阅读说明：本技术 一种改性聚醚、复合原油破乳剂、及其制备方法和应用 (Modified polyether, composite crude oil demulsifier, and preparation method and application thereof ) 是由 饶志刚 倪志国 安进 谢刚儒 王凯建 邓磊 李鹏 于 2020-07-31 设计创作，主要内容包括：本发明是关于一种改性聚醚、复合原油破乳剂、及其制备方法和应用,该改性聚醚的制备方法包括以下步骤：将苯酚类与乙烯胺在50-70℃下常压密封预热30-50min；之后在一搅拌转速下,于N<Sub>2</Sub>或惰性气氛下30min-60min内升温至110-130℃,接着滴加甲醛水溶液,将压力升至0.2-0.6MPa,110-130℃恒温反应2-5小时；在保持之前的搅拌转速下,将第一中间产物中加入碱,在0.2-0.6MPa,110-130℃下,滴加环氧烷基化合物水溶液,恒温恒压搅拌反应5-7小时后,冷却至70-90℃；减压至常压,冷却至室温,中和提纯后,即得改性聚醚。本发明所提供的复合原油破乳剂,其使用的各原料来源广,成本低廉,并且不会给后续中的炼油设备造成腐蚀,从而可节约成本,提高设备的利用率。(The invention relates to a modified polyether, a composite crude oil demulsifier, a preparation method and application thereof, wherein the preparation method of the modified polyether comprises the following steps: sealing and preheating phenols and vinylamine at 50-70 ℃ for 30-50min under normal pressure; then at a stirring speed in N 2 Or raising the temperature to 110-130 ℃ within 30-60 min under inert atmosphere, then dropwise adding a formaldehyde water solution, raising the pressure to 0.2-0.6MPa, and reacting at the constant temperature of 110-130 ℃ for 2-5 hours; under the condition of keeping the stirring speed before the stirring, adding alkali into the first intermediate product, dropwise adding an epoxy alkyl compound aqueous solution at the temperature of 110-130 ℃ under the pressure of 0.2-0.6MPa, stirring at constant temperature and constant pressure for 5-7 hours, and then cooling to 70-90 ℃; reducing the pressure to normal pressure, cooling to room temperature, neutralizing and purifying to obtain the modified polyether. The composite crude oil demulsifier provided by the invention has the advantages of wide source of raw materials, low cost and no generation of oil refining equipment in the follow-up processCorrosion, so that the cost can be saved and the utilization rate of equipment can be improved.)

1. The preparation method of the modified polyether is characterized by comprising the following steps:

a, sealing and preheating a phenol compound and a vinylamine compound at 50-70 ℃ for 30-50min under normal pressure; then at a stirring speed in N₂Or raising the temperature to 110-130 ℃ within 30-60 min under inert atmosphere, then dropping formaldehyde aqueous solution, raising the pressure to 0.2-0.6MPa,reacting at 110-130 ℃ for 2-5 hours to obtain a first intermediate product;

b, under the condition of keeping the stirring speed before, adding alkali into the first intermediate product, dropwise adding an epoxy alkyl compound aqueous solution at the temperature of 110-130 ℃ under the pressure of 0.2-0.6MPa, stirring at constant temperature and constant pressure for reaction for 5-7 hours, and then cooling to 70-90 ℃ to obtain a second intermediate product;

c, decompressing the second intermediate product to normal pressure, cooling to room temperature, neutralizing and purifying to obtain modified polyether;

the cloud point of the modified polyether is 30-35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm^-1And 1300 + 990cm^-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300-^-1Has an O-H telescopic absorption peak between the two and is 1720-1700cm^-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320-^-1And C-O stretching vibration peaks are arranged between the two.

2. The method for preparing modified polyether according to claim 1, wherein in step a, the mass ratio of the phenol compound to the vinylamine compound is (0.8-6): 1.

3. the method of claim 2, wherein in step a, the phenol compound is phenol, o-cresol, m-cresol or p-cresol; the vinylamine compound is diethylenetriamine, diethylenediamine, triethylenediamine or triethylenetetramine.

4. The method for preparing modified polyether according to claim 1, wherein in the step a, the mass ratio of the formaldehyde solution to vinylamine is (0.1-0.6): 1; the concentration of the formaldehyde aqueous solution is 30-35 wt%; the dropping rate of the formaldehyde solution is 30-35 drops/min.

