A bio-based temperature-resistant and salt-resistant microemulsion thickened oil viscosity reducer and a preparation method thereof

Abstract

The application belongs to the technical field of oil exploitation, and particularly relates to a bio-based temperature-resistant and salt-resistant microemulsion thickened oil viscosity reducer and a preparation method thereof. The preparation method is as follows: under the conditions of heating and stirring, an electrolyte is dissolved in water, then rapeseed polyphenol polyoxyethylene ether sodium carboxylate is added, and a solution is prepared; solvent oil is added into the above solution, and alcohol additive is added dropwise under the condition of stirring until the solution is transparent, so that the bio-based temperature-resistant and salt-resistant microemulsion thickened oil viscosity reducer is prepared. The microemulsion thickened oil viscosity reducer has the advantages of simple single-agent synthesis process, simple microemulsion preparation process, small dosage, good viscosity reduction effect and low cost.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of oil exploitation, and particularly relates to a bio-based temperature-resistant and salt-resistant microemulsion thickened oil viscosity reducer and a preparation method thereof. BACKGROUND

[0002] As a strategic mineral resource, oil is related to the economic lifeline and energy security of a country. In recent years, China's dependence on foreign crude oil remains high, and energy security and the stable development of the economy and society are facing major threats. However, most domestic oilfields, especially the old oilfields in the east, are generally characterized by high water flooding recovery and high comprehensive water cut, and it is difficult to further tap the potential. High-temperature and high-salt heavy oil reservoirs are faced with low recovery, high water cut and low water flooding efficiency, and have a large potential for tapping. At present, the oil displacement agent used for the development of conventional oil reservoirs is affected by high temperature and high salinity, and the oil displacement efficiency is low, which cannot meet the development needs of such reservoirs. Therefore, the development of temperature-resistant and salt-resistant thickened oil viscosity reducers is of great significance for improving the recovery of high-temperature and high-salt reservoirs.

[0003] Bio-based surfactants are a kind of natural surfactants, including rapeseed polyphenol, lignin, cardanol and tannic acid, and have the advantages of abundant source, economic and renewable, good biological friendliness and the like. Among them, rapeseed polyphenol has the characteristics of wide source and strong molecular structure plasticity, and will become an important raw material for preparing oilfield chemicals. Due to the poor water solubility of rapeseed polyphenol, molecular modification is usually carried out to improve its water solubility and interfacial activity. In addition, the water-soluble surfactant alone has poor viscosity reduction effect on thickened oil, and needs to be prepared into a microemulsion viscosity reducer to improve its effect. However, the commonly used emulsion viscosity reducer uses a chemical synthetic surfactant which is not temperature-resistant and salt-resistant, resulting in poor adaptability of the viscosity reducer in high-temperature and high-salt reservoirs.

[0004] CN201210202927.4 discloses a microemulsion thickened oil viscosity reducer and a preparation method thereof. The weight ratio of the components of the viscosity reducer is as follows: oil-soluble viscosity reducer 33-37, non-ionic surfactant 16-20, sulfonate anionic surfactant 18-22, Tween-type emulsifier 2-4, isomeric alcohol 3-5, and water 20-24. The above raw materials are prepared into products in a reaction kettle under certain temperature and rotation speed conditions. The microemulsion viscosity reducer is mixed with oilfield hot wastewater to form an aqueous solution, which is injected into the ground for use, has the characteristics of high viscosity reduction rate and strong economy, and can reduce the viscosity of thickened oil by more than 98%. The invention uses a sulfonate anionic surfactant, which precipitates when encountering calcium and magnesium ions, and therefore is not suitable for high-salinity reservoirs.

[0005] Patent CN202310438189.1 discloses a preparation method of a complex surfactant thick oil microemulsion, which comprises non-ionic surfactant APE-9 and two kinds of amphoteric surfactants CAB-35 and BS-12. The complex surfactant thick oil microemulsion has the advantages of small amount of surfactant, low price, simple preparation method, and high viscosity reduction rate of 99.53% to 99.68%, and can achieve the beneficial effect of improving the recovery rate. However, the non-ionic surfactant APE-9 used in the invention is not temperature-resistant, and therefore is not suitable for high-temperature and high-salt oil reservoirs. SUMMARY

[0006] The present application provides a bio-based temperature-resistant and salt-resistant microemulsion thick oil viscosity reducer and a preparation method thereof, aiming at the poor adaptability of current thick oil viscosity reducers for high-temperature and high-salt oil reservoirs. The microemulsion viscosity reducer has the advantages of simple single-agent synthesis process, simple microemulsion preparation process, small amount, good viscosity reduction effect, and low cost.

[0007] Therefore, in order to achieve the above-mentioned purpose, on the one hand, the present application provides a bio-based temperature-resistant and salt-resistant microemulsion thick oil viscosity reducer, the composition and mass components of which are as follows:

[0008]

[0009] The molecular structure of the sodium rapeseed polyoxyethylene ether carboxylate is as follows:

[0010]

[0011] The solvent oil is one of 120#, 200#, 220#, 240#, and 260#.

