阅读说明：本技术 原油破乳剂及其制备方法 (Crude oil demulsifier and preparation method thereof ) 是由 朱晓明 李祥林 李建平 李娜 齐学辉 杨豫新 于 2021-10-22 设计创作，主要内容包括：本发明涉及油田破乳剂及制备方法技术领域,是一种原油破乳剂及其制备方法,前者原料包括聚醚干剂、甲醇和水混合,在适宜温度下搅拌后得到原油破乳剂。本发明制得的原油破乳剂在对乳化原油、原油采出液等进行破乳时,具有脱水速度快,对复杂乳液的破乳能力强,尤其是对含蜡、含压裂液原油、部分油田老化原油具有优异的破乳效果。(The invention relates to the technical field of oil field demulsifiers and preparation methods thereof, in particular to a crude oil demulsifier and a preparation method thereof. The crude oil demulsifier prepared by the invention has the advantages of high dehydration speed and strong demulsification capability on complex emulsion when demulsifying emulsified crude oil, crude oil produced liquid and the like, and particularly has excellent demulsification effect on crude oil containing wax and fracturing fluid and part of aged crude oil in oil fields.)

1. The polyether drying agent is characterized by having a chemical structural formula as follows:wherein R is a starter, m is 0 to 500, n is 0 to 150; the chemical structural formula of the initiator R is as follows:

wherein n in the chemical structural formula of the initiator R is 0-50.

2. The polyether drier as claimed in claim 1, wherein the raw materials comprise, by weight, 0.5 to 30 parts of an initiator, 0.5 to 2 parts of sodium hydroxide, 40 to 85 parts of propylene oxide, and 10 to 30 parts of ethylene oxide, and the polyether drier is obtained by the following method: firstly, adding required amount of initiator and sodium hydroxide into a reaction kettle, stirring and heating to 125-130 ℃, evacuating the reaction kettle, filling nitrogen into the reaction kettle to form a nitrogen atmosphere in the reaction kettle, then adding required amount of propylene oxide, wherein the reaction pressure in the reaction kettle is 0.10-0.25 MPa, and the reaction temperature is 125-130 ℃; and then adding the required amount of ethylene oxide, wherein the reaction pressure is 0.10MPa to 0.25MPa, the reaction temperature is 115 ℃ to 125 ℃, continuing to perform curing reaction for 1 hour after the addition is finished, the reaction temperature is 115 ℃ to 125 ℃, and cooling and discharging to obtain the polyether drying agent after the pressure in the reaction kettle is reduced to normal pressure.

3. The polyether dry formulation according to claim 2, wherein the starting materials of the initiator comprise a molar ratio of 0.5 to 2: 2 to 6 of p-hydroxyacetophenone and formaldehyde, obtained by the following process: adding p-hydroxyacetophenone, formaldehyde and sodium hydroxide with required amount in the amount of 1-5 wt% of the initiator material into a reaction kettle, controlling the temperature in the reaction kettle at 40-50 deg.c and the reaction pressure at 0.2-0.5 MPa, reacting for 2 hr, adding xylene solvent with required amount, heating to 90-95 deg.c and the reaction pressure at 0.2-0.5 MPa, reacting for 2-3 hr, and vacuum refluxing to eliminate water to obtain the initiator.

4. The preparation method of the polyether dry agent according to claim 1 or 3, characterized in that the raw materials comprise 0.5 to 30 parts of initiator, 0.5 to 2 parts of sodium hydroxide, 40 to 85 parts of propylene oxide and 10 to 30 parts of ethylene oxide by weight, and the polyether dry agent is obtained by the following method: firstly, adding required amount of initiator and sodium hydroxide into a reaction kettle, stirring and heating to 125-130 ℃, evacuating the reaction kettle, filling nitrogen into the reaction kettle to form a nitrogen atmosphere in the reaction kettle, then adding required amount of propylene oxide, wherein the reaction pressure in the reaction kettle is 0.10-0.25 MPa, and the reaction temperature is 125-130 ℃; and then adding the required amount of ethylene oxide, wherein the reaction pressure is 0.10MPa to 0.25MPa, the reaction temperature is 115 ℃ to 125 ℃, continuing to perform curing reaction for 1 hour after the addition is finished, the reaction temperature is 115 ℃ to 125 ℃, and cooling and discharging to obtain the polyether drying agent after the pressure in the reaction kettle is reduced to normal pressure.

