CN116253842B - Thickened oil viscosity reducer for displacement of reservoir oil and synthesis method - Google Patents
Thickened oil viscosity reducer for displacement of reservoir oil and synthesis method Download PDFInfo
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Abstract
The invention discloses a thickened oil viscosity reducer for displacement of reservoir oil and a synthesis method thereof, which belong to the technical field of thickened oil viscosity reducers, and the molecular structure of the thickened oil viscosity reducer contains amphoteric oleophylic monomer alkyl block polyether propylene methyl amine ether and oleophylic monomer itaconic acid di-isomeric alkyl ester, so that the thickened oil viscosity reducer has good interfacial activity and can effectively reduce oil-water interfacial tension; the wet turnover capability is good; the emulsion has good emulsifying capacity, can emulsify thick oil and super thick oil into O/W emulsion, thereby greatly reducing the viscosity of the thick oil, and contains four hydrophilic groups of amide, sodium carboxylate, quaternary ammonium and sodium sulfonate in a molecular structure, so that the emulsion has good hard water resistance, can be stably dissolved in water, and can be applied to products such as thick oil viscosity reducer, temperature-resistant salt-resistant thick oil viscosity reducer and the like.
Description
Technical Field
The invention relates to a thickened oil viscosity reducer, in particular to a thickened oil viscosity reducer for oil displacement, and also relates to a method for synthesizing the thickened oil viscosity reducer, in particular to a method for synthesizing the thickened oil viscosity reducer for oil displacement, belonging to the technical field of thickened oil viscosity reducers.
Background
The thick oil and the super thick oil are rich in resources and account for 47.2 percent of the total reserve of the Chinese crude oil, but the exploitation degree of the Chinese thick oil reservoir is less than 16.3 percent due to the high viscosity of the thick oil and the super thick oil and high exploitation difficulty.
At present, the thick oil is mainly driven by high-temperature steam heat to improve the yield, and the heat is required to consume a large amount of natural gas, so that the cost is high, the carbon dioxide emission is large, and the thick oil is gradually replaced by chemical driving.
The thickened oil viscosity-reducing wash oil agent for synergistic polymer flooding disclosed by application number 202210585093.3 in the prior art, as well as a preparation method and application thereof, comprises, by mass, 25% -35% of anionic surfactant, 10% -20% of zwitterionic surfactant, 10% -20% of nonionic surfactant, 10% -20% of low-carbon alcohol and the balance of water. The viscosity-reducing wash oil provided by the invention has the interfacial tension less than or equal to 8.9X10 when being applied to the exploitation of thick oil with the formation temperature of 70 ℃ and the crude oil viscosity of 1314 mPa.s -2 mN/m, viscosity reduction rate is more than or equal to 81.7%, wash oil efficiency is more than or equal to 42.1%, and polymer viscosity retention rate is more than or equal to 97.4%.
As the prior art has complex thick oil components, high colloid and asphaltene contents and large difference of thick oil molecular structures of different blocks, a chemical oil displacement agent needs to be developed specifically according to different oil reservoir conditions, and the thick oil viscosity reducer for oil displacement and a synthesis method are designed for solving the problems.
Disclosure of Invention
The invention mainly aims to provide a thickened oil viscosity reducer for oil displacement and a synthesis method.
The aim of the invention can be achieved by adopting the following technical scheme.
A thickened oil viscosity reducer for oil displacement comprises the following raw materials.
Alkyl block polyether propylene methyl amine ether, itaconic acid di-isomeric alkyl esters.
And 2-4 of acrylamide, sodium acrylate, 2-acrylamide-2-methylpropanesulfonic acid and trimethyl propenyl ammonium chloride are selected.
A synthesis method of a thickened oil viscosity reducer for oil displacement comprises the following steps.
Step one: adding alkyl block polyether propylene methyl amine ether and itaconic acid di-isomeric alkyl ester into a polymerization reaction kettle.
2-4 of acrylamide, sodium acrylate, 2-acrylamide-2-methylpropanesulfonic acid, and trimethylpropenyl ammonium chloride.
Step two: starting the polymerization reaction kettle to carry out electric stirring, heating to maintain the reaction temperature at 35-40 ℃, and stirring for 30-40min to uniformly mix the materials.
Step three: adding an initiator into a polymerization reaction kettle, introducing nitrogen, controlling the reaction temperature at 35-40 ℃ and the reaction time at 6-8h.
Step four: and closing the polymerization reaction kettle, continuously introducing nitrogen for 20min, stopping introducing nitrogen, and sealing the reaction kettle for reaction for 6h.
Step five: and after the sealing reaction is finished, taking the gel in the polymerization reaction kettle out of the reaction kettle, granulating and drying to obtain the thickened oil viscosity reducer.