[0012] The electrolyte is one of NaCl, NaNO3, and CaCl2.

[0013] The alcohol additive is one of propanol, isopropanol, butanol, isobutanol, n-pentanol, and n-hexanol.

[0014] On the other hand, the present application provides a preparation method of a bio-based temperature-resistant and salt-resistant microemulsion thick oil viscosity reducer, which is as follows:

[0015] (1) Under the conditions of heating and stirring, the electrolyte is dissolved in water, and then the sodium rapeseed polyoxyethylene ether carboxylate is added to form a solution;

[0016] (2) The solvent oil is added to the above-mentioned solution, and the alcohol additive is added dropwise under stirring until the solution is transparent, to obtain the bio-based temperature-resistant and salt-resistant microemulsion thick oil viscosity reducer.

[0017] The bio-based temperature-resistant and salt-resistant microemulsion thickened oil viscosity reducer of the present application is a colorless transparent liquid, which is composed of water-soluble surfactant, solvent oil, alcohol additive and electrolyte. As an emulsifier for preparing microemulsion, the synthesized rapeseed polyphenol polyoxyethylene ether carboxylate sodium of the present application has both ethoxy and carboxyl groups on the molecule, which is a typical anionic-nonionic surfactant. The carboxyl group on the molecular structure can effectively reduce the precipitation problem caused by the high-temperature hydrogen bonding of ethoxy, so the temperature resistance is greatly improved. At the same time, the ethoxy has a certain negative charge, which has a good electrostatic protection effect on the carboxylate, reducing the interaction with divalent metal ions, so the calcium and magnesium ion resistance is improved. In addition, the other components in the microemulsion have good temperature resistance and salt resistance, so the prepared microemulsion can withstand high-temperature and high-salt reservoir environment. Compared with water-soluble viscosity reducer, the present application uses the strong emulsifying property of rapeseed polyphenol polyoxyethylene ether carboxylate sodium to prepare a microemulsion with nanoscale oil phase particle size, greatly improving the contact efficiency of solvent oil and thickened oil. In the contact process of solvent oil and thickened oil, rapeseed polyphenol polyoxyethylene ether carboxylate sodium is brought into the oil phase. At this time, the methoxybenzene on the rapeseed polyphenol polyoxyethylene ether carboxylate sodium molecule can enter the colloid-asphaltene glue nuclear structure in the thickened oil, destroy the strong interaction between colloid and asphaltene, and thus realize emulsification and viscosity reduction and dispersion viscosity reduction at the same time, greatly reduce the viscosity of thickened oil and increase the flowability.

[0018] Compared with the prior art, the present application has the following beneficial effects and advantages:

[0019] (1) The rapeseed polyphenol used for synthesizing rapeseed polyphenol polyoxyethylene ether carboxylate sodium is widely available, and the synthesis process is simple and clean without pollution.

[0020] (2) The bio-based microemulsion viscosity reducer of the present application has good temperature resistance and salt resistance, the temperature resistance can reach 120℃, the salt concentration resistance can reach 100000mg / L, and the calcium and magnesium ion concentration resistance can reach 2000mg / L.

[0021] (3) The bio-based microemulsion viscosity reducer of the present application has good surface / interface performance, the surface tension is reduced to below 28mN / m, and the interfacial tension is reduced to below 7x10 -2 mN / m.

[0022] (4) The bio-based microemulsion viscosity reducer of the present application has high-efficiency viscosity reduction characteristics, and can reduce the viscosity of thickened oil with a viscosity of 100000mPa·s by more than 99.0% under the condition of a use concentration of 500mg / L. DETAILED DESCRIPTION

[0023] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not considered critical for the purposes of the invention. The endpoints of the ranges and any values are provided as approximations only and are understood to be open-ended. Thus, the endpoints of the ranges and any values are not to be understood as being stated in a strict sense as the exact dimensions are not considered critical for the purposes of the invention.

[0024] According to the first aspect of the present application, the present application provides a bio-based temperature-resistant and salt-resistant microemulsion thickened oil viscosity reducer, the composition and mass components of the microemulsion viscosity reducer are as follows:

[0025]

[0026] The molecular structure of the sodium rapeseed polyphenol polyoxyethylene ether carboxylate is as follows:

[0027]

[0028] The solvent oil is one of 120#, 200#, 220#, 240#, and 260#.

[0029] The electrolyte is one of NaCl, NaNO3, and CaCl2.

[0030] The alcohol additive is one of propanol, isopropanol, butanol, isobutanol, n-pentanol, and n-hexanol.

[0031] In the present application, preferably, the solvent oil is one of 120#, 200#, and 220#.

[0032] In the present application, preferably, the electrolyte is NaCl or NaNO3.

[0033] In the present application, preferably, the alcohol additive is one of propanol, isopropanol, and butanol.