5. A crude oil demulsifier using the polyether dry agent of any one of claims 1 to 3 as a raw material, which is characterized in that the raw material comprises 40 to 60 percent of the polyether dry agent, 10 to 30 percent of methanol and the balance of water in percentage by weight.

6. The crude oil demulsifier of claim 5, wherein the required amount of polyether drier, methanol and water are mixed, and the crude oil demulsifier is obtained after stirring for 30 to 60 minutes at a temperature of 40 to 50 ℃.

7. The preparation method of the crude oil demulsifier according to claim 5, wherein the required amount of the polyether drier, methanol and water are mixed, and the mixture is stirred at a temperature of 40 ℃ to 50 ℃ for 30 to 60 minutes to obtain the crude oil demulsifier.

Technical Field

The invention relates to the technical field of oil field demulsifiers and preparation methods thereof, in particular to a crude oil demulsifier and a preparation method thereof, and also comprises a polyether drying agent and a preparation method thereof.

Background

The produced fluid demulsification dehydration is very important for the exploitation, gathering and transportation and processing of crude oil. Most oil fields at home and abroad are in the middle and later development stages, and due to the implementation of various oil increasing measures, the produced liquid is complex in emulsification state and stable in emulsion, so that demulsification and dehydration are very difficult, and a plurality of problems are brought to production. In order to break crude oil emulsion, special demulsifier is needed, and many researches are carried out at home and abroad, but the demulsifier which can break and separate the emulsion more effectively is still needed.

Disclosure of Invention

The invention provides a crude oil demulsifier and a preparation method thereof, which overcome the defects of the prior art, have strong demulsification capability on complex emulsion, and particularly have excellent demulsification effect on crude oil containing wax and fracturing fluid and part of aged crude oil in oil fields.

One of the technical schemes of the invention is realized by the following measures: a polyether drier has a chemical structural formula as follows:wherein R is a starter, m is 0 to 500, n is 0 to 150; the chemical structural formula of the initiator R is as follows:

wherein n in the chemical structural formula of the initiator R is 0-50.

The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:

the polyether drying agent comprises, by weight, 0.5-30 parts of an initiator, 0.5-2 parts of sodium hydroxide, 40-85 parts of propylene oxide and 10-30 parts of ethylene oxide, and is obtained by the following method: firstly, adding required amount of initiator and sodium hydroxide into a reaction kettle, stirring and heating to 125-130 ℃, evacuating the reaction kettle, filling nitrogen into the reaction kettle to form a nitrogen atmosphere in the reaction kettle, then adding required amount of propylene oxide, wherein the reaction pressure in the reaction kettle is 0.10-0.25 MPa, and the reaction temperature is 125-130 ℃; and then adding the required amount of ethylene oxide, wherein the reaction pressure is 0.10MPa to 0.25MPa, the reaction temperature is 115 ℃ to 125 ℃, continuing to perform curing reaction for 1 hour after the addition is finished, the reaction temperature is 115 ℃ to 125 ℃, and cooling and discharging to obtain the polyether drying agent after the pressure in the reaction kettle is reduced to normal pressure.

The raw materials of the initiator comprise a molar ratio of 0.5 to 2: 2 to 6 of p-hydroxyacetophenone and formaldehyde, obtained by the following process: adding p-hydroxyacetophenone, formaldehyde and sodium hydroxide with required amount in the amount of 1-5 wt% of the initiator material into a reaction kettle, controlling the temperature in the reaction kettle at 40-50 deg.c and the reaction pressure at 0.2-0.5 MPa, reacting for 2 hr, adding xylene solvent with required amount, heating to 90-95 deg.c and the reaction pressure at 0.2-0.5 MPa, reacting for 2-3 hr, and vacuum refluxing to eliminate water to obtain the initiator.

