阅读说明：本技术 高含蜡原油脱水用破乳剂及其制备方法 (Demulsifier for dehydrating high-wax-content crude oil and preparation method thereof ) 是由 朱晓明 邵宇 李祥林 李建平 高继红 李娜 张坤 杨豫新 于 2021-06-23 设计创作，主要内容包括：本发明涉及原油乳状液破乳技术领域,是一种高含蜡原油脱水用破乳剂及其制备方法,原料按照重量百分比计,包括对羟基苯乙酮氨甲基树脂嵌段聚醚、SP-169、AR树脂嵌段聚醚、过硫酸铵和溶剂,按照下述步骤得到：第一步,向反应器中加入所需量的对羟基苯乙酮氨甲基树脂嵌段聚醚、SP-169、AR树脂嵌段聚醚,得到第一混合物；第二步,将第一混合物加热至40℃至60℃,依次向反应器中加入所需量的溶剂和过硫酸铵,得到第二混合物；第三步,第二混合物在40℃至60℃下保温搅拌反应,得到高含蜡原油脱水用破乳剂。本发明得到的高含蜡原油脱水用破乳剂具有破乳速度快,对高含蜡原油具有很好的低温脱水功能,且能很好地解决压裂液返排液对原油脱水的负面影响。(The invention relates to the technical field of crude oil emulsion demulsification, in particular to a demulsifier for dehydrating high-wax-content crude oil and a preparation method thereof, wherein the demulsifier comprises p-hydroxyacetophenone aminomethyl resin block polyether, SP-169, AR resin block polyether, ammonium persulfate and a solvent in percentage by weight, and is obtained according to the following steps: firstly, adding the required amount of p-hydroxyacetophenone aminomethyl resin block polyether, SP-169 and AR resin block polyether into a reactor to obtain a first mixture; secondly, heating the first mixture to 40-60 ℃, and sequentially adding required amount of solvent and ammonium persulfate into the reactor to obtain a second mixture; and step three, keeping the temperature of the second mixture at 40-60 ℃, stirring and reacting to obtain the demulsifier for dehydrating the high-wax-content crude oil. The demulsifier for dehydrating the high-wax-content crude oil, which is obtained by the invention, has high demulsification speed, has good low-temperature dehydration function on the high-wax-content crude oil, and can well solve the negative influence of the fracturing fluid flowback liquid on the dehydration of the crude oil.)

1. The demulsifier for dehydrating the high-wax-content crude oil is characterized by comprising 10 to 50 percent of p-hydroxyacetophenone aminomethyl resin block polyether, 5 to 20 percent of SP-1695, 0 to 10 percent of ammonium persulfate and 40 to 60 percent of solvent according to weight percentage, and is obtained according to the following steps: firstly, adding the required amount of p-hydroxyacetophenone aminomethyl resin block polyether, SP-169 and AR resin block polyether into a reactor to obtain a first mixture; secondly, heating the first mixture to 40-60 ℃, and sequentially adding required amount of solvent and ammonium persulfate into the reactor to obtain a second mixture; and thirdly, keeping the temperature of the second mixture at 40-60 ℃, stirring and reacting until the second mixture completely reacts, dissolving to form uniform liquid, and obtaining the demulsifier for dehydrating the high-wax-content crude oil.

2. The demulsifier for dehydrating highly waxy crude oil according to claim 1, wherein the solvent is a mixture of methanol and water, wherein the ratio of methanol to water is 1: 1 to 2.

3. The demulsifier for dehydrating highly waxy crude oil according to claim 1 or 2, wherein SP-169 is a polymer of stearyl alcohol, ethylene oxide and propylene oxide.

4. The demulsifier for dehydrating highly waxy crude oil according to claim 1, 2 or 3, wherein the AR resin block polyether is a polymer of an alkyl phenol-formaldehyde resin with ethylene oxide and propylene oxide.

5. The demulsifier for dehydrating highly waxy crude oil according to claim 1, 2, 3 or 4, wherein in the first step, the rotation speed of the reactor is from 100rpm to 200 rpm.

6. The demulsifier for dehydrating highly waxy crude oils according to claim 1, 2, 3, 4 or 5, wherein in the third step, the rotation speed of the stirring is from 100rpm to 200 rpm.

