CN107118753B - Viscosity-variable oil displacement agent composition free of macromolecules as well as preparation method and application thereof - Google Patents
Viscosity-variable oil displacement agent composition free of macromolecules as well as preparation method and application thereof Download PDFInfo
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- CN107118753B CN107118753B CN201710325209.9A CN201710325209A CN107118753B CN 107118753 B CN107118753 B CN 107118753B CN 201710325209 A CN201710325209 A CN 201710325209A CN 107118753 B CN107118753 B CN 107118753B
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- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
Abstract
The invention provides a variable viscosity oil-displacing agent composition free of macromolecules and a preparation method thereof. In parts by weight, theThe oil displacement agent comprises the raw materials of 0.5-10 parts of main agent, 0.5-5 parts of association agent, 0.5-2 parts of synergist and 83-98.5 parts of water. The oil displacement agent is characterized in that: a. the self viscosity is spontaneously generated in water environments with different salinity by 102‑1010A change in magnification; b. the viscosity of the self-viscosity is increased and reduced along with the change of the salinity, and the viscosity is increased and reduced in different salinity ranges; c. the viscosity is increased without the need of polyacrylamide and derivatives thereof, xanthan gum and other common polymer thickeners, and the viscosity increasing effect is much better than that of the polymer thickeners; d. has the capability of reducing the oil-water interfacial tension and emulsifying crude oil. The oil displacement agent is suitable for oil fields developed by water flooding, and the viscosity of the oil displacement agent in an oil reservoir can be changed spontaneously along with the difference of the water salinity of the stratum, so that the oil displacement agent meets the different requirements of different areas in the oil reservoir on the viscosity of the oil displacement agent.
Description
Technical Field
The invention relates to an oil displacement agent composition without high molecules and with variable viscosity, a preparation method and application thereof, in particular to an oil displacement agent composition without high-molecular thickening agent and with viscosity capable of being spontaneously increased and decreased in water environments with different salinity, a preparation method and application thereof, and belongs to the technical field of oil exploitation.
Background
The viscosity is an important property of the oil displacement agent, and the higher viscosity can obviously improve the oil displacement effect of the oil displacement agent. At present, oil displacement agents applied in the petroleum industry need to increase viscosity, added thickeners are generally high molecular substances, including polyacrylamide (HPAM) and derivatives thereof, xanthan gum and the like, and the viscosity generation principle is a steric effect generated after the high molecules are dissolved in water. Due to the strong influence of inorganic salt ions on the dielectric property of the solution, the viscosity of most oil displacement agents is in a decreasing relation with the salinity of the solution, namely, the viscosity of the oil displacement agent is kept to be reduced along with the increase of the salinity of the solution. Once the oil displacement agent with the viscosity decreasing along with the salinity is applied to an oil field with higher salinity, the oil displacement effect is seriously influenced because the viscosity of the oil displacement agent becomes very low. In recent years, although researchers have studied special salt-resistant polymers such as comb-shaped polymers and star-shaped polymers, which can alleviate the influence of salinity on the viscosity of an oil displacement agent, the monotonous decreasing relationship between the viscosity and the salinity cannot be changed.
The viscosity increasing mode of the existing oil displacement agent is realized by high molecules, the viscosity of the solution of the oil displacement agent is more or less negatively affected by salinity no matter the common polymer, xanthan gum or salt-resistant polymer, and the viscosity is reduced without exception after the oil displacement agent is injected into an oil reservoir.
Because the oil displacement agent which can not only increase the viscosity of the oil displacement agent per se but also reduce the viscosity of the oil displacement agent per se along with the increase of the salinity does not exist at present, in order to adapt to oil reservoirs with different salinity, particularly the oil displacement agent which has higher salinity, a variable-viscosity oil displacement agent composition without polymers needs to be developed in addition to the principle of polymer viscosification.
Disclosure of Invention
The invention aims to provide a variable-viscosity oil displacement agent composition without macromolecules as well as a preparation method and application thereof. The viscosity of the oil displacement agent composition can be spontaneously increased and decreased in water environments with different salinity, and the oil displacement agent composition can meet the different requirements of different areas in an oil reservoir on the viscosity of the oil displacement agent.
In order to achieve the above object, the present invention provides a variable viscosity oil-displacing agent composition containing no polymer, which comprises the following raw materials in parts by weight:
in the above oil-displacing agent composition, preferably, the main agent is represented by the general formula R1CON(R2OH)(R3OH) amide type nonionic surfactant, wherein R is1May be a hydrocarbyl or substituted phenyl radical, R2OH may be hydroxyalkyl, hydroxyphenyl, substituted hydroxyphenyl or hydroxycycloalkyl, R3OH may be hydroxyalkyl, hydroxyphenyl, substituted hydroxyphenyl or hydroxycycloalkyl.
