CN107573916B - Low-concentration efficient composite oil displacement composition - Google Patents
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Abstract
The invention relates to the field of oil extraction in oil fields, in particular to a low-concentration high-efficiency compound oil displacement composition, which comprises the following components: sodium lauryl sulfate, N-dodecyl-N-methylpyrrolidine bromide and partially hydrolyzed polyacrylamide. The composition has simple components, adopts an anionic surfactant, a cationic surfactant or an increasable nonionic surfactant and a cosurfactant to form the surfactant oil displacement group respectively, breaks the taboo of using the anionic surfactant and the cationic surfactant at the same time, is further combined with a polymer oil displacement component, fully utilizes the advantages of the surfactant oil displacement and the polymer oil displacement, and can comprehensively improve the oil extraction efficiency. Compared with the common oil displacement composition product, the composition has less dosage when forming an oil displacement solution, can obviously reduce the oil extraction cost, generates great economic benefit and has potential market value.
Description
Technical Field
The invention relates to the field of oil extraction in oil fields, in particular to a low-concentration high-efficiency compound oil displacement composition.
Background
After primary oil recovery and secondary oil recovery, 60 to 70 percent of residual oil still remains underground in most oil fields in China and is difficult to extract, and the oil fields enter a tertiary oil recovery stage at present. The tertiary oil recovery adopts a physical and chemical method, changes the properties, phase states and interface effects of the fluid, and enlarges the swept range of injected water so as to improve the oil displacement efficiency. The current chemical methods for improving the recovery ratio can be divided into alkali flooding, polymer flooding, surfactant flooding and compound flooding developed on the basis of the alkali flooding, the polymer flooding and the surfactant flooding. Alkali flooding presents a serious problem, such as reservoir plugging, scaling, equipment corrosion, and other environmental problems, and currently, few or even some oil fields are prohibited from using alkali flooding. Compared with alkali flooding, polymer flooding and surfactant flooding have many advantages, which can not only effectively avoid the above problems, but also effectively increase sweep efficiency and reduce water-oil fluidity ratio, and the surfactant can greatly reduce oil/water interfacial tension and change wettability, and the combined use of the polymer flooding and the surfactant flooding can effectively improve oil extraction efficiency and bring huge economic benefits.
The prior binary compound oil displacement formula of polymer/surfactant has some defects, the components of the surfactant in the related formula are complex, the mass concentration of the surfactant in the prepared oil displacement solution is mostly 0.3-0.5%, most of the surfactant is prepared by simple active agents (more than 3) and added with cosurfactant, the total mass concentration of the surfactant is still more than 0.1% generally, the dosage is more, and the price of the active agent is far higher than that of the polymer, so the high-concentration active agent increases the economic cost of the oil displacement solution. Meanwhile, the improvement of the binary composite flooding formula still has a space for further improving the oil extraction efficiency.
Disclosure of Invention
The invention aims to solve the technical problem of how to overcome the defects in the prior art and provide a low-concentration high-efficiency composite oil displacement composition.
The technical solution of the invention is as follows: a low-concentration high-efficiency compound oil displacement composition comprises the following components: sodium lauryl sulfate, N-dodecyl-N-methylpyrrolidine bromide and partially hydrolyzed polyacrylamide.
Further comprises fatty alcohol-polyoxyethylene ether AEO-9 and cosurfactant short-chain alcohol
Further, the cosurfactant short-chain alcohol is n-C2～C6An alcohol.
Further, the cosurfactant short-chain alcohol is n-butyl alcohol.
Further, the mass ratio of the sodium dodecyl sulfate to the N-dodecyl-N-methylpyrrolidine bromide is 1: 0.67 to 0.25.
Further, the low-concentration high-efficiency composite oil displacement composition comprises the following components in parts by weight: 25-45 parts of sodium dodecyl sulfate, 5-25 parts of N-dodecyl-N-methylpyrrolidine bromide, 5-20 parts of fatty alcohol-polyoxyethylene ether AEO-9, 5-15 parts of cosurfactant short-chain alcohol and 100-300 parts of partially hydrolyzed polyacrylamide.
Further, the low-concentration high-efficiency composite oil displacement composition comprises the following components in parts by weight: 40 parts of lauryl sodium sulfate, 10 parts of N-dodecyl-N-methylpyrrolidine bromide, 10 parts of fatty alcohol-polyoxyethylene ether AEO-9, 10 parts of cosurfactant short-chain alcohol and 200 parts of partially hydrolyzed polyacrylamide.