5. The method of claim 1, wherein in step b, the base is sodium hydroxide or potassium hydroxide; the mass ratio of the alkali to the vinylamine compound is (0.5-4): 40.

6. the process for producing a modified polyether according to claim 1, wherein in the step b, the alkylene oxide compound is at least one selected from the group consisting of ethylene oxide and propylene oxide; the mass ratio of the epoxy alkyl compound solution to the vinylamine compound is (0.4-2.5): 1; the concentration of the ethylene oxide solution and the concentration of the propylene oxide solution are both 99 wt%; the dropping rate of the ethylene oxide solution and the dropping rate of the propylene oxide solution are both 20-25 drops/min; in the step a and the step b, the rotation speed of the stirring is 150-250 rpm/min.

7. The method of claim 1, further comprising step b1, after step b and before step c: adding at least one of grafting agent and catalyst, and reacting at 80-85 deg.C for 1-2 hr.

8. The method of claim 7, wherein in step b1, the grafting agent is selected from one of acetic anhydride, maleic anhydride, acetic acid, formic acid, concentrated sulfuric acid, and dilauric acid; the mass ratio of the grafting agent to the vinylamine compound is (0.35-1.6): 1; the catalyst is selected from one of p-toluenesulfonic acid, sodium benzene sulfonate, sodium dodecyl sulfate, dibutyltin dilaurate, dicumyl oxide and di-tert-butyl peroxide; the mass ratio of the catalyst to the vinylamine compound is (1-4): 30.

9. the method of claim 7, further comprising, after step b1 and before step c, step b 2: adding cross-linking agent, and heating at 80-85 deg.C for 5-6 hr.

10. The method of claim 9, wherein in step b2, the crosslinking agent is at least one selected from the group consisting of acrylic acid, dibenzoyl peroxide, diisopropylbenzene hydroperoxide, and 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane; the mass ratio of the cross-linking agent to the vinylamine compound is (0.5-0.8): 1.

11. a modified polyether prepared by the process of any one of claims 1-10, wherein the modified polyether has a cloud point of 30 to 35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm^-1And 1300 + 990cm^-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300-^-1An O-H telescopic absorption peak is arranged between the two groups; and at 1720-^-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320-^-1And C-O stretching vibration peaks are arranged between the two.

12. The composite crude oil demulsifier is characterized by comprising the following components in percentage by mass (0.5-2): 1: (1-4): (2-4) the modified polyether, the solvent oil, the surfactant and the alcohol-water solution; the cloud point of the modified polyether is 30-35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm^-1And 1300 + 990cm^-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300-^-1Has an O-H telescopic absorption peak between the two and is 1720-1700cm^-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320-^-1And C-O stretching vibration peaks are arranged between the two.

13. The complex crude oil demulsifier of claim 12, wherein the aqueous alcohol solution is selected from aqueous methanol or aqueous ethanol having a concentration of 95 to 99 wt%; the solvent oil is selected from one of 1000# solvent oil, 1800# solvent oil, 1500# solvent oil, 100# solvent oil and 200# solvent oil; the surfactant is selected from fatty alcohol-polyoxyethylene ether, a penetrating agent JFY, a penetrating agent JFC and a spandex 80/Tween 80/polyether surfactant with the mass ratio of 1:1: 1.

14. The composite crude oil demulsifier of claim 13, wherein the composite crude oil demulsifier is a brown yellow transparent oil-soluble liquid having a density of 0.85 to 0.9g/ml, a viscosity of 30 to 55mpa.s, and a flash point of 61 to 65 ℃.

15. The preparation method of the composite crude oil demulsifier is characterized by comprising the following steps:

heating the modified polyether to 40-60 ℃ at the normal-pressure stirring speed of 100 plus 200rpm/min, sequentially adding the surfactant and the alcohol aqueous solution for 30-60 min, adding the solvent oil, and cooling to room temperature after 30-60 min to obtain the composite crude oil demulsifier; the mass ratio of the modified polyether to the solvent oil to the surfactant to the alcohol-water solution is (2-10): 1: (1-2): (3-10); the cloud point of the modified polyether is 30-35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm^-1And 1300 + 990cm^-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300-^-1Has an O-H telescopic absorption peak between the two and is 1720-1700cm^-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320-^-1And C-O stretching vibration peaks are arranged between the two.

