阅读说明：本技术 一种井下作业油泥砂破乳剂及其制备方法和应用 (Underground operation oil sludge demulsifier and preparation method and application thereof ) 是由 崔仕章 王黎明 宋新旺 郭玉玺 高瑞美 张向红 吴艳青 殷会良 尹凯全 于 2021-11-19 设计创作，主要内容包括：本申请公开了一种井下作业油泥砂破乳剂及其制备方法和应用,属于破乳剂技术领域。一种井下作业油泥砂破乳剂,包括以下重量份的组分,磺酸盐类或季铵盐类两性离子型破乳剂20～35份,氨基酸改性聚醚15～25份,聚醚类降粘剂1～5份,聚丙烯酰胺类沉降剂2～10份,木质素磺酸盐类分散剂1～3份和醇类有机溶剂40～65份；其中,所述氨基酸改性聚醚为多元氨基酸共聚物改性聚乙二醇二乙烯基醚；所述氨基酸改性聚醚的分子量为3500～5000。该井下作业油泥砂破乳剂具有用量少和脱水率高的优点,且适用于大多数油泥砂的处理。(The application discloses a demulsifier for oil sludge sand in downhole operation, a preparation method and application thereof, and belongs to the technical field of demulsifiers. 20-35 parts of sulfonate or quaternary ammonium salt zwitterionic demulsifier, 15-25 parts of amino acid modified polyether, 1-5 parts of polyether viscosity reducer, 2-10 parts of polyacrylamide settling agent, 1-3 parts of lignosulfonate dispersant and 40-65 parts of alcohol organic solvent; wherein the amino acid modified polyether is polyethylene glycol divinyl ether modified by a polybasic amino acid copolymer; the molecular weight of the amino acid modified polyether is 3500-5000. The underground operation oil sludge demulsifier has the advantages of small dosage and high dehydration rate, and is suitable for treating most of oil sludge.)

1. The oil sludge sand demulsifier for downhole operation is characterized by comprising 20-35 parts by weight of sulfonate or quaternary ammonium salt zwitterionic demulsifier, 15-25 parts by weight of amino acid modified polyether, 1-5 parts by weight of polyether viscosity reducer, 2-10 parts by weight of polyacrylamide settling agent, 1-3 parts by weight of lignosulfonate dispersant and 40-65 parts by weight of alcohol organic solvent;

wherein the amino acid modified polyether is polyethylene glycol divinyl ether modified by a polybasic amino acid copolymer;

the molecular weight of the amino acid modified polyether is 3500-5000.

2. The demulsifier for oil sludge sand of downhole operation according to claim 1, wherein the amino acid-modified polyether is prepared by the following method:

placing polyethylene glycol divinyl ether, a polybasic amino acid copolymer and a solvent into a reaction kettle, stirring and reacting for 0.5-2 h at 20-30 ℃, then heating to 50-65 ℃, stirring and reacting for 1-2.5 h, adding a catalyst into the mixed solution, stirring and reacting for 1-2 h at 55-70 ℃, and then carrying out reduced pressure distillation to remove the solvent to obtain the amino acid modified polyether;

wherein the solvent is acetonitrile, dimethylformamide, dimethyl sulfoxide or hexamethylphosphoric triamide.

3. The demulsifier for oil sludge sand of downhole operation according to claim 2, wherein the mass ratio of the polyethylene glycol divinyl ether to the polybasic amino acid copolymer is (20-35): 1.

4. the downhole well servicing oil sands demulsifier of claim 2, wherein the polyamino acid copolymer is copolymerized from 6-aminocaproic acid, glycine, alanine, L-leucine, L-phenylalanine, and L-tryptophan.

5. The downhole operation silt demulsifier of claim 2, wherein the catalyst is selected from an antimony-based catalyst, a titanium-based catalyst, or a zirconium-based catalyst.