The second technical scheme of the invention is realized by the following measures: a preparation method of the polyether dry agent comprises the following raw materials, by weight, 0.5 to 30 parts of an initiator, 0.5 to 2 parts of sodium hydroxide, 40 to 85 parts of propylene oxide and 10 to 30 parts of ethylene oxide, and is obtained by the following method: firstly, adding required amount of initiator and sodium hydroxide into a reaction kettle, stirring and heating to 125-130 ℃, evacuating the reaction kettle, filling nitrogen into the reaction kettle to form a nitrogen atmosphere in the reaction kettle, then adding required amount of propylene oxide, wherein the reaction pressure in the reaction kettle is 0.10-0.25 MPa, and the reaction temperature is 125-130 ℃; and then adding the required amount of ethylene oxide, wherein the reaction pressure is 0.10MPa to 0.25MPa, the reaction temperature is 115 ℃ to 125 ℃, continuing to perform curing reaction for 1 hour after the addition is finished, the reaction temperature is 115 ℃ to 125 ℃, and cooling and discharging to obtain the polyether drying agent after the pressure in the reaction kettle is reduced to normal pressure.

The following is further optimization or/and improvement of the second technical scheme of the invention:

the raw materials of the initiator comprise a molar ratio of 0.5 to 2: 2 to 6 of p-hydroxyacetophenone and formaldehyde, obtained by the following process: adding p-hydroxyacetophenone, formaldehyde and sodium hydroxide with required amount in the amount of 1-5 wt% of the initiator material into a reaction kettle, controlling the temperature in the reaction kettle at 40-50 deg.c and the reaction pressure at 0.2-0.5 MPa, reacting for 2 hr, adding xylene solvent with required amount, heating to 90-95 deg.c and the reaction pressure at 0.2-0.5 MPa, reacting for 2-3 hr, and vacuum refluxing to eliminate water to obtain the initiator.

The third technical scheme of the invention is realized by the following measures: the raw material comprises, by weight, 40% to 60% of the polyether dry agent, 10% to 30% of methanol, and the balance water.

The third technical scheme of the invention is further optimized or/and improved as follows:

the crude oil demulsifier is obtained by the following method: mixing required amount of polyether dry agent, methanol and water, and stirring for 30-60 minutes at 40-50 ℃ to obtain the crude oil demulsifier.

The fourth technical scheme of the invention is realized by the following measures: the raw material comprises 40 to 60 weight percent of polyether dry agent, 10 to 30 weight percent of methanol and the balance of water according to the following method: mixing required amount of polyether dry agent, methanol and water, and stirring for 30-60 minutes at 40-50 ℃ to obtain the crude oil demulsifier.

The crude oil demulsifier prepared by the invention has the advantages of high dehydration speed and strong demulsification capability on complex emulsion when demulsifying emulsified crude oil, crude oil produced liquid and the like, and particularly has excellent demulsification effect on crude oil containing wax and fracturing fluid and part of aged crude oil in oil fields.

Drawings

FIG. 1 shows the reaction scheme of the initiator R.

Detailed Description

The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the invention are mass percentages unless otherwise specified; the solution in the present invention is an aqueous solution in which the solvent is water, for example, a hydrochloric acid solution is an aqueous hydrochloric acid solution, unless otherwise specified; the normal temperature and room temperature in the present invention generally mean a temperature of 15 ℃ to 25 ℃, and are generally defined as 25 ℃.

The invention is further described below with reference to the following examples:

example 1: the crude oil demulsifier is prepared by the following preparation method:

(1) preparation of the initiator: the starting materials of the starter comprise a molar ratio of 0.5 to 2: 2 to 6 of p-hydroxyacetophenone and formaldehyde, obtained by the following process: adding p-hydroxyacetophenone, formaldehyde and sodium hydroxide with required amount in the amount of 1-5 wt% of the initiator material into a reaction kettle, controlling the temperature in the reaction kettle at 40-50 deg.c and the reaction pressure at 0.2-0.5 MPa, reacting for 2 hr, adding xylene solvent with required amount, heating to 90-95 deg.c and the reaction pressure at 0.2-0.5 MPa, reacting for 2-3 hr, and vacuum refluxing to eliminate water to obtain the initiator.