Preferably, the specific synthesis of the alkyl block polyether propylene methyl amine ether in step one is as follows.
S1: adding alkyl block polyether and trioxymethylene into a jacketed reaction kettle, and adding benzene as a solvent according to 2-3 times of the total reactant mass.
S2: the reaction kettle with the closed jacket is fully stirred, the reaction temperature is maintained at 5-15 ℃, and the stirring is carried out for 30min.
S3: placing the HCl storage tank on a balance with a 5Kg measuring range, connecting an outlet of the HCl storage tank with a reaction kettle, slowly introducing HCl gas, determining the addition amount of HCl through the mass change of the HCl storage tank, maintaining the reaction temperature at 5-15 ℃, closing an air inlet valve, and continuing the reaction for 2 hours.
S4: after the reaction is finished, introducing nitrogen from the bottom of the jacketed reaction kettle, taking the residual HCl in the jacketed reaction kettle into a NaOH absorption tower by using nitrogen, detecting tail gas by using wet pH test paper every 10min, and stopping introducing nitrogen after the HCl gas in the jacketed reaction kettle is completely removed if the pH value in 30s is more than 3.
S5: neutralizing the reactant in the jacketed reaction kettle to be neutral by NaOH, standing, filtering, putting the filtrate into a rotary evaporator, and removing solvent benzene by evaporation under the condition of 90 ℃ negative pressure.
S6: adding alkyl block polyether chloromethyl ether and 3-aminopropene into a jacketed reaction kettle according to the molar ratio of 1:1.05-1.10, and adding ammonia water according to 1.2 times of the molar amount of the alkyl block polyether chloromethyl ether.
S7: the jacketed reaction kettle is closed, stirring is started, the reaction temperature is adjusted to 75-80 ℃ and the reaction is carried out for 4 hours.
S8: the jacketed reaction kettle is connected with a vacuum pump, excessive ammonia and water in the reactant are evaporated under a negative pressure state, and the reactant is cooled to room temperature after the evaporation is completed.
S9: adding ethanol with the same mass as the reactant, stirring uniformly, standing for precipitation, filtering by using a G3 sand core funnel, transferring the filtrate to a single-neck flask, and removing the ethanol by using a rotary evaporator under the condition of negative pressure at 90 ℃ to obtain the alkyl block polyether propylene methyl amine ether.
Preferably, the specific synthesis method of the di-isomeric alkyl itaconate in step one is as follows.
Step 1: itaconic acid and alkyl alcohol are added into a three-neck flask according to the molar ratio of 1:2.2-2.6, concentrated sulfuric acid with the total material amount of 0.1-0.5% is added, and a stirring paddle is inserted into the three-neck flask and connected with a condenser.
Step 2: the reaction temperature is selected between 70 ℃ and 100 ℃ according to different reactants, the esterification reaction is carried out for 1h, and the reaction temperature is increased until the added alkyl alcohol can be distilled out.
Step 3: the alkyl alcohol is condensed by a condensing pipe, enters a separating funnel with a 4A molecular sieve, and returns to a three-neck flask after water is absorbed by the 4A molecular sieve, and the reaction is repeated for three times.
Step 4: and titrating the esterification rate by an acid-base titration method, and connecting a three-neck flask with a vacuum pump when the conversion rate is more than or equal to 98%, and completely evaporating the alkyl alcohol under a negative pressure state to obtain the product itaconic acid dialkyl ester.
Preferably, the molar ratio of the alkyl block polyether to the trioxymethylene is 1:0.34-0.38.
Preferably, the mol ratio of the alkyl block polyether chloromethyl ether to the 3-aminopropene is 1:1.05-1.10.
Preferably, the ammonia is added in an amount corresponding to NH therein 3 The molar amount of (2) is 1.2 times that of the alkyl block polyether chloromethyl ether.
Preferably, in the third step, the initiator is sodium persulfate, sodium bisulphite and azodiisobutyronitrile, the ratio is 1:0.5:0.1-0.3, and the total usage amount of the initiator is 0.01-0.06% of the total material amount.
The invention has the beneficial technical effects.
The viscous oil viscosity reducer for oil displacement and the synthesis method provided by the invention have the advantages that the molecular structure contains the amphiphilic lipophilic monomer alkyl block polyether propylene methyl amine ether (GABA) and the lipophilic monomer itaconic acid di-isomeric alkyl ester (DBDI), so that the viscous oil viscosity reducer has good interfacial activity and can effectively reduce the interfacial tension of oil and water; the wet turnover capability is good; has good emulsifying capacity, and can emulsify thick oil and super thick oil into O/W emulsion, thereby greatly reducing the viscosity of thick oil. The molecular structure contains four hydrophilic groups of amide, sodium carboxylate, quaternary ammonium and sodium sulfonate, so that the product has good hard water resistance, can be stably dissolved in water, and can be applied to products such as thick oil viscosity reducer, heat-resistant salt-resistant thick oil viscosity reducer and the like.