6. The downhole operations silt demulsifier of claim 1, wherein the sulfonate-or quaternary ammonium zwitterionic demulsifier is an alkylbenzene sulfonate, a petroleum sulfonate, a quaternary ammonium salt or a quaternary ammonium base.

7. The downhole operations tar sands demulsifier of claim 1, wherein the lignosulfonate dispersant is sodium lignosulfonate, potassium lignosulfonate, calcium lignosulfonate, or alkaline lignin, and the alcohol organic solvent is methanol, ethanol, propanol, isopropanol, ethylene glycol, or benzyl alcohol.

8. The method for preparing the demulsifier for the oil sludge of the downhole operation of any one of claims 1 to 7, which comprises the following steps:

adding 20-35 parts of sulfonate or quaternary ammonium salt zwitterionic demulsifier, 15-25 parts of amino acid modified polyether, 1-5 parts of polyether viscosity reducer, 2-10 parts of polyacrylamide settling agent, 1-3 parts of lignosulfonate dispersant and 40-65 parts of alcohol organic solvent into a stirring kettle, and stirring for 0.5-1.5 hours to obtain the underground operation oil sand demulsifier.

9. The preparation method of the demulsifier for the oil sludge and the oil sands for the downhole operation according to claim 8, wherein the stirring temperature is 50-75 ℃ and the rotation speed is 50-200 r/min.

10. Use of the downhole operations sand demulsifier of any of claims 1-7 in the treatment of downhole operations sand.

Technical Field

The application relates to a demulsifier for oil sludge sand in downhole operation, a preparation method and application thereof, belonging to the technical field of demulsifiers.

Background

Millions of tons of oil-containing silt are generated in the crude oil exploitation process in China, and the oil-containing silt contains a large amount of mineral oil and other harmful substances, belongs to dangerous waste and has great harm to the environment; if the waste water is not treated and directly discharged, not only a large amount of cultivated land is occupied, but also the surrounding soil, water and air are seriously polluted, once the ecological environment is polluted and damaged, the ecological environment is difficult to recover, and serious adverse effects are caused, which is contrary to the gist of saving, environmental protection and scientific development advocated in China. There is therefore a need for an effective treatment of oil-containing silt to meet the requirements of the relevant regulations.

The crude oil contains natural surfactants such as colloid, resin, organic acid and asphaltene, and simultaneously contains a large amount of water, which are adsorbed on the surface of oil water to form an interfacial film with certain strength and tension, so that water drops are difficult to be agglomerated together. Therefore, most of the water is dispersed in the crude oil as extremely fine particles to form a stable crude oil emulsion, which causes great difficulty in oil-water separation. In the process of oil sludge treatment, an oil-water interface membrane needs to be broken first, so that oil and water are separated from each other, and further three-phase separation of oil, water and sludge is realized. In recent years, the chemical demulsification method is the most widely used demulsification method in oil fields, and has the advantages of relatively high dehydration rate, clear oil/water interface, low consumption, low cost, low energy consumption and the like. However, most of the currently used demulsifiers have the characteristics of small dehydration amount, low dehydration speed, poor demulsification effect, small application range and the like, and the treatment efficiency of the oil sludge sand is greatly reduced. Therefore, the search for a novel demulsifier with excellent demulsification performance and strong applicability still faces a great challenge in the future.

Disclosure of Invention

In order to solve the problems, the invention provides the demulsifier for the oil sludge sand in the downhole operation, the preparation method and the application thereof.

The technical scheme adopted by the invention is as follows:

on one hand, the invention provides a downhole operation oil sludge demulsifier, which comprises the following components, by weight, 20-35 parts of sulfonate or quaternary ammonium salt zwitterionic demulsifier, 15-25 parts of amino acid modified polyether, 1-5 parts of polyether viscosity reducer, 2-10 parts of polyacrylamide settling agent, 1-3 parts of lignosulfonate dispersant and 40-65 parts of alcohol organic solvent;

wherein the amino acid modified polyether is polyethylene glycol divinyl ether modified by a polybasic amino acid copolymer;

the molecular weight of the amino acid modified polyether is 3500-5000.