7. The demulsifier for dehydrating highly waxy crude oil according to claim 1, 2, 3, 4, 5 or 6, wherein the reaction time in the third step is from 40min to 60 min.

8. The preparation method of the demulsifier for dehydrating the high-wax crude oil according to any one of claims 2 to 7, which is characterized by comprising the following steps: firstly, adding the required amount of p-hydroxyacetophenone aminomethyl resin block polyether, SP-169 and AR resin block polyether into a reactor to obtain a first mixture; secondly, heating the first mixture to 40-60 ℃, and sequentially adding required amount of solvent and ammonium persulfate into the reactor to obtain a second mixture; and thirdly, keeping the temperature of the second mixture at 40-60 ℃, stirring and reacting until the second mixture completely reacts, dissolving to form uniform liquid, and obtaining the demulsifier for dehydrating the high-wax-content crude oil.

9. The method for preparing the demulsifier for dehydrating the highly waxy crude oil according to claim 8, wherein the solvent is a mixture of methanol and water, wherein the ratio of methanol to water is 1: 1 to 2; or/and SP-169 is a polymer of octadecanol, ethylene oxide and propylene oxide; or/and the AR resin block polyether is a polymer of alkyl phenolic resin, ethylene oxide and propylene oxide.

10. The method for preparing the demulsifier for dehydrating high-wax crude oil according to claim 8 or 9, wherein in the first step, the rotating speed of the reactor is 100rpm to 200 rpm; or/and in the third step, the rotating speed of stirring is 100rpm to 200 rpm; or/and, in the third step, the reaction time is 40min to 60 min.

Technical Field

The invention relates to the technical field of crude oil emulsion demulsification, in particular to a demulsifier for dehydrating crude oil with high wax content and a preparation method thereof.

Background

More than 80% of crude oil produced in China is wax-containing crude oil, and the problems of offshore oil development, low-temperature transportation, multiphase mixed transportation and the like are continuously developed, so that the problem of demulsification and dehydration of the wax-containing crude oil is more prominent. The wax-containing crude oil is characterized by high wax content, high condensation point, large viscosity and poor low-temperature fluidity. The wax component in crude oil is a natural emulsifier, and plays an important role in the stability of crude oil emulsion. The viscosity of the crude oil can be increased, fine wax crystals are easy to form a three-dimensional network structure to gather between water drops or be adsorbed on an oil-water interface to form a mechanical barrier, the sedimentation and collision rates of the water drops are reduced, and the coalescence is hindered, so that the stability of the emulsion is greatly enhanced, and the demulsification difficulty of the crude oil is increased. As the development of domestic oil fields enters the middle and later stages, the content of the produced crude oil water increases sharply, and various oil production processes and yield increasing measures are applied successively to improve the recovery ratio of crude oil in order to stabilize the production of crude oil; compared with the conventional oil extraction measures, the produced fluid property of the oil field chemical demulsification device is greatly changed, the produced fluid is seriously emulsified, the emulsification stability is enhanced, and the dosage of the demulsifier in the oil field chemical demulsification technical application is increased. At present, the conventional demulsifier is not ideal for dehydrating the produced liquid, such as high dehydration temperature, reduced dehydration rate, high oil content of dehydrated water, thickened emulsion layer and the like.

Disclosure of Invention

The invention provides a demulsifier for dehydrating high-wax-content crude oil and a preparation method thereof, overcomes the defects of the prior art, provides a demulsifier with high demulsification speed for dehydrating high-wax-content crude oil, solves the problems of high demulsification difficulty and non-ideal dehydration effect of high-wax-content crude oil, and has a good low-temperature dehydration function on the high-wax-content crude oil.

One of the technical schemes of the invention is realized by the following measures: the demulsifier for dehydrating the crude oil with high wax content comprises, by weight, 10% to 50% of p-hydroxyacetophenone aminomethyl resin block polyether, 5% to 20% of SP-1695% to 20% of AR resin block polyether, 0% to 10% of ammonium persulfate and 40% to 60% of a solvent, and is obtained according to the following steps: firstly, adding the required amount of p-hydroxyacetophenone aminomethyl resin block polyether, SP-169 and AR resin block polyether into a reactor to obtain a first mixture; secondly, heating the first mixture to 40-60 ℃, and sequentially adding required amount of solvent and ammonium persulfate into the reactor to obtain a second mixture; and thirdly, keeping the temperature of the second mixture at 40-60 ℃, stirring and reacting until the second mixture completely reacts, dissolving to form uniform liquid, and obtaining the demulsifier for dehydrating the high-wax-content crude oil.