The oil displacement solution is formed by a low-concentration high-efficiency composite oil displacement composition, the mass concentration of the sodium dodecyl sulfate is 0.025-0.045%, the mass concentration of the N-dodecyl-N-methylpyrrolidine bromide is 0.005-0.025%, the mass concentration of the fatty alcohol-polyoxyethylene ether AEO-9 is 0.005-0.02%, the mass concentration of the cosurfactant short-chain alcohol is 0.005-0.015%, the mass concentration of the partially hydrolyzed polyacrylamide is 0.1-0.3%, and the balance is formation water.
Further, the oil displacement solution formed by the low-concentration high-efficiency composite oil displacement composition is characterized in that the mass concentration of the sodium dodecyl sulfate is 0.04%, the mass concentration of the N-dodecyl-N-methylpyrrolidine bromide is 0.01%, the mass concentration of the fatty alcohol-polyoxyethylene ether AEO-9 is 0.01%, the mass concentration of the cosurfactant short-chain alcohol is 0.01%, the mass concentration of the partially hydrolyzed polyacrylamide is 0.2%, and the balance is formation water.
The low-concentration high-efficiency composite oil displacement composition is simple in component, consists of an anionic surfactant, a cationic surfactant or an increasable nonionic surfactant, a cosurfactant and a polymer oil displacement component, and compared with the conventional composite oil displacement composition in which the anionic surfactant and the cationic surfactant are rarely used at the same time, the anionic surfactant and the cationic surfactant are simultaneously used, so that the compactness and the orderliness of the surfactants at an oil-water interface can be greatly improved, the oil-water interface tension is greatly reduced, and the emulsifying property is enhanced on the basis of reasonable dosage; the surfactant component is further combined with the polymer component, so that the sweep coefficient can be effectively increased, the water-oil fluidity ratio is reduced, and the compound oil displacement composition obviously improves the recovery ratio of crude oil on the whole.
When the composite oil displacement composition is used for forming an oil displacement solution, compared with a conventional product, the composite oil displacement composition has the advantages that the dosage of the surfactant component is less, the surfactant price is higher, the oil displacement cost can be greatly reduced, and the composite oil displacement composition has higher economic benefit.
Drawings
The invention is further illustrated by the following figures and examples.
FIG. 1 shows that the invention discloses a low-concentration high-efficiency composite oil-displacing composition cationic surfactant N-dodecyl-N-methylpyrrolidine bromide1HNMR characterization plot.
Detailed Description
The invention relates to a low-concentration high-efficiency complex oil-displacing composition.
Reagent and instrument preparation
1. Reagent preparation
Anionic surfactant sodium lauryl sulfate; 1-bromododecane, methylpyrrolidine, toluene, tetrahydrofuran; a nonionic surfactant, fatty alcohol-polyoxyethylene ether AEO-9; ethanol, n-butanol, n-hexanol; all above were analytically pure and purchased from Aladdin reagent company. Partially hydrolyzed polyacrylamides (molecular weight 2X 10)7Degree of hydrolysis 23%) was purchased from beijing gazette chemist group ltd.
The anionic surfactant petroleum sulfonate KPS is provided by Xinjiang oil field company of China; the zwitterionic surfactant, alkyl betaine JS-33, is provided by oil field company of eastern Ji of Petroleum, China; the nonionic surfactant alkyl glycoside APG is provided by Shanghai Kai chemical Co., Ltd.
The crude oil for experiments is Jidong oilfield crude oil (the density is 0.962g/mL, the viscosity at 50 ℃ is 608mPa & s, the freezing point is-0.3 ℃, the sulfur content is 0.16 wt%, the wax content is 4.7 wt%, the colloid asphaltene content is 27.6 wt%, and the acid value of the crude oil is 3.3 mgKOH/g); experimental water based on oil field formation water(Na++K+Total concentration 490Mg/L, Mg2+Concentration 11mg/L, Ca2+Concentration 33mg/L, Cl-At a concentration of 279mg/L, SO4 2-Concentration 43mg/L, HCO3Concentration 868mg/L, CO3 2-Concentration 25 mg/L).
2. Instrument preparation
High temperature and high pressure flow tester, purchased from petroleum research instruments ltd, haian county.