[0034] The sodium rapeseed polyphenol polyoxyethylene ether carboxylate is prepared from rapeseed polyphenol through etherification and carboxylation.

[0035] The preparation method of the sodium rapeseed polyphenol polyoxyethylene ether carboxylate is as follows:

[0036] (1) The rapeseed polyphenol and the first catalyst are put into a reaction kettle at 30-40℃; under high temperature, high pressure, and anaerobic conditions, the etherification reaction is carried out by passing in ethylene oxide, and then the acid is neutralized to obtain the rapeseed polyphenol polyoxyethylene ether;

[0037] (2) adding the second catalyst into the rapeseed polyphenol polyoxyethylene ether at 50-70℃, then adding CH2CH2ClNaO2 to perform carboxylation, adding acid to neutralize after the reaction, and extracting with ethanol to obtain the product rapeseed polyphenol polyoxyethylene ether sodium carboxylate.

[0038] In the application, preferably, based on 1 mol of rapeseed polyphenol, the amount of the first catalyst and ethylene oxide is 0.01-0.1 mol and 2-100 mol, respectively.

[0039] More preferably, based on 1 mol of rapeseed polyphenol, the amount of the first catalyst and ethylene oxide is 0.01-0.03 mol and 2-50 mol, respectively.

[0040] In the application, preferably, the first catalyst is one of sodium hydroxide solid, potassium hydroxide solid, and calcium hydroxide solid, and the mass ratio of the first catalyst to rapeseed polyphenol is 0.02-0.1:1.

[0041] In the application, preferably, the high temperature and high pressure is a temperature of 120-150℃ and a pressure of 0.1-0.4 MPa.

[0042] In the application, preferably, the etherification reaction time is 1-10 h.

[0043] In the application, preferably, based on 1 mol of rapeseed polyphenol polyoxyethylene ether, the amount of the second catalyst and CH2CH2ClNaO2 is 0.02-0.1 mol and 1-3 mol, respectively.

[0044] More preferably, based on 1 mol of rapeseed polyphenol polyoxyethylene ether, the amount of the second catalyst and CH2CH2ClNaO2 is 0.03-0.05 mol and 1-2 mol, respectively.

[0045] In the application, preferably, the second catalyst is one of sodium hydroxide solid, potassium hydroxide solid, and calcium hydroxide solid, and the mass ratio of the second catalyst to rapeseed polyphenol polyoxyethylene ether is 0.01-0.1:1.

[0046] In the application, preferably, the carboxylation reaction time is 5-12 h.

[0047] According to a more specific preferred embodiment, the preparation method of the rapeseed polyphenol polyoxyethylene ether sodium carboxylate specifically comprises the following steps:

[0048] (1) adding rapeseed polyphenol and a first catalyst into a high-pressure reaction kettle, and stirring at a constant temperature of 30-40℃ for 1-3 h;

[0049] (2) After the reaction is completed, nitrogen is flushed into the reactor to replace the air in the reactor, the autoclave is sealed, vacuum is applied, ethylene oxide is introduced, the temperature is raised to 120-150℃, the pressure is raised to 0.1-0.4 MPa, and the reaction is kept for 1-10 h; after the reaction is completed, the reaction solution is cooled to below 50℃ by circulating water, 10 wt% hydrochloric acid is added for neutralization, and rapeseed polyphenol polyoxyethylene ether is obtained;

[0050] (3) In a three-necked flask, rapeseed polyphenol polyoxyethylene ether is added, nitrogen is introduced to replace the air in the three-necked flask, and after stirring and heating to 50-70℃, sodium hydroxide is added, constant temperature stirring is carried out for 1-3 h; then CH2CH2ClNaO2 is added, and the reaction is carried out for 5-12 h; 10 wt% hydrochloric acid is used to adjust the pH to 7-8, and the reaction solution is placed in an ethanol solution and refluxed for 2-3 h to obtain the product rapeseed polyphenol polyoxyethylene ether sodium carboxylate.

[0051] The synthesis reaction equation of the rapeseed polyphenol polyoxyethylene ether sodium carboxylate is as follows:

[0052]

[0053] In a second aspect, the application provides a preparation method of a bio-based temperature-resistant and salt-resistant microemulsion thickened oil viscosity reducer, and the preparation method is as follows:

[0054] (1) Under heating and stirring conditions, an electrolyte is dissolved in water, and then rapeseed polyphenol polyoxyethylene ether sodium carboxylate is added to form a solution;

[0055] (2) Solvent oil is added to the above solution, and an alcohol additive is added dropwise under stirring conditions until the solution is transparent to obtain a bio-based temperature-resistant and salt-resistant microemulsion thickened oil viscosity reducer.

[0056] Preferably, the heating temperature in step (1) is 20-40℃, and the stirring speed is 200-300 rpm.

[0057] Preferably, the stirring speed in step (2) is 200-300 rpm, and the stirring time is 2-5 h.

[0058] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction, and in order to avoid unnecessary repetition, the application will not describe various possible combinations again.