Drawings
FIG. 1 is a schematic diagram showing the molecular formula of a viscous oil viscosity-reducing agent for oil displacement and a synthesis method according to a preferred embodiment of the invention.
FIG. 2 is a molecular structure diagram of dialkyl itaconate in accordance with a preferred embodiment of the present invention.
FIG. 3 is a molecular structure diagram of an alkyl block polyether propylene methyl amine ether in accordance with a preferred embodiment of the present invention.
Detailed Description
In order to make the technical solution of the present invention more clear and obvious to those skilled in the art, the present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
As shown in fig. 1-3, the thickened oil viscosity reducer for oil displacement provided in the embodiment comprises the following raw materials.
Alkyl block polyether propylene methyl amine ether, itaconic acid di-isomeric alkyl esters.
And 2-4 of acrylamide, sodium acrylate, 2-acrylamide-2-methylpropanesulfonic acid and trimethyl propenyl ammonium chloride are selected.
A synthesis method of a thickened oil viscosity reducer for oil displacement comprises the following steps.
Step one: adding alkyl block polyether propylene methyl amine ether and itaconic acid di-isomeric alkyl ester into a polymerization reaction kettle.
2-4 of acrylamide, sodium acrylate, 2-acrylamide-2-methylpropanesulfonic acid, and trimethylpropenyl ammonium chloride.
Step two: starting the polymerization reaction kettle to carry out electric stirring, heating to maintain the reaction temperature at 35-40 ℃, and stirring for 30-40min to uniformly mix the materials.
Step three: adding an initiator into a polymerization reaction kettle, introducing nitrogen, controlling the reaction temperature at 35-40 ℃ and the reaction time at 6-8h.
Step four: and closing the polymerization reaction kettle, continuously introducing nitrogen for 20min, stopping introducing nitrogen, and sealing the reaction kettle for reaction for 6h.
Step five: and after the sealing reaction is finished, taking the gel in the polymerization reaction kettle out of the reaction kettle, granulating and drying to obtain the thickened oil viscosity reducer.
In this example, the specific synthesis of the alkyl block polyether propylene methyl amine ether in step one is as follows.
S1: adding alkyl block polyether and trioxymethylene into a jacketed reaction kettle, and adding benzene as a solvent according to 2-3 times of the total reactant mass.
S2: the reaction kettle with the closed jacket is fully stirred, the reaction temperature is maintained at 5-15 ℃, and the stirring is carried out for 30min.
S3: placing the HCl storage tank on a balance with a 5Kg measuring range, connecting an outlet of the HCl storage tank with a reaction kettle, slowly introducing HCl gas, determining the addition amount of HCl through the mass change of the HCl storage tank, maintaining the reaction temperature at 5-15 ℃, closing an air inlet valve, and continuing the reaction for 2 hours.
S4: after the reaction is finished, introducing nitrogen from the bottom of the jacketed reaction kettle, taking the residual HCl in the jacketed reaction kettle into a NaOH absorption tower by using nitrogen, detecting tail gas by using wet pH test paper every 10min, and stopping introducing nitrogen after the HCl gas in the jacketed reaction kettle is completely removed if the pH value in 30s is more than 3.
S5: neutralizing the reactant in the jacketed reaction kettle to be neutral by NaOH, standing, filtering, putting the filtrate into a rotary evaporator, and removing solvent benzene by evaporation under the condition of 90 ℃ negative pressure.
S6: adding alkyl block polyether chloromethyl ether and 3-aminopropene into a jacketed reaction kettle according to the molar ratio of 1:1.05-1.10, and adding ammonia water according to 1.2 times of the molar amount of the alkyl block polyether chloromethyl ether.
S7: the jacketed reaction kettle is closed, stirring is started, the reaction temperature is adjusted to 75-80 ℃ and the reaction is carried out for 4 hours.
S8: the jacketed reaction kettle is connected with a vacuum pump, excessive ammonia and water in the reactant are evaporated under a negative pressure state, and the reactant is cooled to room temperature after the evaporation is completed.
S9: adding ethanol with the same mass as the reactant, stirring uniformly, standing for precipitation, filtering by using a G3 sand core funnel, transferring the filtrate to a single-neck flask, and removing the ethanol by using a rotary evaporator under the condition of negative pressure at 90 ℃ to obtain the alkyl block polyether propylene methyl amine ether.