Preparation of di, cationic surfactant
The cationic surfactant N-dodecyl-N-methylpyrrolidine bromide is autonomously synthesized by a laboratory according to the method recorded by the prior literature, and the method comprises the following specific steps: (1) slowly dripping 1-bromododecane into a toluene solution of methyl pyrrolidine under the conditions of stirring and nitrogen protection; (2) after the dropwise addition is finished, heating the mixture to about 75 ℃, and reacting for 48 hours under the protection of nitrogen; (3) cooling the reactant after the reaction is finished, performing rotary evaporation to remove excessive toluene, performing suction filtration, and recrystallizing the product with tetrahydrofuran for at least three times to obtain a white powdery solid; (4) drying the obtained product in a vacuum drying oven at 60 ℃ for 48h1HNMR was characterized and used.
Third, example
The components and contents of the low-concentration high-efficiency composite flooding composition are selected and dissolved in experimental water to form flooding solutions of examples 1-14, and the components and contents are shown in Table 1.
TABLE 1 EXAMPLES 1-14 flooding solutions compositions and contents tabulated
Fourth, oil displacement effect experiment
1. Experimental procedure
The indoor simulated oil displacement experiment is carried out on a high-temperature high-pressure flow tester, and the method comprises the following specific steps:
(1) the sand filling core is self-made by 80-100 meshes of quartz sand by adopting a wet filling method, and the mass m of a blank sand filling pipe before sand filling is recorded0g and sand filledMass m1g；
(2) After the solid water is saturated, taking down the sand filling pipe, and weighing the wet weight of the sand filling pipe as m2g, determining the pore volume of the artificial rock core;
V＝(m2-m1-m0) /ρ, where V is the pore volume, cm3(ii) a Rho is the density of experimental water, g/cm3
(3) Placing the sand filling pipe in the step (2) in a constant temperature device at 65 ℃ (oil field stratum temperature), displacing core water with crude oil at the speed of 2.0mL/min until oil just comes out of a core outlet, and recording the volume V of the water out1Determining irreducible water saturation, Sw＝(V-V1)/V×100％，SwIrreducible water saturation,%; v2＝V-V1，V2Is the total crude oil volume in the core, cm3；
(4) Displacing with experimental water at a rate of 2.0mL/min, displacing with water until the water content of the outlet is more than 95%, and calculating the recovery ratio of crude oil, wherein R is (sigma V)i)/V2R is crude oil recovery ratio,%; sigma ViIs the volume of crude oil in the produced fluid, cm3；
(5) The injection speed was kept constant and the flooding solutions of examples 1-14 of 0.5PV were injected separately;
(6) and (5) continuing the experimental water drive until the water content at the outlet end reaches more than 95%, and calculating the crude oil recovery ratio.
2. Results of the experiment
The flooding efficiency of each example is shown in table 2.
Table 2 oil displacement efficiency tables of examples 1 to 14
3. Analysis of experiments
(1) From the experimental results of examples 1-4, it can be known that when the mass ratio of the sodium dodecyl sulfate to the N-dodecyl-N-methylpyrrolidine bromide is between 3:2 and 4:1, the recovery ratio of crude oil can be effectively improved by more than 20%; the mass ratio of the two is too large or too small, and the application effect is obviously poor; considering that the cost of N-dodecyl-N-methylpyrrolidine bromide is relatively high, the mass ratio of sodium dodecyl sulfate to N-dodecyl-N-methylpyrrolidine bromide in the mixed active agent is preferably 4: 1.
(2) The experimental results of the examples 4 to 6 show that the polymer concentration in the formula also has obvious influence on the oil displacement effect, and the experimental effect is obviously superior to that of the formula with the mass concentration of 0.1% when the mass concentration of 0.2% is achieved; but the concentration is increased to 0.3 percent, and the improvement degree is smaller when the recovery ratio is higher than 0.2 percent. The increase in polymer concentration has a greater effect on solution formulation time and increases cost, so the polymer concentration in the formulation is preferably 0.2%.
(3) From the experimental results of examples 4 and 7-9, it can be known that the recovery ratio can be improved by adding the nonionic surfactant fatty alcohol-polyoxyethylene ether AEO-9, and the preferable concentration is 0.01%.
(4) As can be seen from the experimental results of examples 10 to 14, the addition of the co-surfactant n-butanol contributes to the enhancement of the recovery efficiency more than other alcohols, and the preferred concentration is 0.01%.