16. A demulsification dehydration method of water-in-oil emulsified oil is characterized by comprising the following steps:

the complex crude oil demulsifier of any one of claims 12 to 14 is diluted with a methanol aqueous solution with a concentration of 95 to 99 wt%, and then added to the water-in-oil emulsified oil liquid, mixed uniformly, and demulsified and dehydrated.

17. The method for demulsifying and dehydrating of claim 16 wherein the dilution ratio is 1 (8-10); the demulsification temperature is 30-80 ℃.

Technical Field

The invention belongs to the field of oilfield chemical additives, and particularly relates to a modified polyether, a composite crude oil demulsifier, and a preparation method and application thereof.

Background

Crude oil is a very complex multi-component mixture composed primarily of hydrocarbons of different molecular weights, structures and properties, as well as non-hydrocarbon compounds and impurities. At present, oil field exploitation enters a high water-cut period, and various enhanced oil recovery technical measures are applied, so that the water content of a crude oil emulsion is increased greatly, and the difficulty of crude oil dehydration is increased. Because the crude oil and the water are strongly mixed to form the emulsified crude oil with different stabilities, the dehydration difficulty of the crude oil is increased, and the prior demulsifier can not be adapted to the requirements of demulsification and dehydration treatment of the crude oil with high water content or thick oil and crude oil with high wax content; the main reasons are as follows: the dehydration temperature of the crude oil is reduced, wax in the crude oil is separated out, the viscosity of the emulsified crude oil is increased, the emulsified crude oil is usually in a water-in-oil state, and demulsifier molecules are difficult to disperse in the crude oil and cannot rapidly act on an oil-water interface film.

At present, the demulsifier used in Ilac Luke oil West Guerna second-stage oil field has poor adaptability, raised well head back pressure, unstable and reduced daily liquid yield, slow crude oil dehydration rate and higher heat energy consumption.

Disclosure of Invention

In view of the above, the main object of the present invention is to provide a modified polyether, a composite crude oil demulsifier, a preparation method and an application thereof, wherein the composite crude oil demulsifier has the advantages of strong demulsification capability, good permeability, good solubility in crude oil, high dehydration speed, etc.

The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The preparation method of the modified polyether provided by the invention comprises the following steps:

a, sealing and preheating a phenol compound and a vinylamine compound at 50-70 ℃ for 30-50min under normal pressure; then heating to 110-130 ℃ in N2 or inert atmosphere within 30-60 min under a stirring rotation speed, then dropwise adding a formaldehyde water solution, raising the pressure to 0.2-0.6MPa, and reacting at the constant temperature of 110-130 ℃ for 2-5 hours to obtain a first intermediate product;

b, under the condition of keeping the stirring speed before, adding alkali into the first intermediate product, dropwise adding an epoxy alkyl compound aqueous solution at the temperature of 110-130 ℃ under the pressure of 0.2-0.6MPa, stirring at constant temperature and constant pressure for reaction for 5-7 hours, and then cooling to 70-90 ℃ to obtain a second intermediate product;

c, decompressing the second intermediate product to normal pressure, cooling to room temperature, neutralizing and purifying to obtain modified polyether;

the cloud point of the modified polyether is 30-35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm^-1And 1300 + 990cm^-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300-^-1Has an O-H telescopic absorption peak between the two and is 1720-1700cm^-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320-^-1And C-O stretching vibration peaks are arranged between the two.

The purpose of the invention and the technical problem to be solved are further realized by adopting the following technical scheme.

Preferably, in the preparation method of the modified polyether, in the step a, the mass ratio of the phenol compound to the vinylamine compound is (0.8-6): 1.

preferably, in the preparation method of the modified polyether, in step a, the phenol compound is phenol, o-cresol, m-cresol or p-cresol.

Preferably, in the preparation method of the modified polyether, in step a, the vinylamine compound is diethylenetriamine, diethylenediamine, triethylenediamine or triethylenetetramine.

Preferably, in the preparation method of the modified polyether, in the step a, the mass ratio of the formaldehyde solution to the vinylamine compound is (0.1-0.6): 1; the concentration of the formaldehyde aqueous solution is 30-35 wt%; the dropping rate of the formaldehyde solution is 30-35 drops/min.