More preferably, said R1The hydrocarbon group is selected from straight-chain hydrocarbon group with carbon number of 1-38, branched-chain hydrocarbon group with carbon number of 1-38, aromatic hydrocarbon group with carbon number of 6-38 and cyclic hydrocarbon group with carbon number of 3-38, and the hydrocarbon group can be saturated hydrocarbon group or unsaturated hydrocarbon group; further preferably, the cyclic hydrocarbon group having a carbon number of 3 to 38 is a cycloalkyl group having a carbon number of 6 to 38;
the R is1The substituent of the substituted phenyl is selected from halogen element, amino, nitro, hydroxyl, aldehyde group, carboxyl, straight chain alkyl and branched chain alkyl with carbon number of 1-38 substituted or unsubstituted by halogen element, ketone group with carbon number of 0-38 and alkoxy with carbon number of 0-38; further preferably, said R1The number of the substituted positions in the substituted phenyl can be 1-5, and the position relation among the substituents can be one or the combination of more of ortho-position, meta-position and para-position;
the R is2OH and R3The hydroxyalkyl groups represented by OH are independently selected from linear hydroxyalkyl groups having 1 to 6 carbon atoms and branched hydroxyalkyl groups having 1 to 6 carbon atoms;
the R is2OH and R3The substituent of the substituted hydroxyphenyl group represented by OH is independently selected from linear alkyl and branched alkyl with carbon number of 1-4, halogen element, amino, nitro, hydroxyl, aldehyde group, ketone group, alkoxy and carboxyl; further preferably, theR2OH and R3The number of the substitution positions in the substituted hydroxyphenyl group represented by OH can be 1-5 respectively and the position relation among the substituents can be one or the combination of more of ortho-position, meta-position and para-position;
the R is2OH and R3The hydroxycycloalkyl groups represented by OH are each independently selected from hydroxycycloalkyl groups having 6 to 10 carbon atoms.
In the oil-displacing agent composition, the general formula R of the main agent1CON(R2OH)(R3OH), particularly preferably, the R1Is saturated aliphatic hydrocarbon group with carbon number of 1-38, unsaturated aliphatic hydrocarbon group with carbon number of 1-38, halogenated phenyl or halogenated tolyl, and the R2OH and R3Each OH is independently selected from hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxyisopropyl.
In the above oil-displacing agent composition, preferably, the association agent is an anionic surfactant; more preferably, the association agent comprises a polyoxyethylene type anionic surfactant; further preferably, the polyoxyethylene type anionic surfactant is a substituted polyoxyethylene ether sulfate and/or a substituted polyoxyethylene ether sulfonate. Among them, the substituent is preferably selected from an alkoxy group having 1 to 38 carbon atoms and an alkylphenoxy group having 6 to 38 carbon atoms.
In the above oil-displacing agent composition, preferably, the synergist is a hydrocarbyl sulfate; more preferably, the synergist is an alkyl sulfate having a carbon number of 8-30.
According to an embodiment of the present invention, preferably, the viscosity-variable oil displacement agent composition raw material composition without the macromolecule comprises, in parts by weight: 2-10 parts of main agent, 1-5 parts of association agent, 0.5-2 parts of synergist and 83-96.5 parts of water to supplement to 100 parts.
According to an embodiment of the present invention, preferably, the variable viscosity oil-displacing agent composition containing no polymer is prepared by: adding 0.5-10 parts (more preferably 2-10 parts) of main agent into 83-98.5 parts (more preferably 83-96.5 parts) of water at room temperature, stirring for 4-8 hours to obtain a main agent aqueous solution, heating to 38-42 ℃, adding 0.5-5 parts (more preferably 1-5 parts) of association agent into the main agent aqueous solution, stirring for 1-3 hours, cooling to room temperature, adding 0.5-2 parts of synergist, stirring for 1-3 hours, and standing for 18-30 hours to obtain the oil displacement agent composition with variable viscosity and without polymers.