4. Experimental comparison of preferred embodiment 11 with conventional flooding compositions
Comparative product 1: the anionic surfactant petroleum sulfonate KPS (wt%) is 0.15, and the content of the partially hydrolyzed polyacrylamide (wt%) is 0.2;
comparative product 2: 0.15 of petroleum sulfonate KPS (wt%) of anionic surfactant, 0.01 of n-butyl alcohol (wt%) and 0.2 of partially hydrolyzed polyacrylamide (wt%);
comparative product 3: 0.15 weight percent of zwitterionic surfactant alkyl betaine JS-33 and 0.2 weight percent of partially hydrolyzed polyacrylamide;
comparative product 4: 0.15 weight percent of zwitterionic surfactant alkyl betaine JS-33, 0.01 weight percent of n-butyl alcohol and 0.2 weight percent of partially hydrolyzed polyacrylamide;
comparative product 5: 0.15 percent of nonionic surfactant alkyl glycoside APG (wt percent) and 0.2 percent of partially hydrolyzed polyacrylamide (wt percent);
comparative product 6: 0.15 percent of nonionic surfactant alkyl glycoside APG (wt%), 0.01 percent of n-butyl alcohol (wt%) and 0.2 percent of partially hydrolyzed polyacrylamide (wt%).
The comparative products 1 to 6 were subjected to the oil displacement test described above, and compared with example 11, the oil displacement efficiency is shown in table 3.
Table 3 example 11 and the oil displacement efficiency table of the commonly used oil displacement composition
| Item | Water drive recovery ratio (%) | Enhanced recovery (%) |
| Example 11 | 33.4 | 32.9 |
| Comparative product 1 | 27.3 | 13.5 |
| Comparative product 2 | 34.1 | 14.3 |
| Comparative product 3 | 29.1 | 15.7 |
| Comparative product 4 | 24.9 | 12.3 |
| Comparative product 5 | 30.2 | 17.1 |
| Comparative product 6 | 27.6 | 14.9 |
Through the comparison experiment, the oil displacement performance of the surfactant of the composite oil displacement composition is still obviously superior to that of the surfactant of the common oil displacement composition under the condition of low concentration (0.07 wt%), and the high efficiency of the composition is further verified.
Fifth, oil displacement mechanism analysis
The key point in the formula of the composition is that an anion and cation surfactant compound system is adopted, which is very rare in the conventional surfactant formula system for oil displacement, and as mentioned above, the system has high efficiency.
The basic principle of the surfactant for improving the recovery ratio is mainly to reduce the number of capillary tubes by reducing the oil-water interfacial tension and form an oil-in-water emulsion by emulsification. The key to the two effects is whether the surfactant can be closely and orderly arranged at the oil-water interface. The conventional anionic surfactant system has relatively loose arrangement on the interface due to electrostatic repulsion between head groups, while the nonionic surfactant has relatively poor arrangement order on the interface due to the chain structure of hydrophilic groups and hydrophobic groups.
In the oil displacement composition, an anionic and cationic surfactant compound system is adopted, and traditional researches suggest that the anionic and cationic surfactants are compounded for use and particularly generate precipitates when the concentration ratio is 1: 1. The method effectively avoids the production of precipitates by reducing the total concentration of the surfactant, controlling the proportion of the anionic surfactant and the cationic surfactant and the like. Due to the electrostatic attraction effect between the head bases, the tightness and the order of the surfactant on an oil-water interface can be greatly improved. The molecular structure shows that the lauryl sodium sulfate head group is relatively small, and the N-lauryl-N-methyl pyrrolidine bromide head group is relatively large, so that a single N-lauryl-N-methyl pyrrolidine bromide head group is easier to interact with a plurality of lauryl sodium sulfate head groups, and when the mass ratio of the lauryl sodium sulfate to the N-lauryl-N-methyl pyrrolidine bromide is between 3:2 and 4:1, the compatibility of the lauryl sodium sulfate and the N-lauryl-N-methyl pyrrolidine bromide is best, the oil-water interfacial tension can be greatly reduced, the emulsifying property is enhanced, and the crude oil recovery rate is effectively improved.
Because the hydrophilic head groups of the ionic surfactant are relatively large, the head groups are closely arranged on the oil-water interface, but the hydrophobic chains are relatively loose. The hydrocarbon chain has certain flexibility, can generate certain bending, and is not beneficial to the orderly and compact arrangement of the active agent. The nonionic surfactant and the cosurfactant are added, so that gaps entering hydrophobic chains of the ionic surfactant can be effectively filled, and the mixed surfactant molecules on an oil-water interface are more closely arranged through the compatibility synergistic effect among carbon chains with different lengths, so that the oil-water interface activity of a system is further enhanced, and the crude oil recovery rate is greatly improved by over 10 percent.
The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes or modifications made in accordance with the spirit of the present disclosure are intended to be covered by the scope of the present disclosure.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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