[0059] Furthermore, various different embodiments of the application can also be combined in any manner, as long as they do not deviate from the idea of the application, and they should also be considered as disclosed by the application.

[0060] The application will be further described below with reference to specific examples.

[0061] In the present application, the devices or equipment used are all conventional devices or equipment known in the art and are all commercially available.

[0062] In the following examples and comparative examples, the various reagents used are all commercially available chemical pure reagents unless otherwise specified.

[0063] Example 1

[0064] (1) In a high-pressure reaction kettle, 1 mol of rapeseed polyphenol and 0.01 mol of sodium hydroxide solid were added, and stirred at 30°C for 3 h;

[0065] (2) After the reaction was completed, nitrogen was flushed into the reaction kettle to replace the air, the high-pressure kettle was sealed, vacuumed, 2 mol of ethylene oxide was introduced, the temperature was raised to 120°C, the pressure was raised to 0.3 MPa, and the reaction was kept for 1 h; after the reaction was completed, the reaction liquid was cooled to below 50°C by circulating water, 10 wt% hydrochloric acid was added for neutralization, and rapeseed polyphenol polyoxyethylene ether was obtained;

[0066] (3) In a three-necked flask, 1 mol of rapeseed polyphenol polyoxyethylene ether was added, nitrogen was introduced to replace the air in the three-necked flask, 0.03 mol of sodium hydroxide solid was added after stirring and heating to 50°C, and constant temperature stirring was carried out for 1 h; then 1 mol of CH2CH2ClNaO2 was added, and the reaction was carried out for 5 h; 10 wt% hydrochloric acid was used to adjust the pH to 7-8, and the reaction liquid was placed in an ethanol solution for refluxing for 2 h to obtain the product rapeseed polyphenol polyoxyethylene ether sodium carboxylate A1.

[0067] Example 2

[0068] (1) In a high-pressure reaction kettle, 1 mol of rapeseed polyphenol and 0.02 mol of potassium hydroxide solid were added, and stirred at 32°C for 2 h;

[0069] (2) After the reaction was completed, nitrogen was flushed into the reaction kettle to replace the air, the high-pressure kettle was sealed, vacuumed, 10 mol of ethylene oxide was introduced, the temperature was raised to 125°C, the pressure was raised to 0.2 MPa, and the reaction was kept for 2 h; after the reaction was completed, the reaction liquid was cooled to below 50°C by circulating water, 10 wt% hydrochloric acid was added for neutralization, and rapeseed polyphenol polyoxyethylene ether was obtained;

[0070] (3) In a three-necked flask, 1 mol of rapeseed polyphenol polyoxyethylene ether was added, nitrogen was introduced to replace the air in the three-necked flask, 0.04 mol of potassium hydroxide solid was added after stirring and heating to 60°C, and constant temperature stirring was carried out for 3 h; then 1 mol of CH2CH2ClNaO2 was added, and the reaction was carried out for 10 h; 10 wt% hydrochloric acid was used to adjust the pH to 7-8, and the reaction liquid was placed in an ethanol solution for refluxing for 2 h to obtain the product rapeseed polyphenol polyoxyethylene ether sodium carboxylate A2.

[0071] Example 3

[0072] (1) In the high-pressure reactor, 1 mol of rapeseed polyphenol, 0.05 mol of calcium hydroxide solid, and 35°C constant temperature stirring for 1 h;

[0073] (2) After the reaction, nitrogen was injected to replace the air in the reactor, the autoclave was sealed, vacuum was applied, 20 mol of ethylene oxide was introduced, the temperature was raised to 140°C, the pressure was raised to 0.2 MPa, and the reaction was kept for 3 h; after the reaction was completed, the water was cooled to below 50°C, 10 wt% hydrochloric acid was added for neutralization, and rapeseed polyphenol polyoxyethylene ether was obtained;

[0074] (3) In a three-necked flask, 1 mol of rapeseed polyphenol polyoxyethylene ether was added, nitrogen was introduced to replace the air in the three-necked flask, stirring was performed, the temperature was raised to 55°C, 0.04 mol of sodium hydroxide solid was added, constant temperature stirring was performed for 2 h; then 2 mol of CH2CH2ClNaO2 was added, the reaction was performed for 6 h; 10 wt% hydrochloric acid was used to adjust the pH to 7-8, the reaction liquid was placed in an ethanol solution for reflux for 3 h, and the product rapeseed polyphenol polyoxyethylene ether sodium carboxylate A3 was obtained.