According to an embodiment of the present invention, preferably, the viscosity-variable oil-displacing agent composition without polymer has its own viscosity capable of 10 at different salinity2-1010The change in magnification. More preferably, the viscosity-variable oil-displacing agent composition without the polymer has a change in viscosity of itself ranging from 0.1 mPa-s to 2 x 10 at different salinity8mPa·s。
The oil displacement agent composition provided by the invention has the following characteristics: a. the self viscosity can spontaneously generate 10 in water environments with different salinity2-1010A change in magnification; b. the viscosity of the self-viscosity-variable-salt-free water-based seawater desalination system is changed along with the increase of salinity, namely, the viscosity is increased and reduced, and the changes of two different trends occur in different salinity ranges; c. the viscosity is increased without the need of polyacrylamide, derivatives thereof, xanthan gum and other common polymer thickeners, and the viscosity is much higher than the tackifying effect of the polymer thickeners; d. has the capability of reducing the oil-water interfacial tension and emulsifying crude oil. The oil displacement agent composition provided by the invention is particularly suitable for exploiting residual crude oil in oil fields which have passed through a water-flooding development stage.
In the invention, the change of the self viscosity of the oil displacement agent composition along with the increase of salinity has viscosity increase and viscosity reduction effect, and the mechanism of the special property is that the main agent nonionic surfactant and the association agent anionic surfactant respectively react in low, medium and high salinity environments to generate low-viscosity spherical micelles, high-viscosity rod micelles and low-viscosity spherical micelles, which are shown in formulas (1) to (3):
low salinity environment: main agent (solution) + association agent (solution) → spherical micelles (low viscosity) (1),
medium salinity environment: main agent (solution) + association agent (solution) → rod-like micelles (high viscosity) (2),
high salinity environment: main agent (solution) + association agent (solution) → spherical micelles (low viscosity) (3).
The synergist anionic surfactant of the invention has the effect of making the viscosity of the spherical micelle generated by the reaction higher.
In addition, the invention also provides a preparation method of the oil displacement agent composition with variable viscosity, which comprises the following steps: adding 0.5-10 parts (more preferably 2-10 parts) of main agent into 83-98.5 parts (more preferably 83-96.5 parts) of water at room temperature, stirring for 4-8 hours to obtain a main agent aqueous solution, heating to 38-42 ℃, adding 0.5-5 parts (more preferably 1-5 parts) of association agent into the main agent aqueous solution, stirring for 1-3 hours, cooling to room temperature, adding 0.5-2 parts of synergist, stirring for 1-3 hours, and standing for 18-30 hours to obtain the oil displacement agent composition with variable viscosity and without polymers.
In addition, the invention also provides the application of the variable viscosity oil displacement agent composition without macromolecules in the exploitation of crude oil remained in an oil field which has passed through a water-flooding development stage.
In the above application, the oil field may be a sandstone reservoir or a carbonate reservoir.
In the above application, preferably, the permeability of the oil field after water flooding development is in the range of 1 μm2To 10000 μm2。
In the above application, preferably, the viscosity of the crude oil after water flooding development of the oil field is in the range of 0.1mPa · s to 1 × 103mPa·s。
In the above application, the oil field is an oil field which has been subjected to water flooding development, and the injection water for such water flooding may be fresh water or salt water, i.e., the salinity of the injection water is not limited. Preferably, the salinity of the formation water of the oil field after water-flooding development is 5 x 102mg/L to 2X 105mg/L, and may have differences in different regions.
The viscosity of the oil displacement agent composition provided by the invention can be reduced along with the increase of salinity within a certain salinity range, and can also be increased along with the increase of salinity within a certain salinity range. The oil displacement agent composition can adapt to oil reservoirs with different salinity, particularly oil reservoirs with high salinity. Such reservoirs are the major part of reservoirs that have been found and therefore have a wide range of applications. In addition, the oil displacement agent composition has the capability of reducing the oil-water interfacial tension and emulsifying crude oil on the premise of adapting to the oil reservoir performance with different salinity, can improve the oil displacement efficiency and the recovery ratio, and creates higher economic benefit and social benefit. In addition, the oil displacement composition disclosed by the invention can realize the change of viscosity through the conversion of micelle shapes between a spherical shape and a rod shape under different salinity, does not contain high-molecular polymers, increases the viscosity by utilizing the steric hindrance effect of the high-molecular polymers compared with the traditional method, and has innovation on the chemical mechanism. The oil displacement composition is suitable for the exploitation of common low-permeability and medium-high permeability oil reservoirs in the middle and later periods of water flooding so as to improve the recovery ratio, has the advantage of viscosity increase and decrease change in the oil reservoirs compared with polymer flooding, is suitable for the different requirements of different areas in the oil reservoirs on the viscosity of an oil displacement agent, and has a more remarkable effect of expanding swept volume.
Drawings
FIG. 1 is a flow chart of a method of making a variable viscosity oil-displacing agent composition of the present invention.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides an oil displacement agent composition with variable viscosity, which comprises the following raw materials in parts by weight: principal agent-C12H25CON(C2H4OH)(C2H4OH)5 parts, association agent-fatty alcohol polyoxyethylene ether sodium sulfate 3 parts, synergist-lauryl sodium sulfate 1 part and water 91 parts.