In this example, the specific synthesis of the dialkyl itaconate in step one is as follows.
Step 1: itaconic acid and alkyl alcohol are added into a three-neck flask according to the molar ratio of 1:2.2-2.6, concentrated sulfuric acid with the total material amount of 0.1-0.5% is added, and a stirring paddle is inserted into the three-neck flask and connected with a condenser.
Step 2: the reaction temperature is selected between 70 ℃ and 100 ℃ according to different reactants, the esterification reaction is carried out for 1h, and the reaction temperature is increased until the added alkyl alcohol can be distilled out.
Step 3: the alkyl alcohol is condensed by a condensing pipe, enters a separating funnel with a 4A molecular sieve, and returns to a three-neck flask after water is absorbed by the 4A molecular sieve, and the reaction is repeated for three times.
Step 4: and titrating the esterification rate by an acid-base titration method, and connecting a three-neck flask with a vacuum pump when the conversion rate is more than or equal to 98%, and completely evaporating the alkyl alcohol under a negative pressure state to obtain the product itaconic acid dialkyl ester.
In this example, the molar ratio of the alkyl block polyether to trioxymethylene is 1:0.34-0.38.
In this example, the ammonia was added in an amount corresponding to NH 3 The molar amount of (2) is 1.2 times that of the alkyl block polyether chloromethyl ether.
In this embodiment, in the third step, the initiator is sodium persulfate, sodium bisulphite, and azobisisobutyronitrile, the ratio is 1:0.5:0.1-0.3, and the total usage amount of the initiator is 0.01-0.06% of the total material amount.
The alkyl block polyether propylene methyl amine ether monomer shown in figure 3 is an amphoteric monomer with nonionic property and weak cationic property, has strong action with colloid and asphaltene in crude oil, and has good emulsifying capability and oil-water interfacial tension.
Wherein R is 1 Represents a C8-C22 fatty alcohol or a C8-C12 alkylphenol; n represents the amount of polyoxyethylene ether and can be any number from 3 to 10 according to the performance requirements of the product; m represents the amount of polyoxypropylene ether and may be any number from 2 to 6 depending on the product performance requirements.
The di-isomeric alkyl itaconate (DBDI) shown in fig. 2 has stronger lipophilicity, better effect with saturated hydrocarbon and aromatic hydrocarbon in crude oil, and good oil-water interfacial tension after polymerization.
Wherein R is 2 Representative isomeric alkyl alcohols include: isopropanol, isobutanol, isoamyl alcohol, and the like.
After the polymerization of the acrylamide, the molecular carbon chain can be flexible, and meanwhile, the acrylamide has good hydrophilicity, so that the viscosity of the aqueous solution of the polymeric surfactant can be improved, and the stability of the aqueous solution of the polymeric surfactant in water can be improved.
The sodium acrylate has extremely strong hydrophilicity, can improve the hard water resistance and the thermal stability of the surface polymerization agent, has certain emulsifying capacity, and can improve the emulsifying and viscosity reducing capacity of the product.
The sodium acrylamide-2-methylpropanesulfonate can improve the calcium and magnesium ion resistance of the product and the stability of the surface-accumulating agent in oil reservoirs with higher calcium and magnesium ion content.
The trimethyl propenyl ammonium chloride is a short-chain cationic monomer, can improve the calcium and magnesium ion resistance of the product, has certain interfacial activity, and can improve the stability of O/W emulsion formed by crude oil and the product.
Example 1
Synthesis and application of salt-resistant thickened oil viscosity reducer.
200g of nonylphenol block polyether NP-EO (10) PO (3) was added to the jacketed kettle, 7.92g of trioxymethylene was added, and 500g of benzene was added as a solvent.
The reaction vessel was closed and stirred well, and the reaction temperature was maintained at 10-15 ℃.
After stirring for 30min, 13.12g of HCl gas is slowly introduced, the reaction temperature is maintained at 10-15 ℃, the air inlet valve is closed, and the reaction is continued for 2h.
After the reaction is completed, nitrogen is introduced from the bottom of the reaction kettle, the residual HCl in the kettle is brought into a NaOH absorption tower by using nitrogen, after 30min, the reaction kettle is detected by using wet pH test paper, pH=4 is stopped within 30s, the nitrogen is introduced, and the reactant is neutralized to be neutral by using NaOH.
Standing, filtering, placing the filtrate into a rotary evaporator, and removing solvent benzene to obtain nonylphenol block polyether chloromethyl ether.
240g of nonylphenol block polyether chloromethyl ether was taken and placed in a reaction vessel, 17.07g of 3-aminopropene was added, and 30g of aqueous ammonia (23%) was added.