The amino acid modified polyether is prepared by the following method:

placing polyethylene glycol divinyl ether, a polybasic amino acid copolymer and a solvent into a reaction kettle, stirring and reacting for 0.5-2 h at 20-30 ℃, then heating to 50-65 ℃, stirring and reacting for 1-2.5 h, adding a catalyst into the mixed solution, stirring and reacting for 1-2 h at 55-70 ℃, and then carrying out reduced pressure distillation to remove the solvent to obtain the amino acid modified polyether;

wherein the solvent is acetonitrile, dimethylformamide, dimethyl sulfoxide or hexamethylphosphoric triamide; preferably, the solvent is dimethylformamide.

Preferably, the mass ratio of the polyethylene glycol divinyl ether to the polybasic amino acid copolymer is (20-35): 1, more preferably (25-30): 1, more preferably 28: 1.

preferably, the polyamino acid copolymer is copolymerized from 6-aminocaproic acid, glycine, alanine, L-leucine, L-phenylalanine, and L-tryptophan.

Preferably, the catalyst is selected from an antimony-based catalyst, a titanium-based catalyst or a zirconium-based catalyst.

Preferably, the antimony-based catalyst is antimony trioxide, antimony acetate or ethylene glycol antimony, more preferably antimony trioxide; the titanium catalyst is titanium tetrachloride; the zirconium based catalyst is zirconium phosphate.

Preferably, the sulfonate or quaternary ammonium zwitterionic demulsifier is an alkylbenzene sulfonate, a petroleum sulfonate, a quaternary ammonium salt or a quaternary ammonium base, more preferably an alkylbenzene sulfonate.

Preferably, the polyether viscosity reducer is polyether acrylate, and the polyacrylamide settling agent is polyacrylic acid-acrylamide.

Preferably, the lignosulfonate-type dispersant is sodium lignosulfonate, potassium lignosulfonate, calcium lignosulfonate or alkaline lignin, more preferably sodium lignosulfonate; the alcohol organic solvent is methanol, ethanol, propanol, isopropanol, ethylene glycol or benzyl alcohol, and preferably ethylene glycol.

In another aspect, the invention provides a preparation method of the demulsifier for oil sludge sand for downhole operation, which comprises the following steps:

adding 20-35 parts of sulfonate or quaternary ammonium salt zwitterionic demulsifier, 15-25 parts of amino acid modified polyether, 1-5 parts of polyether viscosity reducer, 2-10 parts of polyacrylamide settling agent, 1-3 parts of lignosulfonate dispersant and 40-65 parts of alcohol organic solvent into a stirring kettle, and stirring for 0.5-1.5 hours to obtain the underground operation oil sand demulsifier.

Preferably, the stirring temperature is 50-75 ℃, and the rotating speed is 50-200 r/min.

In another aspect, the invention protects the application of any one of the above described downhole operation oil sludge demulsifiers or any one of the downhole operation oil sludge demulsifiers obtained by the above described preparation methods in downhole operation oil sludge treatment.

Benefits of the present application include, but are not limited to:

1. in the oil sludge demulsifier for downhole operation, a large number of amino groups on the polybasic amino acid copolymer can be gathered on an oil-water interface film, so that the adsorption effect with water molecules is enhanced, and the dehydration rate is improved; carboxyl in the polybasic amino acid copolymer and hydroxyl in polyethylene glycol divinyl ether are subjected to esterification reaction, so that the molecular weight of the amino acid modified polyether is increased, the area covered by the amino acid modified polyether on an oil-water interface is larger, and the demulsification effect is better. The synergistic effect of the zwitterionic demulsifier and the amino acid modified polyether overcomes the defects of large using amount and small application range of the zwitterionic demulsifier, and the compound demulsifier with good comprehensive dehydration effect is obtained.