(2) Preparation of polyether drying agent: the polyether drying agent comprises, by weight, 0.5-30 parts of an initiator, 0.5-2 parts of sodium hydroxide, 40-85 parts of propylene oxide and 10-30 parts of ethylene oxide, and is prepared by the following method: firstly, adding required amount of initiator and sodium hydroxide into a reaction kettle, stirring and heating to 125-130 ℃, evacuating the reaction kettle, filling nitrogen into the reaction kettle to form a nitrogen atmosphere in the reaction kettle, then adding required amount of propylene oxide, wherein the reaction pressure in the reaction kettle is 0.10-0.25 MPa, and the reaction temperature is 125-130 ℃; and then adding the required amount of ethylene oxide, wherein the reaction pressure is 0.10MPa to 0.25MPa, the reaction temperature is 115 ℃ to 125 ℃, continuing to perform curing reaction for 1 hour after the addition is finished, the reaction temperature is 115 ℃ to 125 ℃, and cooling and discharging to obtain the polyether drying agent after the pressure in the reaction kettle is reduced to normal pressure.

(3) Preparing a crude oil demulsifier: the raw materials comprise 40 to 60 weight percent of polyether dry agent, 10 to 30 weight percent of methanol and the balance of water; mixing required amount of polyether dry agent, methanol and water, and stirring for 30-60 minutes at 40-50 ℃ to obtain the crude oil demulsifier.

The reaction formula of the polyether drying agent is as follows:

wherein R is an initiator;

m is 0 to 500, n is 0 to 150;

PO isEO is

The reaction formula of the initiator R is shown in figure 1, and in figure 1, n is 0-50.

The crude oil demulsifier prepared according to the invention has the advantages of high dehydration speed and strong demulsification capability on complex emulsion when demulsifying emulsified crude oil, crude oil produced liquid and the like, and particularly has excellent demulsification effect on wax-containing, fracturing fluid-containing crude oil and part of aged oil in oil fields. The following specific application cases are described.

Example 2: the crude oil demulsifier is prepared by the following preparation method:

(1) preparation of the initiator: adding 108 kg of p-hydroxyacetophenone, 61 kg of formaldehyde and 6 kg of sodium hydroxide into a reaction kettle, controlling the temperature to be 40-42 ℃ and the reaction pressure to be 0.2MPa, adding a dimethylbenzene solvent after reacting for 2 hours, dissolving non-liquid substances in the reaction kettle into liquid, heating to 90 ℃, controlling the reaction pressure to be 0.3MPa, reacting for 3 hours, and carrying out vacuum reflux to remove water to obtain the initiator.

(2) Preparation of polyether drying agent: firstly, 100 kg of initiator and 8 kg of sodium hydroxide are added into a reaction kettle, stirring is started, heating is carried out to 130 ℃, evacuation and nitrogen filling are carried out, 525 kg of propylene oxide is slowly added, and the reaction pressure is controlled to be 0.22MPa and the reaction temperature is controlled to be 132 ℃. And slowly adding 288 kg of ethylene oxide, wherein the reaction pressure is 0.18MPa, the reaction temperature is 120 ℃ and 5 ℃, continuing to perform curing reaction for 1 hour after the addition is finished, the reaction temperature is 120 ℃ and 5 ℃, and cooling to normal temperature after the pressure in the reaction kettle returns to zero (namely normal pressure) to obtain the polyether drying agent.

(3) Preparing a crude oil demulsifier: 450 kg of polyether drying agent, 200 kg of methanol and 350 kg of water are added into a reaction kettle, the temperature is raised to 50 ℃, the mixture is stirred for 30 minutes, the temperature is reduced to normal temperature, and then the mixture is discharged.