The reaction kettle is closed, stirring is started, and the reaction temperature is adjusted to 75-80 ℃.
After 4h of reaction, a vacuum pump is connected, excessive ammonia and water in the reactant are evaporated under a negative pressure state, and the reactant is cooled to room temperature after the evaporation is completed.
Adding ethanol with the same mass as the reactant, stirring uniformly, standing for precipitation, filtering with a G3 sand core funnel, removing ethanol in the filtrate with a rotary evaporator to obtain the final active lipophilic monomer alkyl block polyether propylene methyl amine ether (GABA).
200g of itaconic acid is added into a three-neck flask, 138.58g of isopropanol is added, 1g of concentrated sulfuric acid is added into the three-neck flask, a stirring paddle is inserted into the three-neck flask, a condenser is connected, the reaction temperature is 80-85 ℃, the esterification reaction is carried out for 1h, the reaction temperature is increased until the added alkyl alcohol can be distilled out, the alkyl alcohol enters a separating funnel provided with a 4A molecular sieve after being condensed by a condensing tube, and after water is absorbed by the 4A molecular sieve, the alkyl alcohol is returned to the three-neck flask to continue the reaction for three times.
Titrating the esterification rate by an acid-base titration method, connecting a three-neck flask with a vacuum pump when the conversion rate is more than or equal to 98%, and completely evaporating out isopropanol under a negative pressure state to obtain a final product, namely itaconic acid diisopropyl ester (DBDI), wherein the molecular formula is shown as follows:
21.07g of GABA, 10.23g of DBDI, 127.07g of acrylamide, 44.91g of sodium acrylate, 6.48g of trimethyl propenyl ammonium chloride and 480g of ultrapure water are added into a reaction kettle, 0.35g of potassium persulfate and 0.17g of sodium bisulphite are dissolved into 10g of ultrapure water, the reaction kettle is added, nitrogen is introduced, the reaction temperature is controlled at 35-40 ℃, after the reaction kettle is closed, the nitrogen is continuously introduced for 20min, the nitrogen introduction is stopped, the reaction kettle is sealed, the reaction temperature is increased to 70 ℃ after 4h, and the reaction is continued for 3h. And after the reaction is finished, taking the gel out of the reaction kettle, granulating and drying.
Obtaining the final amphoteric polymer surfactant. The structural general formula is shown as follows.
And (5) analyzing product performance.
The viscosity of the thickened oil in the area of the island 9 of the victory oil field is 16284 mPa.s, and the thickened oil belongs to medium-viscosity thickened oil; the mineralization degree of injected water is 6581mg/L, and the mineralization degree is moderate; the stratum temperature is 70 ℃, and the block is suitable for viscosity reduction and displacement of thick oil.
And detecting the synthetic product according to the technical requirement of the thickened oil viscosity reducer for synergistic polymer flooding of the standard Q/SH CG0156-2021 of the petrochemical industry.
Example 2
Synthesis and application of low-tension thick oil viscosity-reducing oil displacement agent.
200g of nonylphenol block polyether NP-EO (3) PO (5) was added to the jacketed kettle, 10.3g of trioxymethylene was added thereto, and 500g of benzene was added thereto as a solvent. The reaction vessel was closed and stirred well, and the reaction temperature was maintained at 10-15 ℃. After stirring for 30min, 17.1g of HCl gas is slowly introduced, the reaction temperature is maintained at 10-15 ℃, the air inlet valve is closed, and the reaction is continued for 2h. After the reaction is completed, nitrogen is introduced from the bottom of the reaction kettle, the residual HCl in the kettle is brought into a NaOH absorption tower by using nitrogen, after 40min, the reaction kettle is detected by using wet pH test paper, pH=5 is stopped within 30s, the nitrogen is introduced, and the reactant is neutralized to be neutral by using NaOH. Standing, filtering, placing the filtrate into a rotary evaporator, and removing solvent benzene to obtain nonylphenol block polyether chloromethyl ether.
190g of nonylphenol block polyether chloromethyl ether were taken and placed in a reaction vessel, 17.3g of 3-aminopropene was added, and 31g of aqueous ammonia (23%) was added.
And (3) closing the reaction kettle, starting stirring, adjusting the reaction temperature to 75-80 ℃, connecting a vacuum pump after the reaction is carried out for 4 hours, evaporating excessive ammonia and water in the reactant under a negative pressure state, and cooling the reactant to room temperature after the evaporation is completed.
Adding ethanol with the same mass as the reactant, stirring uniformly, standing for precipitation, filtering with a G3 sand core funnel, removing ethanol in the filtrate with a rotary evaporator to obtain the final active lipophilic monomer alkyl block polyether propylene methyl amine ether (GABA).