2. The preparation method of the underground operation oil sludge sand demulsifier is simple, has low requirements on production environment, can be used and manufactured at any time, can work together with the oil sludge sand treatment process, and can not generate the problem that the demulsification effect is influenced due to the fact that the demulsifier is sealed for a long time.

3. The application range of the operation oil sludge sand demulsifier is wide, the oil sludge sand demulsification separation process is particularly suitable for underground operation, the demulsification effect is good, the oil sludge sand separation and recovery efficiency is high, a small amount of oil sludge sand can achieve a good demulsification effect, and the problem of high treatment cost of the existing oil sludge sand is solved.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

According to one aspect of the invention, the invention provides a demulsifier for oil sludge and sand in downhole operation, which comprises, by weight, 20-35 parts of sulfonate or quaternary ammonium salt zwitterionic demulsifier, 15-25 parts of amino acid modified polyether, 1-5 parts of polyether viscosity reducer, 2-10 parts of polyacrylamide settling agent, 1-3 parts of lignosulfonate dispersant and 40-65 parts of alcohol organic solvent;

wherein the amino acid modified polyether is polyethylene glycol divinyl ether modified by a polybasic amino acid copolymer;

the molecular weight of the amino acid modified polyether is 3500-5000.

Preferably, the zwitterionic demulsifier is an alkyl benzene sulphonate, a petroleum sulphonate, a quaternary ammonium salt or a quaternary ammonium base, more preferably an alkyl benzene sulphonate.

Preferably, the polyether viscosity reducer is polyether acrylate, and the polyacrylamide settling agent is polyacrylic acid-acrylamide.

Preferably, the lignosulfonate dispersant is sodium lignosulfonate, potassium lignosulfonate, calcium lignosulfonate or alkaline lignin, more preferably sodium lignosulfonate; the alcohol organic solvent is methanol, ethanol, propanol, isopropanol, ethylene glycol or benzyl alcohol, and preferably ethylene glycol.

The amino acid modified polyether is prepared by the following method:

placing polyethylene glycol divinyl ether, a polybasic amino acid copolymer and a solvent into a reaction kettle, stirring and reacting for 0.5-2 h at 20-30 ℃, then heating to 50-65 ℃, stirring and reacting for 1-2.5 h, adding a catalyst into the system, stirring and reacting for 1-2 h at 55-70 ℃, and then carrying out reduced pressure distillation to remove the solvent to obtain amino acid modified polyether;

wherein the solvent is acetonitrile, dimethylformamide, dimethyl sulfoxide or hexamethylphosphoric triamide; preferably, the solvent is dimethylformamide.

Preferably, the mass ratio of the polyethylene glycol divinyl ether to the polybasic amino acid copolymer is (20-35): 1, more preferably (25-30): 1, more preferably 28: 1.

preferably, the polyamino acid copolymer is copolymerized from 6-aminocaproic acid, glycine, alanine, L-leucine, L-phenylalanine, and L-tryptophan.

Preferably, the catalyst is selected from an antimony-based catalyst, a titanium-based catalyst or a zirconium-based catalyst;

preferably, the antimony-based catalyst is antimony trioxide, antimony acetate or ethylene glycol antimony, more preferably antimony trioxide; the titanium catalyst is titanium tetrachloride; the zirconium based catalyst is zirconium phosphate.

According to another aspect of the invention, the invention provides a preparation method of any one of the underground operation oil sludge demulsifiers, which comprises the following steps:

adding 20-35 parts of sulfonate or quaternary ammonium salt zwitterionic demulsifier, 15-25 parts of amino acid modified polyether, 1-5 parts of polyether viscosity reducer, 2-10 parts of polyacrylamide settling agent, 1-3 parts of lignosulfonate dispersant and 40-65 parts of alcohol organic solvent into a stirring kettle, and stirring for 0.5-1.5 hours to obtain the downhole operation oil sand demulsifier.

Preferably, the stirring temperature is 50-75 ℃, and the rotating speed is 50-200 r/min.

