 15 drops per second. After the completion of the dropwise addition, the polymerization reaction was further completed by keeping the temperature for 1.5 hours.

S4: and reducing the temperature to 62-65 ℃, respectively adding 0.1 part of tert-butyl hydroperoxide and 0.06 part of sodium metabisulfite twice, and preserving the temperature for 1 hour to further polymerize unreacted monomers, thereby improving the conversion rate.

S5: and adding 0.02 part of chain terminator p-tert-butyl catechol, slowly cooling, stopping the reaction after 0.5h, cooling to 35-40 ℃, and adjusting the pH value to 7-8 by using ammonia water to obtain the copolymer emulsion.

S6: the resulting emulsion was added to saturated brine, stirred to break the emulsion, the solids filtered and washed thoroughly with deionized water to remove unreacted monomer, and then air dried at 25 ℃ to give a copolymer solid.

S7: copolymer was mixed with dodecyltrimethylammonium chloride and water according to a 58: 2: 40 at 30 deg.c, stirring for 30 min at 500rpm, cooling to room temperature, filtering to remove impurities, and obtaining a novel polymer demulsifier with a molecular formula shown in fig. 1.

According to the novel high-molecular copolymer demulsifier and the preparation method thereof, the prepared copolymer demulsifier has the characteristics of environmental friendliness, no polyether and high molecular weight, and the organic silicon surfactant is introduced during compounding, so that the demulsification speed is higher and the demulsification effect is better.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.