[0075] Example 4

[0076] (1) In the high-pressure reactor, 1 mol of rapeseed polyphenol, 0.06 mol of sodium hydroxide solid, and 36°C constant temperature stirring for 1 h;

[0077] (2) After the reaction, nitrogen was injected to replace the air in the reactor, the autoclave was sealed, vacuum was applied, 50 mol of ethylene oxide was introduced, the temperature was raised to 130°C, the pressure was raised to 0.3 MPa, and the reaction was kept for 5 h; after the reaction was completed, the water was cooled to below 50°C, 10 wt% hydrochloric acid was added for neutralization, and rapeseed polyphenol polyoxyethylene ether was obtained;

[0078] (3) In a three-necked flask, 1 mol of rapeseed polyphenol polyoxyethylene ether was added, nitrogen was introduced to replace the air in the three-necked flask, stirring was performed, the temperature was raised to 65°C, 0.05 mol of potassium hydroxide solid was added, constant temperature stirring was performed for 3 h; then 1.5 mol of CH2CH2ClNaO2 was added, the reaction was performed for 8 h; 10 wt% hydrochloric acid was used to adjust the pH to 7-8, the reaction liquid was placed in an ethanol solution for reflux for 3 h, and the product rapeseed polyphenol polyoxyethylene ether sodium carboxylate A4 was obtained.

[0079] Example 5

[0080] (1) In the high-pressure reactor, 1 mol of rapeseed polyphenol, 0.08 mol of potassium hydroxide solid, and 38°C constant temperature stirring for 2 h;

[0081] (2) After the reaction is completed, nitrogen is flushed into the reaction kettle to replace the air in the reaction kettle, the autoclave is sealed, vacuum is applied, 80 mol of ethylene oxide is introduced, the temperature is raised to 135°C, the pressure is raised to 0.1 MPa, and the reaction is kept for 8 h; after the reaction is completed, the reaction liquid is cooled to below 50°C by circulating water, 10 wt% hydrochloric acid is added for neutralization, and rapeseed polyphenol polyoxyethylene ether is obtained;

[0082] (3) 1 mol of rapeseed polyphenol polyoxyethylene ether is added to a three-necked flask, nitrogen is introduced to replace the air in the three-necked flask, and after stirring and heating to 50°C, 0.03 mol of calcium hydroxide solid is added, constant temperature stirring is carried out for 1 h; then 1.6 mol of CH2CH2ClNaO2 is added, and the reaction is carried out for 9 h; 10 wt% hydrochloric acid is used to adjust the pH to 7-8, the reaction liquid is placed in an ethanol solution and refluxed for 2 h, and the product rapeseed polyphenol polyoxyethylene ether sodium carboxylate A5 is obtained.

[0083] Example 6

[0084] (1) In the high-pressure reaction kettle, 1 mol of rapeseed polyphenol and 0.1 mol of calcium hydroxide solid are added, and constant temperature stirring is carried out at 40°C for 3 h;

[0085] (2) After the reaction is completed, nitrogen is flushed into the reaction kettle to replace the air in the reaction kettle, the autoclave is sealed, vacuum is applied, 100 mol of ethylene oxide is introduced, the temperature is raised to 150°C, the pressure is raised to 0.4 MPa, and the reaction is kept for 10 h; after the reaction is completed, the reaction liquid is cooled to below 50°C by circulating water, 10 wt% hydrochloric acid is added for neutralization, and rapeseed polyphenol polyoxyethylene ether is obtained;

[0086] (3) 1 mol of rapeseed polyphenol polyoxyethylene ether is added to a three-necked flask, nitrogen is introduced to replace the air in the three-necked flask, and after stirring and heating to 70°C, 0.05 mol of calcium hydroxide solid is added, constant temperature stirring is carried out for 2 h; then 2 mol of CH2CH2ClNaO2 is added, and the reaction is carried out for 12 h; 10 wt% hydrochloric acid is used to adjust the pH to 7-8, the reaction liquid is placed in an ethanol solution and refluxed for 3 h, and the product rapeseed polyphenol polyoxyethylene ether sodium carboxylate A6 is obtained.

[0087] Example 7

[0088] (1) In a three-necked flask with a stirrer and a thermometer, 25 g of water is added, then 5 g of NaC is added, and stirring is carried out at 20°C and 300 rpm until dissolution, then 10 g of rapeseed polyphenol polyoxyethylene ether sodium carboxylate A1 is added, and uniform solution is obtained by continuous stirring;

[0089] (2) 20 g of 120# solvent oil is added to the above solution, and stirring is carried out at 200 rpm for 2 h; at this temperature and speed, 1 g of propanol is slowly added dropwise until the solution is transparent, and a bio-based temperature-resistant and salt-resistant microemulsion thick oil viscosity reducer B1 is obtained.

[0090] Example 8

[0091] (1) In a three-necked flask with stirrer and thermometer, 32 g of water was added, followed by 7 g of NaNO3, and dissolved by stirring at 20°C and 250 rpm, followed by 10 g of rapeseed polyphenol polyoxyethylene ether carboxylic acid sodium A2, and continued to be stirred to obtain a uniform solution;

[0092] (2) 35 g of 200# solvent oil was added to the above solution, and stirred at 300 rpm for 2 h; at this temperature and speed, 2 g of isopropyl alcohol was slowly added dropwise until the solution was transparent, to obtain a bio-based temperature-resistant and salt-resistant microemulsion thick oil viscosity reducer B2.

