CN109971448B - Twin-chain surfactant type thickened oil viscosity reducer - Google Patents
Twin-chain surfactant type thickened oil viscosity reducer Download PDFInfo
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- CN109971448B CN109971448B CN201910327127.7A CN201910327127A CN109971448B CN 109971448 B CN109971448 B CN 109971448B CN 201910327127 A CN201910327127 A CN 201910327127A CN 109971448 B CN109971448 B CN 109971448B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
- C07C233/65—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
Abstract
The invention discloses a thickened oil viscosity reducer formed by twin-chain surfactants. The heavy oil viscosity reducer with the twin-chain surfactant type has strong interface adsorption and can form 10 degrees of adsorption with crude oil‑3mN·m‑1The interfacial tension is reduced to 10 in 5-10 minutes, and the effect time is short‑3mN·m‑1(ii) a The invention has the characteristics of rigidity, salt resistance and high temperature resistance, can form pi-pi interaction with asphaltene molecules, is inserted into an asphaltene molecule aggregate, breaks the network structure of the aggregate, and thus reduces viscosity; can be used alone or together with polymer to form a binary oil displacement system, and can be used in tertiary oil recovery to improve the recovery rate of crude oil.
Description
Technical Field
The invention belongs to the technical field of oil field processing, and relates to a heavy oil viscosity reducer of a twin-chain surfactant type.
Background
The thickened oil is mainly a mixture of various hydrocarbons and non-hydrocarbons, and the crude oil has different physical properties when the relative contents of various components are different. The crude oil containing much normal paraffin has high solidifying point, and the crude oil containing much colloid and asphaltene has high viscosity. For crude oil, the contents and compositions of solid hydrocarbons, asphaltenes and colloids are the main factors determining the fluidity of the crude oil, and the heavy oil has particularly high contents of asphaltenes and colloids, complex structures and large molecular weights. Research on asphaltene and colloid shows that the molecules of the asphaltene and the colloid contain hydroxyl, carboxyl or amino which can form hydrogen bonds, and the asphaltene and the colloid have surface activity per se. Therefore, there are strong interactions between colloid molecules, asphaltene molecules, and between colloid and asphaltene molecules, and the aromatic fused ring planes of asphaltene molecules are stacked one on top of the other and fixed by hydrogen bonds between polar groups to form asphaltene particles. Colloid molecules are piled up on the surface of the asphaltene particles in an overlapping mode through aromatic fused ring planes and are fixed by hydrogen bonds to form a coating layer of the asphaltene particles, and the particles can be connected with each other through the hydrogen bonds, so that the high viscosity of the thick oil is caused.
The viscosity reduction of the thick oil is an important link in oil field production, and the surfactant type thick oil viscosity reducer can efficiently disperse or emulsify the thick oil, remarkably reduce the flow resistance of the thick oil, reduce the energy consumption in the exploitation process, improve the exploitation efficiency and increase the exploitation benefit. The thickened oil viscosity reducer containing the biphenyl structure can generate pi-pi interaction with aromatic condensed rings in asphaltene molecules, so that the thickened oil viscosity reducer is inserted into the asphaltene molecules to break the network structure of the asphaltene molecules, thereby reducing the viscosity and having excellent viscosity reduction effect.
Disclosure of Invention
The invention aims to provide a twin-chain surfactant type heavy oil viscosity reducer. The surfactant type heavy oil viscosity reducer with the twin chain can reduce the oil-water interfacial tension to be ultra-low, and is suitable for being applied to tertiary oil recovery to improve the crude oil recovery rate.
The invention claims a compound shown in a formula I,
in the formula I, R1＝CnH2n+1，n＝2～32；R2＝CnH2n+1，n＝2～32。
Specifically, the R is1And R2The total number of carbon atoms in (A) may be specifically 10 to 20; more particularly 15 to 18; and may be C16H33。
The invention provides a method for preparing the compound shown in the formula I, which comprises the following steps: 3,3',4,4' -biphenyl tetracarboxylic dianhydride shown in formula II and RNH2Carrying out condensation reaction to obtain;
the RNH2Wherein R is at least one of alkyl with 2-32, 4-16, 4-10, 10-16, 10-12 or 12-16 carbon atoms.
In the above method, R is specifically at least one of a butyl group, an octyl group, a dodecyl group, and a hexadecyl group;
3,3',4,4' -biphenyl tetracarboxylic dianhydride and RNH shown in the formula II2The feeding molar ratio of (1): 0.5 to 0.51; specifically 1: 0.501;
in the condensation reaction step, the temperature is 10-15 ℃; the time is 2 to 18 hours;
the method further comprises the following steps: after the condensation step, the solids content of the system is adjusted to 5-7 wt% (e.g., 6 wt%) for 2 hours before the cold bath is removed. Stirring was carried out at room temperature for 12 hours to allow the reaction to proceed more thoroughly and to increase the yield.