According to a further aspect of the invention, the invention provides the use of any one of the above-mentioned demulsifiers for oil sludge sand for downhole operations or any one of the above-mentioned demulsifiers for oil sludge sand for downhole operations obtained by the preparation method, in the treatment of oil sludge sand for downhole operations.

The following examples and comparative examples may provide reference to a person having ordinary skill in the art to practice the present invention or verify the effects. These examples do not limit the scope of the claims.

Example 1:

a preparation method of a demulsifier for oil sludge sand in downhole operation comprises the following steps:

(1) placing polyethylene glycol divinyl ether, a polybasic amino acid copolymer and dimethylformamide into a reaction kettle, wherein the mass ratio of the polyethylene glycol divinyl ether to the polybasic amino acid copolymer is 28: 1, stirring and reacting for 1h at 25 ℃, then heating to 57 ℃, stirring and reacting for 1.5h, adding antimony trioxide into the system, stirring and reacting for 1.5h at 65 ℃, and then distilling under reduced pressure to remove the solvent to obtain amino acid modified polyether;

(2) adding 28 parts of alkylbenzene sulfonate, 20 parts of amino acid modified polyether, 3 parts of polyether acrylate, 6 parts of polyacrylic acid-acrylamide, 2 parts of sodium lignosulfonate and 53 parts of ethylene glycol into a stirring kettle, stirring at 65 ℃ and at a rotating speed of 120r/min for 1h to obtain the oily sand demulsifier for downhole operation.

Example 2:

a preparation method of a demulsifier for oil sludge sand in downhole operation comprises the following steps:

(1) placing polyethylene glycol divinyl ether, a polybasic amino acid copolymer and acetonitrile into a reaction kettle, wherein the mass ratio of the polyethylene glycol divinyl ether to the polybasic amino acid copolymer is 20: 1, stirring and reacting for 1h at 25 ℃, then heating to 57 ℃, stirring and reacting for 1.5h, adding ethylene glycol antimony into the system, stirring and reacting for 1.5h at 65 ℃, and then distilling under reduced pressure to remove the solvent to obtain amino acid modified polyether;

(2) adding 20 parts of petroleum sulfonate, 15 parts of amino acid modified polyether, 3 parts of polyether acrylate, 6 parts of polyacrylic acid-acrylamide, 2 parts of potassium lignosulfonate and 53 parts of methanol into a stirring kettle, stirring at 65 ℃ and at a rotating speed of 120r/min for 1h to obtain the oily sand demulsifier for downhole operation.

Example 3:

a preparation method of a demulsifier for oil sludge sand in downhole operation comprises the following steps:

(1) placing polyethylene glycol divinyl ether, a polybasic amino acid copolymer and dimethyl sulfoxide into a reaction kettle, wherein the mass ratio of the polyethylene glycol divinyl ether to the polybasic amino acid copolymer is 24: 1, stirring and reacting for 1h at 25 ℃, then heating to 57 ℃, stirring and reacting for 1.5h, adding antimony acetate into the system, stirring and reacting for 1.5h at 65 ℃, and then distilling under reduced pressure to remove the solvent to obtain amino acid modified polyether;

(2) adding 24 parts of alkylbenzene sulfonate, 17 parts of amino acid modified polyether, 3 parts of polyether acrylate, 6 parts of polyacrylic acid-acrylamide, 2 parts of calcium lignosulfonate and 53 parts of ethanol into a stirring kettle, stirring at 65 ℃ and at a rotating speed of 120r/min for 1h to obtain the oily sand demulsifier for downhole operation.