[0093] Example 9

[0094] (1) In a three-necked flask with stirrer and thermometer, 35 g of water was added, followed by 7 g of CaCl2, and dissolved by stirring at 40°C and 200 rpm, followed by 10 g of rapeseed polyphenol polyoxyethylene ether carboxylic acid sodium A3, and continued to be stirred to obtain a uniform solution;

[0095] (2) 30 g of 200# solvent oil was added to the above solution, and stirred at 200 rpm for 3 h; at this temperature and speed, 3 g of butanol was slowly added dropwise until the solution was transparent, to obtain a bio-based temperature-resistant and salt-resistant microemulsion thick oil viscosity reducer B3.

[0096] Example 10

[0097] (1) In a three-necked flask with stirrer and thermometer, 42 g of water was added, followed by 6 g of NaCl, and dissolved by stirring at 30°C and 200 rpm, followed by 10 g of rapeseed polyphenol polyoxyethylene ether carboxylic acid sodium A4, and continued to be stirred to obtain a uniform solution;

[0098] (2) 25 g of 220# solvent oil was added to the above solution, and stirred at 250 rpm for 35 h; at this temperature and speed, 4 g of propyl alcohol was slowly added dropwise until the solution was transparent, to obtain a bio-based temperature-resistant and salt-resistant microemulsion thick oil viscosity reducer B4.

[0099] Example 11

[0100] (1) In a three-necked flask with stirrer and thermometer, 55 g of water was added, followed by 6 g of NaNO3, and dissolved by stirring at 25°C and 300 rpm, followed by 10 g of rapeseed polyphenol polyoxyethylene ether carboxylic acid sodium A5, and continued to be stirred to obtain a uniform solution;

[0101] (2) 30 g of 240# solvent oil was added to the above solution, and stirred at 280 rpm for 4 h; at this temperature and speed, 3 g of isopropyl alcohol was slowly added dropwise until the solution was transparent, to obtain a bio-based temperature-resistant and salt-resistant microemulsion thick oil viscosity reducer B5.

[0102] Example 12

[0103] (1) In a three-necked flask with a stirrer and a thermometer, 64 g of water was added, followed by 5 g of CaCl2, which was dissolved by stirring at 35°C and 250 rpm, followed by 10 g of rapeseed polyphenol polyoxyethylene ether sodium carboxylate A6, and uniform solution was obtained by continuing to stir;

[0104] (2) 40 g of 260# solvent oil was added to the above solution, and stirred at 300 rpm for 5 h; at this temperature and speed, 5 g of butanol was slowly added dropwise until the solution was transparent, to obtain a bio-based temperature-resistant and salt-resistant microemulsion thickened oil viscosity reducer B6.

[0105] Example 13 Test of surface tension and interfacial tension

[0106] The bio-based temperature-resistant and salt-resistant microemulsion thickened oil viscosity reducers B1-B3 of the present application and the oil field in use petroleum sulfonate were diluted to a 500 mg / L solution, and the surface tension was determined according to the pull ring method in SY / T 5370-2018 “Method for Determining Surface and Interfacial Tension”, and the interfacial tension was tested by the pendant drop method. The test area crude oil had a viscosity of 93560 mPa·s at 50°C, and the test results of surface tension and interfacial tension are shown in Table 1.

[0107] As can be seen from Table 1, the bio-based temperature-resistant and salt-resistant microemulsion thickened oil viscosity reducers B1-B3 of the present application have a surface tension of less than 28 mN / m and an interfacial tension of less than 7×10 -2 mN / m when the concentration is 500 mg / L, while the surface tension of the comparative example petroleum sulfonate is 30.5±1.1 mN / m, and the interfacial tension is (12.3±0.4)×10 -2 mN / m, which is significantly higher than the present application.

[0108] Example 14 Determination of viscosity reduction rate

[0109] The crude oil used in this experiment was the same as in Example 13, and the bio-based temperature-resistant and salt-resistant microemulsion thickened oil viscosity reducers B1-B3 of the present application and the oil field in use petroleum sulfonate were prepared into a 500 mg / L solution, and the evaluation method referred to Q / SH10201519-2016 “General Technical Conditions for Thickened Oil Viscosity Reducers”

[0110]

[0111] In the formula:

[0112] f — viscosity reduction rate, %;

[0113] μ0 — initial viscosity of crude oil at 50°C, mPa·s;

[0114] μ - viscosity of crude oil after viscosity reduction, mPa s.

[0115] The test results are shown in Table 1.

[0116] As can be seen from Table 1, the bio-based temperature-resistant and salt-resistant microemulsion heavy oil viscosity reducer B1-B3 of the application has a viscosity reduction rate of more than 99% at a use concentration of 500 mg / L, while the viscosity reduction rate of the petroleum sulfonate of the comparative example is 56.3±0.5%, which is significantly lower than that of the application.