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

the solvent is a mixture of methanol and water, wherein the ratio of methanol to water is 1: 1 to 2.

The SP-169 is a polymer of stearyl alcohol, ethylene oxide and propylene oxide.

The AR resin block polyether is a polymer of alkyl phenolic resin, ethylene oxide and propylene oxide.

In the first step, the rotation speed of the reactor is 100rpm to 200 rpm.

In the third step, the rotation speed of the stirring is 100rpm to 200 rpm.

In the third step, the reaction time is 40min to 60 min.

The second technical scheme of the invention is realized by the following measures: a preparation method of a demulsifier for dehydrating high-wax-content crude oil is carried out according to the following steps: firstly, adding the required amount of p-hydroxyacetophenone aminomethyl resin block polyether, SP-169 and AR resin block polyether into a reactor to obtain a first mixture; secondly, heating the first mixture to 40-60 ℃, and sequentially adding required amount of solvent and ammonium persulfate into the reactor to obtain a second mixture; and thirdly, keeping the temperature of the second mixture at 40-60 ℃, stirring and reacting until the second mixture completely reacts, dissolving to form uniform liquid, and obtaining the demulsifier for dehydrating the high-wax-content crude oil.

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

the solvent is a mixture of methanol and water, wherein the ratio of methanol to water is 1: 1 to 2; or/and SP-169 is a polymer of octadecanol, ethylene oxide and propylene oxide; or/and the AR resin block polyether is a polymer of alkyl phenolic resin, ethylene oxide and propylene oxide.

In the first step, the rotating speed of the reactor is 100rpm to 200 rpm; or/and in the third step, the rotating speed of stirring is 100rpm to 200 rpm; or/and, in the third step, the reaction time is 40min to 60 min.

The demulsifier for dehydrating the high-wax-content crude oil, which is obtained by the invention, has high demulsification speed, has good low-temperature dehydration function on the high-wax-content crude oil, and can well solve the negative influence of the fracturing fluid flowback liquid on the dehydration of the crude oil.

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 present invention are all mass percentages unless otherwise specified.

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

example 1: the demulsifier for dehydrating the high-wax-content crude oil comprises, by weight, 10-50% of p-hydroxyacetophenone aminomethyl resin block polyether, 5-20% of SP-1695-20% of AR resin block polyether, 0-10% of ammonium persulfate and 40-60% of a solvent, and is obtained according to the following steps: firstly, adding the required amount of p-hydroxyacetophenone aminomethyl resin block polyether, SP-169 and AR resin block polyether into a reactor to obtain a first mixture; secondly, heating the first mixture to 40-60 ℃, and sequentially adding required amount of solvent and ammonium persulfate into the reactor to obtain a second mixture; and thirdly, keeping the temperature of the second mixture at 40-60 ℃, stirring and reacting until the second mixture completely reacts, dissolving to form uniform liquid, and obtaining the demulsifier for dehydrating the high-wax-content crude oil.

Example 2: the demulsifier for dehydrating the high-wax-content crude oil comprises, by weight, 10% or 50% of p-hydroxyacetophenone aminomethyl resin block polyether, 5% or 20% of SP-1695% or 20% of AR resin block polyether, 0% or 10% of ammonium persulfate or 40% or 60% of solvent, and is obtained according to the following steps: firstly, adding the required amount of p-hydroxyacetophenone aminomethyl resin block polyether, SP-169 and AR resin block polyether into a reactor to obtain a first mixture; secondly, heating the first mixture to 40 ℃ or 60 ℃, and sequentially adding required amount of solvent and ammonium persulfate into the reactor to obtain a second mixture; and thirdly, keeping the temperature of the second mixture at 40 ℃ or 60 ℃, stirring and reacting until the second mixture completely reacts, dissolving to form uniform liquid, and obtaining the demulsifier for dehydrating the high-wax-content crude oil.

Example 3: as an optimization of the above example, the solvent is a mixture of methanol and water, wherein the ratio of methanol to water is 1: 1 to 2.

Example 4: as optimization of the above embodiment, SP-169 is a polymer of stearyl alcohol, ethylene oxide and propylene oxide.