200g of itaconic acid and 300.9g of isoamyl alcohol are added into a three-neck flask, 1.5g of concentrated sulfuric acid is added into the three-neck flask, a stirring paddle is inserted into the three-neck flask, a condenser is connected, the reaction temperature is 80-85 ℃, and the esterification reaction is carried out for 1h. Connecting a vacuum pump, increasing the reaction temperature until the added isoamyl alcohol can be distilled out, condensing the isoamyl alcohol by a condensing tube, then entering a separating funnel with a 4A molecular sieve, and returning alkyl alcohol to a three-neck flask to continue the reaction after water is absorbed by the 4A molecular sieve. And repeating the process for three times, titrating the esterification rate by an acid-base titration method, connecting a three-neck flask with a vacuum pump when the conversion rate is more than or equal to 98%, and completely evaporating out the isopropanol under a negative pressure state to obtain the final product of the diisopropyl itaconate (DBDI), wherein the molecular formula is shown as follows.
。
Into the reaction vessel were charged 46.02g of GABA, 19.36g of DBDI, 118.81g of acrylamide, 49.41g of sodium acrylate, 6.48g of trimethylpropenyl ammonium chloride, 480g of ultrapure water. 0.35g of potassium persulfate and 0.17g of sodium hydrogensulfite were dissolved in 10g of ultrapure water and charged into the reaction vessel. Introducing nitrogen, controlling the reaction temperature at 35-40 ℃, closing the reaction kettle, continuing introducing nitrogen for 20min, stopping introducing nitrogen, and sealing the reaction kettle. After 4 hours of reaction, the reaction temperature was raised to 70℃and the reaction was continued for 3 hours. And after the reaction is finished, taking the gel out of the reaction kettle, granulating, and drying to obtain the final amphoteric polymer surfactant, wherein the structural general formula of the final amphoteric polymer surfactant is shown as follows.
And (5) analyzing product performance.
A Lu Shengshang-2 zone of the victory oil field, wherein the viscosity 817 mPa.s of thick oil in the zone is lower; the mineralization degree of injected water is 3614mg/L, and the content of calcium and magnesium ions is less. Therefore, the viscosity of the thickened oil is reduced, and meanwhile, the oil-water interfacial tension is greatly reduced, so that a good oil displacement effect can be achieved.
And detecting the synthetic product according to the technical requirement of the thickened oil viscosity reducer for synergistic polymer flooding of the standard Q/SH CG0156-2021 of the petrochemical industry.
。
Example 3
Synthesis and application of a temperature-resistant salt-resistant thickened oil viscosity-reducing oil displacement agent.
200g of coconut oil alcohol block polyether C14-EO (9) PO (5) is added into a jacketed reaction kettle, 7.34g of trioxymethylene is added, and 400g of benzene is added as a solvent. The reaction vessel was closed and stirred well, and the reaction temperature was maintained at 10-15 ℃.
After stirring for 30min, 12.32g of HCl gas is slowly introduced, the reaction temperature is maintained at 10-15 ℃, the air inlet valve is closed, and the reaction is continued for 2h.
After the reaction is completed, nitrogen is introduced from the bottom of the reaction kettle, the residual HCl in the kettle is brought into a NaOH absorption tower by using nitrogen, after 40min, the reaction kettle is detected by using wet pH test paper, pH=5 is stopped within 30s, the nitrogen is introduced, and the reactant is neutralized to be neutral by using NaOH.
Standing, filtering, placing the filtrate into a rotary evaporator, and removing solvent benzene to obtain the coco-oleyl-block polyether chloromethyl ether.
。
210g of coconut oil alcohol block polyether chloromethyl ether was taken and placed in a reaction kettle, 13.95g of 3-aminopropene was added, and 24.55g of ammonia water (23%) was added.
The reaction kettle is closed, stirring is started, and the reaction temperature is adjusted to 75-80 ℃. After 4h of reaction, a vacuum pump is connected, excessive ammonia and water in the reactant are evaporated under a negative pressure state, and the reactant is cooled to room temperature after the evaporation is completed.
Adding ethanol with the same mass as the reactant, stirring uniformly, standing for precipitation, filtering with a G3 sand core funnel, removing ethanol in the filtrate with a rotary evaporator to obtain the final active lipophilic monomer alkyl block polyether propylene methyl amine ether (GABA).
200g of itaconic acid and 227.52g of isoamyl alcohol are added into a three-neck flask, 1.3g of concentrated sulfuric acid is added into the three-neck flask, a stirring paddle is inserted into the three-neck flask, a condenser is connected, the reaction temperature is 80-85 ℃, and the esterification reaction is carried out for 1h. Connecting a vacuum pump, increasing the reaction temperature until the added isobutanol can be distilled out, condensing the isobutanol through a condensing tube, then entering a separating funnel with a 4A molecular sieve, and returning the isobutanol to a three-neck flask after water is absorbed by the 4A molecular sieve to continue the reaction. The process is repeated three times, and the esterification rate is titrated by an acid-base titration method.