[0117] Example 15: Test of temperature resistance and salt resistance

[0118] (1) The bio-based temperature-resistant and salt-resistant microemulsion heavy oil viscosity reducer B1-B3 of the application and the petroleum sulfonate of Shengli Chemical Plant were prepared into 500 mg / L solutions with distilled water, and then NaCl and CaCl2 were added to make the concentrations in the solutions be 100000 mg / L and 2000 mg / L, respectively. The above prepared solutions were placed in an oven at 120℃ for 24 h.

[0119] (2) The viscosity reduction rates on the crude oil in Example 13 were tested according to the method of Example 14, and the test results are shown in Table 2.

[0120] As can be seen from Table 2, the bio-based temperature-resistant and salt-resistant microemulsion heavy oil viscosity reducer B1-B3 of the application has good temperature resistance and salt resistance, the temperature resistance can reach 120℃, the salt concentration resistance can reach 100000 mg / L, and the calcium and magnesium ion concentration resistance can reach 2000 mg / L.

[0121] Example 10: Test of adaptability of crude oil

[0122] (1) The bio-based temperature-resistant and salt-resistant microemulsion heavy oil viscosity reducer B1-B3 of the application and the petroleum sulfonate of Shengli Chemical Plant were prepared into 500 mg / L solutions with different block produced fluids. The viscosity of the crude oil of block one at 50℃ was 21563 mPa s, the salinity was 12304 mg / L, and the calcium and magnesium ion concentration was 335 mg / L; the viscosity of the crude oil of block two at 50℃ was 53689 mPa s, the salinity was 36871 mg / L, and the calcium and magnesium ion concentration was 698 mg / L; the viscosity of the crude oil of block three at 50℃ was 86048 mPa s, the salinity was 63871 mg / L, and the calcium and magnesium ion concentration was 1056 mg / L.

[0123] (2) The viscosity reduction rates on the crude oils of different blocks were tested according to the method of Example 14, and the test results are shown in Table 3.

[0124] As can be seen from Table 3, the bio-based temperature-resistant and salt-resistant microemulsion heavy oil viscosity reducer B1-B3 of the application has a viscosity reduction rate of more than 99% on crude oils with different salinities and viscosities, while the viscosity reduction rate of the petroleum sulfonate of the comparative example is less than 60%, which shows that the bio-based temperature-resistant and salt-resistant microemulsion heavy oil viscosity reducer of the application has strong adaptability.

[0125] Table 1 Surface tension, interfacial tension, viscosity reduction test results

[0126]

[0127]

[0128] Table 2 Temperature resistance and salt resistance test results

[0129] Name Viscosity reduction, % [B1] 99.8±0.3 [B2] 99.9±0.4 [B3] 99.6±0.4 Petroleum sulfonate 32.5±0.3

[0130] Table 3 Viscosity reduction test results of bio-based microemulsion viscosity reducer on different blocks of heavy oil

[0131]

[0132]

[0133] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A bio-based temperature-tolerant and salt-resistant microemulsion thick oil viscosity reducer, characterized in that, The microemulsion thickened oil viscosity reducer comprises the following components and mass components: The molecular structure formula of the rapeseed polyphenol polyoxyethylene ether carboxylic acid sodium is as follows: The solvent oil is one of 120#, 200#, 220# and 240#; The electrolyte is one of NaCl, NaNO3 and CaCl2; The alcohol additive is one of propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol and n-pentyl alcohol.

2. The bio-based temperature-tolerant and salt-resistant microemulsion thickened oil viscosity reducer according to claim 1, characterized in that, The solvent oil is one of 120#, 200# and 220#.

3. The bio-based temperature-tolerant and salt-resistant microemulsion thickened oil viscosity reducer according to claim 1, characterized in that, The electrolyte is NaCl or NaNO3.

4. The bio-based temperature-tolerant and salt-resistant microemulsion thickened oil viscosity reducer of claim 1, characterized in that, The alcohol additive is one of propyl alcohol, isopropyl alcohol and butyl alcohol.

5. The bio-based temperature-tolerant and salt-resistant microemulsion thickened oil viscosity reducer of claim 1, wherein, The preparation method of the rapeseed polyphenol polyoxyethylene ether carboxylic acid sodium comprises the following steps: (1) the rapeseed polyphenol and the first catalyst are put into a reaction kettle under the condition of 30-40 ℃; under the condition of high temperature, high pressure and no oxygen, the etherification reaction is carried out by introducing ethylene oxide, then acid is added for neutralization, and the rapeseed polyphenol polyoxyethylene ether is obtained; (2) the second catalyst is added to the rapeseed polyphenol polyoxyethylene ether under the condition of 50-70 ℃, then CH2CH2ClNaO2 is added for carboxylation reaction, after the reaction is completed, acid is added for neutralization, and the product rapeseed polyphenol polyoxyethylene ether carboxylic acid sodium is obtained by ethanol extraction.