The condensation reaction is carried out in a solvent; the solvent is specifically selected from at least one of NMP, dichloromethane and toluene.
In addition, the thick oil viscosity reducer taking the compound shown in the formula I as an active ingredient also belongs to the protection scope of the invention.
The heavy oil viscosity reducer claimed by the invention comprises the compound shown in the formula I provided by the invention.
The viscosity reducer for thickened oil can also comprise mineralized water;
the dosage ratio of the compound shown in the formula I to the mineralized water is specifically 1 mg: 0.5-100 mL; specifically, 1 mg: 0.5-5 mL.
The heavy oil viscosity reducer can be used for onshore high-viscosity heavy oil viscosity reduction pipeline transportation, and can also be applied to ordinary low-permeability oil reservoirs, carbonate oil reservoirs, conventional sandstone oil reservoirs or polymer injection to improve the recovery efficiency.
The method for preparing the thick oil viscosity reducer comprises the following steps: the compound shown in the formula I and mineralized water are stirred for 0.2-0.5 h at the temperature of 25-95 ℃ to obtain the compound.
In addition, the application of the thickened oil viscosity reducer provided by the invention in reducing the viscosity of thickened oil or tertiary oil recovery also belongs to the protection scope of the invention.
Specifically, the dosage ratio of the thickened oil viscosity reducer to the thickened oil is 1 g: 1-100 g;
the salinity range tolerated by the thick oil viscosity reducer is as follows: the total mineralization is 0-40000ppm, and the total concentration of calcium and magnesium ions is 0-3000 ppm.
The thickened oil viscosity reducer with the twin-chain surfactant type provided by the invention has the following beneficial effects:
1. the twin chain surface active type heavy oil viscosity reducer provided by the invention can be a pure substance of twin chain surface active agents with a single carbon chain length or a mixture of twin chain surface active agents with multiple carbon chain lengths, and has strong synergistic effect when being used with other surface active agents or being compounded with polymers for oil displacement. The thick oil viscosity reducer has strong oil-water interface adsorption tendency, and is assembled in situ to form a predetermined interface layer, so that the oil-water interface tension is reduced to be lower than 10-3mN·m-1After the induced adsorption on the interface, the interface layer generated by assembly is less influenced by the composition of crude oil, and has good oil reservoir adaptability. The viscosity reducer for thickened oil also has the following excellent characteristics:
2. the twin-chain surfactant type heavy oil viscosity reducer provided by the invention has strong interface adsorption tendency, and can form 10 with crude oil without adding any auxiliary agent-3mN·m-1The ultra-low interfacial tension is short in effect time, and the oil-water interfacial tension can be reduced to 10 in 5-10 minutes-3mN·m-1。
3. The twin-chain surfactant type heavy oil viscosity reducer provided by the invention can still well reduce the interfacial tension at the temperature of 45-95 ℃ and under a higher mineralization degree, and has good salt resistance and good thermal stability.
4. The invention has the advantages of relatively single composition, stable product effect, simple process, easy control of reaction, low use concentration, strong applicability to different oil phases and strong broad spectrum.
5. The invention has the characteristics of rigidity, salt resistance and high temperature resistance, can form pi-pi interaction with asphaltene molecules, is inserted into an asphaltene molecule aggregate, breaks the network structure of the aggregate, and thus reduces viscosity; can be used alone or together with polymer to form a binary oil displacement system, and can be used in tertiary oil recovery to improve the recovery rate of crude oil.
Drawings
FIG. 1 shows the NMR spectrum of the product obtained in example 1.
FIG. 2 shows the NMR spectrum of the product obtained in example 2.
FIG. 3 is a nuclear magnetic spectrum of the product obtained in example 3.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are all commercially available from the open.
Example 1
The preparation method of the heavy oil viscosity reducer with the twin-chain surfactant type comprises the following steps: octylamine and 3,3',4,4' -biphenyltetracarboxylic dianhydride were used for the reaction.
Adding NMP solvent and octylamine reaction raw material into a reaction vessel with a mechanical stirrer, a nitrogen inlet and a cold water bath at 10-15 ℃, introducing nitrogen, and stirring for 20 minutes to obtain a clear solution. Then, 0.501 time octylamine corresponding to molar equivalent of BPDA was added in one batch, and solvent NMP was added to wash residual dianhydride, and the solid content of the reaction solution was adjusted to 6 wt%. The cold bath was taken out after 2 hours. Stirring for 12 hours at room temperature, filtering and purifying to obtain the dialkyl amide biphenyl dicarboxylic acid.
The structure of the product was confirmed as shown in FIG. 1. As can be seen from the figure, the product has a correct structure and is the target product.
Example 2
The preparation method of the heavy oil viscosity reducer with the twin-chain surfactant type comprises the following steps: butylamine, octylamine, dodecylamine, hexadecylamine and 3,3',4,4' -biphenyltetracarboxylic dianhydride were used for the reaction.