Preferably, in the preparation method of the modified polyether, in the step b, the alkali is sodium hydroxide solution or potassium hydroxide solution; the mass ratio of the alkali to the vinylamine compound is (0.5-4): 40.

preferably, in the preparation method of the modified polyether, in the step b, the alkylene oxide compound is at least one selected from ethylene oxide and propylene oxide; the mass ratio of the epoxy alkyl compound solution to the vinylamine compound is (0.4-2.5): 1; the concentration of the ethylene oxide solution and the concentration of the propylene oxide solution are both 99 wt%; the dropping speed of the ethylene oxide solution and the dropping speed of the propylene oxide solution are both 20-25 drops/min.

Preferably, in the preparation method of the modified polyether, in the step a and the step b, the rotation speed of the stirring is 150-250 rpm/min.

Preferably, the preparation method of the modified polyether further comprises step b1 after step b and before step c: adding at least one of grafting agent and catalyst, and reacting at 80-85 deg.C for 1-2 hr.

Preferably, in the preparation method of the modified polyether, in step b1, the grafting agent is selected from one of acetic anhydride, maleic anhydride, acetic acid, formic acid, concentrated sulfuric acid and dilauric acid; the mass ratio of the grafting agent to the vinylamine compound is (0.35-1.6): 1.

preferably, in the step b1, the catalyst is selected from one of p-toluenesulfonic acid, sodium benzenesulfonate, sodium dodecylsulfate, dibutyltin dilaurate, dicumyl oxide (DCP), and di-tert-butyl peroxide (DTBP); the mass ratio of the catalyst to the vinylamine compound is (1-4): 30.

preferably, the preparation method of the modified polyether further comprises a step b2 after the step b1 and before the step c: adding cross-linking agent, and heating at 80-85 deg.C for 5-6 hr.

Preferably, in the step b2, the crosslinking agent is at least one selected from the group consisting of acrylic acid, dibenzoyl peroxide, diisopropylbenzene hydroperoxide and 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane; the mass ratio of the cross-linking agent to the vinylamine compound is (0.5-0.8): 1.

the purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. According to the modified polyether provided by the invention, the cloud point of the modified polyether is 30-35 ℃; the infrared spectrum of the modified polyether is 1265-1220cm^-1And 1300 + 990cm^-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300-^-1Has an O-H telescopic absorption peak between the two and is 1720-1700cm^-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320-^-1C-O stretching vibration peaks are arranged between the two groups; the modified polyether is prepared by the method.

The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. The invention provides a composite crude oil demulsifier, which is prepared from the following components in percentage by mass (0.5-2): 1: (1-4): (2-4) the modified polyether, the solvent oil, the surfactant and the alcohol-water solution; the cloud point of the modified polyether is 30-35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm^-1And 1300 + 990cm^-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300-^-1Has an O-H telescopic absorption peak between the two and is 1720-1700cm^-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320-^-1And C-O stretching vibration peaks are arranged between the two.

The purpose of the invention and the technical problem to be solved are further realized by adopting the following technical scheme.

Preferably, the method for preparing the complex crude oil demulsifier comprises the step of preparing the complex crude oil demulsifier, wherein the alcohol aqueous solution is selected from methanol aqueous solution or ethanol aqueous solution, and the concentration of the alcohol aqueous solution is 95-99 wt%.

Preferably, the preparation method of the complex crude oil demulsifier is described above, wherein the mineral spirit is selected from one of 1000# mineral spirit, 1800# mineral spirit, 1500# mineral spirit, 100# mineral spirit and 200# mineral spirit.

Preferably, in the preparation method of the composite crude oil demulsifier, the surfactant is selected from fatty alcohol-polyoxyethylene ether, a penetrant JFY, a penetrant JFC, and one of span 80/tween 80/polyether surfactant in a mass ratio of 1:1: 1.

Preferably, in the preparation method of the composite crude oil demulsifier, the composite crude oil demulsifier is a brown yellow transparent oil-soluble liquid, the density is 0.85-0.9g/ml, the viscosity is 30-55mpa.s, and the flash point is 61-65 ℃.