6. The bio-based temperature-tolerant and salt-resistant microemulsion thickened oil viscosity reducer according to claim 5, characterized in that, Based on 1 mole of rapeseed polyphenol, the use amount of the first catalyst and ethylene oxide is 0.01-0.1 mole and 2-100 moles respectively.

7. The bio-based temperature-tolerant and salt-resistant microemulsion thickened oil viscosity reducer according to claim 6, characterized in that, Based on 1 mole of rapeseed polyphenol, the use amount of the first catalyst and ethylene oxide is 0.01-0.03 mole and 2-50 moles respectively.

8. The bio-based temperature-tolerant and salt-resistant microemulsion thickened oil viscosity reducer according to claim 5, characterized in that, The first catalyst is one of sodium hydroxide solid, potassium hydroxide solid and calcium hydroxide solid, and the mass ratio with the rapeseed polyphenol is 0.02-0.1:

1.

9. The bio-based temperature-tolerant and salt-resistant microemulsion thickened oil viscosity reducer according to claim 5, characterized in that, The high temperature and high pressure is 120-150 ℃ and 0.1-0.4 MPa.

10. The bio-based temperature-tolerant and salt-resistant microemulsion thickened oil viscosity reducer of claim 5, wherein, The etherification reaction time is 1-10 h.

11. The bio-based temperature-tolerant and salt-resistant microemulsion thickened oil viscosity reducer according to claim 5, characterized in that, Based on 1 mole of rapeseed polyphenol polyoxyethylene ether, the use amount of the second catalyst and CH2CH2ClNaO2 is 0.02-0.1 mole and 1-3 moles respectively.

12. The bio-based temperature-tolerant and salt-resistant microemulsion thickened oil viscosity reducer of claim 11, wherein, Based on 1 mole of rapeseed polyphenol polyoxyethylene ether, the use amount of the second catalyst and CH2CH2ClNaO2 is 0.03-0.05 mole and 1-2 moles respectively.

13. The bio-based temperature-tolerant and salt-resistant microemulsion thickened oil viscosity reducer of claim 5, wherein, The second catalyst is one of sodium hydroxide solid, potassium hydroxide solid and calcium hydroxide solid, and the mass ratio with the rapeseed polyphenol polyoxyethylene ether is 0.01-0.1:

1.

14. The bio-based temperature-tolerant and salt-resistant microemulsion thickened oil viscosity reducer of claim 5, wherein, The carboxylation reaction time is 5-12 h.

15. The bio-based temperature-tolerant and salt-resistant microemulsion thickened oil viscosity reducer of claim 5, wherein, The preparation method of the rapeseed polyphenol polyoxyethylene ether carboxylic acid sodium comprises the following steps: (1) the rapeseed polyphenol and the first catalyst are put into a reaction kettle under the condition of 30-40 ℃; under the condition of high temperature, high pressure and no oxygen, the etherification reaction is carried out by introducing ethylene oxide, then acid is added for neutralization, and the rapeseed polyphenol polyoxyethylene ether is obtained; (2) the second catalyst is added to the rapeseed polyphenol polyoxyethylene ether under the condition of 50-70 ℃, then CH2CH2ClNaO2 is added for carboxylation reaction, after the reaction is completed, acid is added for neutralization, and the product rapeseed polyphenol polyoxyethylene ether carboxylic acid sodium is obtained by ethanol extraction. (3) In a three-necked flask, rapeseed polyphenol polyoxyethylene ether is added, nitrogen is filled to replace the air in the three-necked flask, and after stirring and heating to 50-70℃, sodium hydroxide is added, constant temperature stirring is carried out for 1-3h; then CH2CH2ClNaO2 is added, and the reaction is carried out for 5-12h; 10wt% hydrochloric acid is used to adjust the pH to 7-8, the reaction solution is placed in an ethanol solution to reflux for 2-3h, and the product rapeseed polyphenol polyoxyethylene ether carboxylic acid sodium is obtained.

16. The method of producing a bio-based temperature-tolerant, salt-tolerant, microemulsion, viscous oil viscosity reducer according to any one of claims 1 to 15, characterized in that, The preparation method is as follows: (1) Under the conditions of heating and stirring, the electrolyte is dissolved in water, and then the rapeseed polyphenol polyoxyethylene ether carboxylic acid sodium is added to mix into a solution; (2) Solvent oil is added to the above solution, and alcohol additive is added dropwise under stirring until the solution is transparent to prepare a bio-based temperature-resistant and salt-resistant microemulsion thick oil viscosity reducer.

17. The preparation method of a bio-based temperature-resistant and salt-resistant microemulsion thick oil viscosity reducer according to claim 16, characterized in that, The heating temperature in step (1) is 20-40℃, and the stirring speed is 200-300rpm.

18. The preparation method of a bio-based temperature-resistant and salt-resistant microemulsion thick oil viscosity reducer according to claim 16, characterized in that, In step (2), the stirring speed is 200-300rpm, and the stirring time is 2-5h.

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