Example 5: as an optimization of the above embodiment, the AR resin block polyether is a polymer of an alkyl phenol resin with ethylene oxide and propylene oxide.

Example 6: as an optimization of the above example, in the first step, the rotation speed of the reactor is 100rpm to 200 rpm.

Example 7: as an optimization of the above embodiment, in the third step, the rotation speed of the stirring is 100rpm to 200 rpm.

Example 8: as an optimization of the above example, in the third step, the reaction time is 40min to 60 min.

The synthetic method of p-hydroxyacetophenone aminomethyl resin block polyether is disclosed in Chinese invention patent ZL201510714648.X, which is produced by Clarityne New science Australian oil and gas technology GmbH, and can be replaced by other similar products; the AR resin polyether is produced by Clarithromi New science Australian oil and gas technology GmbH, and can be replaced by other similar products; SP-169 and ammonium persulfate were all commercially available products.

In the present invention, the ammonium persulfate may be replaced with an oxidizing agent such as potassium persulfate.

Example 9: the demulsifier for dehydrating the high-wax-content crude oil is carried out according to the following method: firstly, adding 35% of p-hydroxyacetophenone aminomethyl resin block polyether, 5% of SP-169 and 10% of AR resin block polyether into a reactor to obtain a first mixture; secondly, heating the first mixture to 40 ℃, and sequentially adding 45% of solvent and 5% of ammonium persulfate into the reactor to obtain a second mixture; and thirdly, keeping the temperature of the second mixture at 40 ℃, stirring and reacting for 40min until the second mixture completely reacts, and dissolving to form uniform liquid to obtain the demulsifier for dehydrating the high-wax-content crude oil.

Example 10: the demulsifier for dehydrating the high-wax-content crude oil is carried out according to the following method: firstly, adding 30% of p-hydroxyacetophenone aminomethyl resin block polyether, 5% of SP-169 and 10% of AR resin block polyether into a reactor to obtain a first mixture; step two, heating the first mixture to 60 ℃, and sequentially adding 45% of solvent and 10% of ammonium persulfate into the reactor to obtain a second mixture; and thirdly, keeping the temperature of the second mixture at 60 ℃, stirring and reacting for 40min until the second mixture completely reacts, and dissolving to form uniform liquid to obtain the demulsifier 1 for dehydrating the high-wax-content crude oil.

The dehydration rate comparison test was performed using a conventional demulsifier (a KXDF demulsifier being used in an oil field) and the demulsifier for dehydrating highly waxy crude oil and the demulsifier 1 for dehydrating highly waxy crude oil prepared in examples 9 and 10 of the present invention. The test object is crude oil in a Clarity oil field Anma lake oil field, the crude oil adopts a large-area horizontal well fracturing oil extraction mode in the oil field development process, so that the crude oil contains a large amount of flowback liquid of fracturing liquid, and the average wax content of the crude oil is 14%. The content of water in the crude oil of the Clarity oil field and the Cycloma lake oil field is 37 percent by weight, the concentration of a demulsifier in the crude oil is 80ppm, and the dehydration temperature is 40 ℃ to 50 ℃.

According to the standard SY/T5281-2000 crude oil demulsifier use performance detection method (bottle test method) in the oil and gas industry of the people's republic of China, a bottle test demulsification dehydration test is carried out on the Claritide thick oil at different temperatures, and an artificial oscillation method is adopted as an oscillation method of a dehydration test bottle in the test. The results of the dehydration test at 40 ℃ with the crude oil from the ramayy oil field rama lake oil field are shown in table 1.

As can be seen from table 1, the blank sample without demulsifier had a dehydration rate of 0 in 2 hours and a dehydration rate of 88.3% in 2 hours for the KXDF demulsifier, whereas the demulsifiers for dehydrating highly waxy crude oils prepared in examples 9 and 10 and the demulsifier for dehydrating highly waxy crude oils 1 had dehydration rates of 98.5% and 99% in 2 hours, respectively, and the dehydration effect was very significant.

In conclusion, the demulsifier for dehydrating the crude oil with high wax content, which is obtained by the invention, has high demulsification speed, has good low-temperature dehydration function on the crude oil with high wax content, and can well solve the negative influence of the fracturing fluid flowback liquid on the dehydration of the crude oil.

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.