When the conversion rate is more than or equal to 98%, the three-neck flask is connected with a vacuum pump, and isobutanol is completely distilled off under a negative pressure state, so that the final product diisobutanol itaconate (DBDI) is obtained, and the molecular formula is shown as follows.
17.41g of GABA, 17.77g of DBDI, 78.26g of acrylamide, 34.52g of sodium acrylate, 49.58g of 2-acrylamido-2-methylpropanesulfonic acid, 12.45g of trimethylammonium chloride and 480g of ultrapure water were charged into the reaction vessel. 0.35g of potassium persulfate and 0.17g of sodium hydrogensulfite were dissolved in 10g of ultrapure water and charged into the reaction vessel. Introducing nitrogen, controlling the reaction temperature at 35-40 ℃, closing the reaction kettle, continuing introducing nitrogen for 20min, stopping introducing nitrogen, and sealing the reaction kettle. After 4 hours of reaction, the reaction temperature was raised to 70℃and the reaction was continued for 3 hours. And after the reaction is finished, taking the gel out of the reaction kettle, granulating and drying to obtain the final amphoteric polymer surfactant. The structural general formula is shown as follows.
Analyzing the performance of the product;
the reclamation of the oil extraction factory in the current river of the victory oil field is-119, the viscosity of the thickened oil of the block is 53209 mPa.s, and the block belongs to super thickened oil; the mineralization degree of injected water is 72011mg/L, the mineralization degree is higher, and the stratum temperature is 130 ℃.
Therefore, the thickened oil viscosity-reducing oil displacement agent needs to be stably dissolved under high mineralization degree and is not flocculated; maintaining the viscosity reduction rate and stability at high temperature; has certain interfacial tension reducing capability.
And detecting the synthetic product according to the technical requirement of the thickened oil viscosity reducer for synergistic polymer flooding of the standard Q/SH CG0156-2021 of the petrochemical industry.
2-4 of acrylamide, sodium acrylate, 2-acrylamide-2-methylpropanesulfonic acid and trimethyl propenyl ammonium chloride, wherein the acrylamide can improve the molecular flexibility of the high molecular surfactant and improve the water solubility; sodium acrylate can play roles in resisting monovalent ions such as sodium, potassium and the like; 2-acrylamide-2-methylpropanesulfonic acid can greatly improve the capability of the macromolecular surfactant for resisting divalent ions such as calcium, magnesium and the like; the trimethyl propenyl ammonium chloride is matched with the two lipophilic monomers provided by the invention, so that the effect of improving the interfacial activity can be achieved.
The high molecular surfactant has the viscosity similar to that of polyacrylamide for oil extraction, and can play a certain role in profile control; the oil-displacing agent has good crude oil emulsifying capacity and good oil-displacing effect; the oil-water interfacial tension can reach (1-5) x 10 -2 mN/m has certain low tension oil displacement capacity. The amphoteric polymer surfactant provided by the invention can be applied to a thickened oil viscosity reducer, a thickened oil viscosity reducer oil displacement agent and a conventional oilfield profile control and displacement integrated agent.
The above is merely a further embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and any person skilled in the art will be able to apply equivalents and modifications according to the technical solution and the concept of the present invention within the scope of the present invention disclosed in the present invention.
Claims (5)
1. The thickened oil viscosity reducer for oil displacement is characterized in that: the preparation method comprises the following raw materials:
alkyl block polyether propylene methyl amine ether, itaconic acid di-isomeric alkyl esters;
2-4 of acrylamide, sodium acrylate, 2-acrylamide-2-methylpropanesulfonic acid and trimethyl propenyl ammonium chloride are selected;
the alkyl block polyether propylene methyl amine ether has the molecular structure as follows:
；
wherein R is 1 Represents a C8-C22 fatty alcohol or a C8-C12 alkylphenol; n is equal to 3-10; m is equal to 2-6;
the molecular structure of the itaconic acid di-isomeric alkyl ester is as follows:wherein R is 2 Represents an isopolyol including isobutanol, isopropanol, isoamyl alcohol.