Example 4:

a preparation method of a demulsifier for oil sludge sand in downhole operation comprises the following steps:

(1) placing polyethylene glycol divinyl ether, a polybasic amino acid copolymer and dimethylformamide into a reaction kettle, wherein the mass ratio of the polyethylene glycol divinyl ether to the polybasic amino acid copolymer is 32: 1, stirring and reacting for 1h at 25 ℃, then heating to 57 ℃, stirring and reacting for 1.5h, adding titanium tetrachloride into the system, stirring and reacting for 1.5h at 65 ℃, and then distilling under reduced pressure to remove the solvent to obtain amino acid modified polyether;

(2) adding 30 parts of quaternary ammonium base, 23 parts of amino acid modified polyether, 3 parts of polyether acrylate, 6 parts of polyacrylic acid-acrylamide, 2 parts of alkaline lignin and 53 parts of isopropanol into a stirring kettle, stirring at 65 ℃ and at a rotating speed of 120r/min for 1h to obtain the downhole operation oil sand demulsifier.

Example 5:

a preparation method of a demulsifier for oil sludge sand in downhole operation comprises the following steps:

(1) placing polyethylene glycol divinyl ether, a polybasic amino acid copolymer and hexamethylphosphoric triamide into a reaction kettle, wherein the mass ratio of the polyethylene glycol divinyl ether to the polybasic amino acid copolymer is 35: 1, stirring and reacting for 1h at 25 ℃, then heating to 57 ℃, stirring and reacting for 1.5h, adding zirconium phosphate into the system, stirring and reacting for 1.5h at 65 ℃, and then distilling under reduced pressure to remove the solvent to obtain amino acid modified polyether;

(2) adding 35 parts of quaternary ammonium salt, 25 parts of amino acid modified polyether, 3 parts of polyether acrylate, 6 parts of polyacrylic acid-acrylamide, 2 parts of calcium lignosulfonate and 53 parts of benzyl alcohol into a stirring kettle, stirring at 65 ℃ and at a rotating speed of 120r/min for 1h to obtain the downhole operation oil sand demulsifier.

Comparative example 1

The demulsifier was prepared in the same manner as in example 1, except that the mass ratio of polyethylene glycol divinyl ether to the polyamino acid copolymer in step (1) was 10: 1.

comparative example 2

The demulsifier was prepared in the same manner as in example 1, except that the mass ratio of polyethylene glycol divinyl ether to the polyamino acid copolymer in step (1) was 45: 1.

comparative example 3

The demulsifier was prepared in the same manner as in example 1 except that the catalyst in step (1) was iron oxide.

Comparative example 4

A demulsifier was prepared in the same manner as in example 1 except that the step (1) was removed and the amino acid-modified polyether in the step (2) was replaced with polyethylene glycol divinyl ether.

Comparative example 5

The demulsifier was prepared in the same manner as in example 1, except that the alkylbenzene sulfonate was replaced with extracellular protein-based secretion of Bacillus mojavensis in step (2).

Comparative example 6

The demulsifier was prepared in the same manner as in example 1 except that 10 parts of alkylbenzene sulfonate was used in step (2).

Comparative example 7

The demulsifier was prepared in the same manner as in example 1 except that 40 parts of alkylbenzene sulfonate was used in step (2).

Comparative example 8

The demulsifier was prepared in the same manner as in example 1 except that 8 parts of the amino acid-modified polyether was used in step (2).

Comparative example 9

A demulsifier was prepared in the same manner as in example 1 except that 35 parts of the amino acid-modified polyether was used in step (2).

Evaluation of the demulsifier for the oil sludge of the downhole operation:

the demulsifiers of examples 1 to 5 and comparative examples 1 to 9 were subjected to evaluation of dehydration effect, the Daqing oil field, the Bohai oil field and the Tarim oil field were all suitable objects for the demulsifier of the present invention, and Table 1 shows that thick oil produced liquid from the Tarim oil field is treated as an object, and the dehydration effect is as follows:

TABLE 1 evaluation of dewatering Effect

As can be seen from the table 1, the dehydration rate of the demulsifier for the oil sludge sand in the downhole operation is up to more than 90%, the dosage is less, the application range is wide, and the problem of oil-water separation in the treatment process of the oil sludge sand is solved.

The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.