The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. The invention provides a preparation method of a composite crude oil demulsifier, which comprises the following steps:

heating the modified polyether to 40-60 ℃ at the normal-pressure stirring speed of 100 plus 200rpm/min, sequentially adding the surfactant and the alcohol aqueous solution for 30-60 min, adding the solvent oil, and cooling to room temperature after 30-60 min to obtain the composite crude oil demulsifier; the cloud point of the modified polyether is 30-35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm^-1And 1300 + 990cm^-12C-O telescopic vibration absorption peaks are respectively arranged between the two adjacent vibration absorption peaks, and the peak length is 3300-^-1Has an O-H telescopic absorption peak between the two and is 1720-1700cm^-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320-^-1And C-O stretching vibration peaks are arranged between the two.

The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. The invention provides a demulsification and dehydration method of water-in-oil emulsified oil, which comprises the following steps:

diluting the composite crude oil demulsifier with methanol aqueous solution, adding the demulsifier into the water-in-oil emulsified oil, uniformly mixing, and performing demulsification and dehydration.

Preferably, the method for demulsifying and dehydrating the water-in-oil emulsified oil liquid comprises the steps of preparing the methanol aqueous solution with the concentration of 95-99 wt%; the dilution ratio is 1 (8-10); the demulsification temperature is 30-80 ℃.

Compared with the prior art, the modified polyether, the composite crude oil demulsifier, the preparation method and the application thereof have the following advantages:

1. the composite crude oil demulsifier has the advantages of wide source of raw materials, low cost and no corrosion to subsequent oil refining equipment, thereby saving the cost and improving the utilization rate of the equipment.

2. The composite crude oil demulsifier provided by the invention is used for producing and extracting oil in Ilack Lukexigulna second-stage oil fields, has good surface property and permeability, can be quickly dissolved in Ilack Lukexigulna second-stage oil field crude oil, reduces the heat energy consumption and the electric power cost of local first-stage and second-stage oil extraction plants and gathering and transportation stations, has the advantages of high dehydration rate and high dehydration degree, and can be suitable for special environments such as acidification operation.

3. The composite crude oil demulsifier provided by the invention can obviously reduce the load of the pumping unit and stabilize the daily liquid production amount when being added into a single well of an oil field in the secondary stage of Ilake Lux Welchurona.

4. The preparation method of the composite crude oil demulsifier can realize automatic continuous production, has high mechanization degree, and is suitable for popularization and industrial production.

The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.

Detailed Description

To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to the specific embodiments, features and properties of the modified polyether, the composite crude oil demulsifier, and the preparation method thereof according to the present invention with reference to the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

The following materials or reagents are commercially available unless otherwise specified.

The invention provides a preparation method of modified polyether, which comprises the following steps:

a, sealing and preheating a phenol compound and a vinylamine compound at 50-70 ℃ for 30-50min under normal pressure; then stirring at a stirring speed of 150-250rpm/min under N₂Or raising the temperature to 110-130 ℃ within 30-60 min under inert atmosphere, then dropwise adding a formaldehyde water solution, raising the pressure to 0.2-0.6MPa, and reacting at the constant temperature of 110-130 ℃ for 2-5 hours to obtain a first intermediate product;

b, adding alkali into the first intermediate product, dropwise adding an epoxy alkyl compound aqueous solution at the temperature of 110-130 ℃ under the pressure of 0.2-0.6MPa, reacting for 5-7 hours at constant temperature and constant pressure, and cooling to 70-90 ℃ to obtain a second intermediate product;

c, decompressing the second intermediate product to normal pressure, cooling to room temperature, neutralizing and purifying to obtain modified polyether;

the cloud point of the modified polyether is 30-35 degrees; the infrared spectrum of the modified polyether is 1265-1220cm^-1And 1300 + 990cm^-12C-O stretching vibration absorption peaks are respectively arranged between the modified polyether and the polyether, which indicates that the aromatic ether exists in the modified polyether; at 3300 and 2800cm^-1An O-H telescopic absorption peak is formed between the modified polyether and the polyether, which indicates that hydroxyl exists in the modified polyether; at 3300 and 2800cm^-1Has a wide and strong O-H telescopic absorption peak between the two and is 1720-1700cm^-1C-O absorption vibration peak is arranged between the two, and the absorption vibration peak is 1200cm at 1320-^-1The stretching vibration peak of C-O is formed between the two, which indicates that the modified polyether has carboxyl.