2. The method for synthesizing the thickened oil viscosity reducer for oil displacement according to claim 1, which is characterized in that: the method comprises the following steps:
step one: adding 2-4 of alkyl block polyether propylene methyl amine ether, itaconic acid di-isomeric alkyl ester, acrylamide, sodium acrylate, 2-acrylamide-2-methylpropanesulfonic acid and trimethyl propenyl ammonium chloride into a polymerization reaction kettle;
step two: starting the polymerization reaction kettle to perform electric stirring, heating to maintain the reaction temperature at 35-40 ℃, and stirring for 30-40min to uniformly mix the materials;
step three: adding an initiator into a polymerization reaction kettle, introducing nitrogen, controlling the reaction temperature to be 35-40 ℃ and the reaction time to be 6-8 hours;
step four: closing the polymerization reaction kettle, continuously introducing nitrogen for 20min, stopping introducing nitrogen, and sealing the reaction kettle for reaction for 6h;
step five: and after the sealing reaction is finished, taking the gel in the polymerization reaction kettle out of the reaction kettle, granulating and drying to obtain the thickened oil viscosity reducer.
3. The method for synthesizing the thickened oil viscosity reducer for oil displacement according to claim 2, which is characterized in that: the specific synthesis method of the alkyl block polyether propylene methyl amine ether in the step one comprises the following steps:
s1: adding alkyl block polyether and trioxymethylene into a jacketed reaction kettle, and adding benzene as a solvent according to 2-3 times of the total reactant mass;
s2: fully stirring the closed jacket reaction kettle, maintaining the reaction temperature at 5-15 ℃, and stirring for 30min;
s3: placing an HCl storage tank on a balance with a 5Kg measuring range, connecting an outlet of the HCl storage tank with a reaction kettle, slowly introducing HCl gas, determining the addition amount of HCl through the mass change of the HCl storage tank, maintaining the reaction temperature at 5-15 ℃, closing an air inlet valve, and continuing the reaction for 2 hours;
s4: after the reaction is finished, introducing nitrogen from the bottom of the jacketed reaction kettle, taking the residual HCl in the jacketed reaction kettle into a NaOH absorption tower by using nitrogen, detecting tail gas by using wet pH test paper every 10min, and stopping introducing nitrogen after the HCl gas in the jacketed reaction kettle is completely removed if the pH value in 30s is more than 3;
s5: neutralizing reactants in a jacket reaction kettle to be neutral by NaOH, standing, filtering, putting filtrate into a rotary evaporator, and removing solvent benzene by evaporation under the condition of negative pressure at 90 ℃ to obtain alkyl block polyether chloromethyl ether;
s6: adding alkyl block polyether chloromethyl ether and 3-aminopropene into a jacketed reaction kettle according to the molar ratio of 1:1.05-1.10, and adding ammonia water according to 1.2 times of the molar amount of the alkyl block polyether chloromethyl ether;
s7: closing the jacketed reaction kettle, starting stirring, adjusting the reaction temperature to 75-80 ℃ and reacting for 4 hours;
s8: connecting the jacketed reaction kettle with a vacuum pump, evaporating excessive ammonia and water in the reactant under a negative pressure state, and cooling the reactant to room temperature after the evaporation is completed;
s9: adding ethanol with the same mass as the reactant, stirring uniformly, standing for precipitation, filtering by using a G3 sand core funnel, transferring the filtrate to a single-neck flask, and removing the ethanol by using a rotary evaporator under the condition of negative pressure at 90 ℃ to obtain the alkyl block polyether propylene methyl amine ether.
4. The method for synthesizing the thickened oil viscosity reducer for oil displacement according to claim 2, which is characterized in that: the specific synthesis method of the itaconic acid di-isomer alkyl ester in the first step comprises the following steps:
step 1: adding itaconic acid and isopolyalkyl alcohol according to a molar ratio of 1:2.2-2.6 into a three-neck flask, adding concentrated sulfuric acid with a total material amount of 0.1-0.5%, inserting a stirring paddle into the three-neck flask, and connecting a condenser, wherein the added material amount is the mass of the added material amount;
step 2: the reaction temperature is selected between 70 ℃ and 100 ℃ according to different reactants, esterification reaction is carried out for 1h, and the reaction temperature is increased until the added isomeric alkyl alcohol can be distilled out;
step 3: the isomeric alkyl alcohol is condensed by a condensing tube, enters a separating funnel with a 4A molecular sieve, returns to a three-neck flask after water is absorbed by the 4A molecular sieve, and continues to react for three times;
step 4: and titrating the esterification rate by an acid-base titration method, connecting a three-neck flask with a vacuum pump when the conversion rate is more than or equal to 98%, and completely evaporating the isomeric alkyl alcohol under a negative pressure state to obtain the product itaconic acid di-isomeric alkyl ester.
5. The method for synthesizing the thickened oil viscosity reducer for oil displacement according to claim 3, which is characterized in that: the molar ratio of the alkyl block polyether to the trioxymethylene is 1:0.34-0.38.
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