Adding NMP solvent and alkylamine with the mol percentages of 3.5 mol%, 5.5 mol%, 16 mol% and 75 mol% in sequence into a reaction vessel with a mechanical stirrer, a nitrogen inlet and a cold water bath and at the temperature of 10-15 ℃, introducing nitrogen, stirring for 20 minutes and obtaining a clear solution. Then, 0.501 times the total molar equivalent of BPDA for each alkylamine was added in one batch, and a solvent NMP was added to wash the residual dianhydride, and the solid content of the reaction solution was adjusted to 6 wt%. The cold bath was taken out after 2 hours. Stirring for 12 hours at room temperature, filtering and purifying to obtain the dialkyl amide biphenyl dicarboxylic acid.
The structure of the product was confirmed as shown in FIG. 2. As can be seen from the figure, the product has a correct structure and is the target product.
Example 3
The preparation method of the heavy oil viscosity reducer with the twin-chain surfactant type comprises the following steps: hexadecylamine and 3,3',4,4' -biphenyl tetracarboxylic dianhydride were used for the reaction.
Adding NMP solvent and hexadecylamine serving as a reaction raw material into a reaction vessel with a mechanical stirrer, a nitrogen inlet and a cold water bath at 10-15 ℃, introducing nitrogen, and stirring for 20 minutes to obtain a clear solution. Then, 0.501 times of hexadecylamine corresponding to molar equivalent of BPDA was added in one batch, and solvent NMP was added to wash residual dianhydride, and the solid content of the reaction solution was adjusted to 6 wt%. The cold bath was taken out after 2 hours. Stirring for 12 hours at room temperature, filtering and purifying to obtain the dialkyl amide biphenyl dicarboxylic acid.
The structure of the product was confirmed as shown in FIG. 3. As can be seen from the figure, the product has a correct structure and is the target product.
Example 4
The viscosity reducing effect of the thickened oil viscosity reducer of the twin-chain surfactant type prepared in examples 1 to 3 was measured.
Sodium chloride 3.0 xl 0 was used4Preparing the heavy oil viscosity reducer with twin-chain surfactant types with different concentrations by mg/L saline water. At the temperature of 65 ℃, adding 25ml of an electro-stripped crude oil sample of a certain oil field in Bohai sea into a 50ml test tube with a plug, continuously adding 25ml of a thickened oil viscosity reducer solution with a surfactant type twin chain, tightly covering a test tube plug, and then oscillating manually or placing the test tube in an oscillation box, horizontally oscillating for 80-100 times, wherein the amplitude is more than 20 cm. After being fully mixed, the viscosity of a mixed system after the viscosity reduction of the thick oil is measured by using a Brookfield viscometer at 65 ℃, and the viscosity reduction rate of the thick oil is calculated according to the following formula:
the results are shown in Table 1.
Table 1, examples 1-3 viscosity reduction results for heavy oil viscosity reducers with twin-chain surfactant types
From table 1, it can be seen that the thickened oil viscosity reducer of the twin-chain surfactant type prepared in examples 1 to 3 has a good thickened oil viscosity reduction effect, and the thickened oil viscosity reducer prepared in example 2 has an optimal viscosity reduction effect on thickened oils of different viscosities.
Claims (9)
1. A thickened oil viscosity reducer which takes the compound shown in the formula I as an active ingredient;
in the formula I, R1＝CnH2n+1，n＝2～32；R2＝CnH2n+1，n＝2～32。
2. The viscosity reducer for thick oil according to claim 1, characterized in that: the R is1And R2Are all C16H33。
3. A viscosity reducer for thickened oil comprises a compound shown as a formula I;
in the formula I, R1＝CnH2n+1，n＝2～32；R2＝CnH2n+1，n＝2～32。
4. The viscosity reducer for thick oil according to claim 3, characterized in that: the R is1And R2Are all C16H33。
5. The thick oil viscosity reducer according to claim 3 or 4, characterized in that: the thick oil viscosity reducer also comprises mineralized water;
the dosage ratio of the compound shown in the formula I to the mineralized water is specifically 1 mg: 0.5-100 mL.
6. The viscosity reducer for thick oil according to claim 5, characterized in that: the dosage ratio of the compound shown in the formula I to the mineralized water is 1 mg: 0.5-5 mL.
7. A process for preparing the thick oil viscosity reducer of any one of claims 3-6, comprising: the compound shown in the formula I and mineralized water are stirred for 0.2-0.5 h at the temperature of 25-95 ℃ to obtain the compound.
8. The use of the thick oil viscosity reducer of any one of claims 3-6 in reducing the viscosity of thick oil or in tertiary oil recovery.
9. Use according to claim 8, characterized in that: the dosage ratio of the thickened oil viscosity reducer to the thickened oil is 1 g: 1-100 g;
the salinity range tolerated by the thick oil viscosity reducer is as follows: the total mineralization is 0-40000ppm, and the total concentration of calcium and magnesium ions is 0-3000 ppm.
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