Example 3: the crude oil demulsifier is prepared by the following preparation method:

(1) preparation of the initiator: 133 kg of p-hydroxyacetophenone, 84 kg of formaldehyde and 7 kg of sodium hydroxide are added into a reaction kettle, the temperature is controlled to be 40-43 ℃, the reaction pressure is controlled to be 0.3MPa, a certain amount of dimethylbenzene solvent is added after the reaction is carried out for 2 hours, non-liquid substances in the reaction kettle are dissolved into liquid, the temperature is raised to 93 ℃, the reaction pressure is controlled to be 0.4MPa, the reaction is carried out for 2 hours, and the initiator is obtained after the water is removed by vacuum reflux.

(2) Preparation of polyether drying agent: firstly, 100 kg of initiator and 10 kg of sodium hydroxide are added into a reaction kettle, stirring is started, heating is carried out to 132 ℃, evacuation and nitrogen filling are carried out, then 900 kg of propylene oxide is slowly dripped, and the reaction pressure is controlled at 0.22MPa and the reaction temperature is 130 ℃. And slowly dropwise adding 250 kg of ethylene oxide, wherein the reaction pressure is 0.22MPa, the reaction temperature is 120 ℃ or 5 ℃, continuously curing and reacting for 1 hour after dropwise adding is finished, the reaction temperature is 120 ℃ or 5 ℃, and cooling and discharging to obtain the polyether drying agent after the pressure in the reaction kettle is reduced to zero.

(3) Preparing a crude oil demulsifier: 450 kg of polyether drying agent, 200 kg of methanol and 350 kg of water are added into a reaction kettle, the temperature is raised to 44 ℃, the mixture is stirred for 45 minutes, the temperature is reduced to normal temperature, and the materials are discharged.

Application case 1: the crude oil of the oil field of the Clamayma lake belongs to crude oil with high wax content, and the produced fluid contains a large amount of fracturing fluid which is difficult to process; the crude oil demulsifier prepared in example 2 was evaluated with the produced liquid of crude oil from the kraimama lake.

In the crude oil produced liquid of the Claritama lake oil field, the content of inorganic and organic impurities is 10 to 15 percent, and the content of emulsified water is 11 to 25 percent.

Application case 2: aged crude oil of a sewage station in six-nine areas of a Clamayi oil field contains more water treatment agents, the crude oil is seriously emulsified, and the dehydration is difficult. The crude oil demulsifier prepared in example 2 was evaluated from aged crude oil in a sewage station in the six-nine areas of a kramayi oil field.

Crude oil density of aged crude oil of sewage station in six-nine areas of Clarity oil field is 0.9200g/cm³To 0.981g/cm³An acid value of 1.49mgKOH/g to 9.80mgKOH/g, a gum content of 16.33% to 34.7%; belongs to thick oil with high colloid content and high density. The ageing oil also contains a large amount of emulsified water, 2 to 3 percent of mud or slag, 0.5 percent of acid, alkali or salt, surfactant and the like.

In the evaluation test process, reference is made to GB/T8929-2006 crude oil water content measurement (distillation method) and SY/T5281-2018 demulsifier use performance detection method (bottle test method).

The demulsification and dehydration test data of aged crude oil in the sewage station in the six-nine areas of the Clamayi oil field are shown in a table 1, and the demulsification and dehydration test data of crude oil produced liquid in the Mahu oil field are shown in a table 2.

As can be seen from the dehydration rate data, the interface condition and the water color shown in tables 1 to 2, the crude oil demulsifier prepared in the embodiment 2 can effectively perform demulsification and dehydration on aged crude oil in sewage stations in the six-nine areas of a Claritian oil field and crude oil produced liquid in a Mahu oil field, and has high dehydration speed and high dehydration efficiency.

The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.

TABLE 1 Craya oilfield six-nine zone sewage station aged crude oil demulsification dehydration test

TABLE 2 demulsification dehydration test of crude oil produced liquid from Ma lake oil field