As shown in fig. 1, the oil-displacing agent composition is prepared by the following steps: adding the main agent C into 91 parts of water at room temperature in parts by weight12H25CON(C2H4OH)(C2H4OH)5 parts and then stirring for 6 hours to obtain a main agent aqueous solution, heating to 38 ℃, adding 3 parts of association agent sodium alcohol ether sulfate into the main agent aqueous solution, stirring for 2 hours, cooling to room temperature, adding 1 part of synergist sodium dodecyl sulfate, stirring for 2 hours, and standing for 24 hours to obtain a clear transparent solution, namely the variable viscosity oil-displacing agent composition without macromolecules.
In order to illustrate the irreplaceability of the main agent, the association agent and the synergist in the oil displacement system, three comparative experiments are specially set, namely the main agent is cancelled, the association agent is cancelled and the synergist is cancelled on the basis of the compound system of the embodiment.
Control systems 1-1: the raw materials comprise the following components in parts by weight: association agent-3 parts of fatty alcohol-polyoxyethylene ether sodium sulfate, synergist-1 part of lauryl sodium sulfate and 91 parts of water.
The oil-displacing agent composition of the control system 1-1 was prepared by the following steps: adding 3 parts by weight of fatty alcohol-polyoxyethylene ether sodium sulfate into 91 parts by weight of water at room temperature, stirring for 2 hours, adding 1 part by weight of lauryl sodium sulfate, stirring for 2 hours, and standing for 24 hours to obtain a clear and transparent solution, namely the oil-displacing agent composition without the main agent.
Control systems 1-2: the raw materials comprise the following components in parts by weight: principal agent-C12H25CON(C2H4OH)(C2H4OH)5 parts, synergist-sodium dodecyl sulfate 1 part and water 91 parts.
The oil-displacing agent composition of the control system 1-2 was prepared by the following steps: adding the main agent C into 91 parts of water at room temperature in parts by weight12H25CON(C2H4OH)(C2H4OH)5 parts, stirring for 6 hours to obtain a main agent aqueous solution, adding 1 part of sodium dodecyl sulfate into the main agent aqueous solution, stirring for 2 hours, and standing for 24 hours to obtain a clear and transparent solution, namely the oil-displacing agent composition containing no association agent.
Control systems 1-3: the raw materials comprise the following components in parts by weight: principal agent-C12H25CON(C2H4OH)(C2H4OH)5 parts, association agent-fatty alcohol-polyoxyethylene ether sodium sulfate 3 parts and water 91 parts.
The oil-displacing agent compositions of the control systems 1-3 were prepared by the following steps: adding the main agent C into 91 parts of water at room temperature in parts by weight12H25CON(C2H4OH)(C2H4OH)5 parts, stirring for 6 hours to obtain a main agent aqueous solution, heating to 38 ℃, adding 3 parts of fatty alcohol-polyoxyethylene ether sodium sulfate into the main agent aqueous solution, stirring for 2 hours, cooling to room temperature, and standing for 24 hours to obtain a clear transparent solution, namely the oil-displacing agent composition without the synergist.
The oil-water interfacial tension of the oil displacement agent composition at different salinity is measured according to the rotating drop method in SY/Y5370-1999, and the viscosity of the oil displacement agent composition at different salinity is measured according to the rotating method in GB/T10247-2008. Wherein the results obtained are measured at different salinity for the oil displacing agent composition without dilution (i.e. salinity is controlled by dosing salt to the oil displacing agent composition). The results are shown in Table 1.
As can be seen from Table 1, the viscosity of the oil-displacing agent composition of example 1 by itself can spontaneously develop up to 1X 10 in water environments of different salinity6The viscosity of the oil displacement agent composition changes along with the increase of salinity by a multiple of change, namely, the viscosity is increased and the viscosity is reduced, and the change of two different trends occurs in different salinity ranges; and the oil-displacing agent composition reduces the oil-water interfacial tension from 18-24mN/m to 4.5-7.7 x 10 at different salinity-2mN/m, has the capability of reducing oil-water interfacial tension and emulsifying crude oil.
In the case where any one of the main agent, the association agent and the synergist in the combination formula is absent, as shown in the comparison systems 1-1, 1-2 and 1-3, the effect of the large change in viscosity of the examples cannot be achieved, and it is proved that the three components need to be matched with each other and are absent.
TABLE 1
Example 2
The embodiment provides an oil displacement agent composition with variable viscosity, which comprises the following raw materials in parts by weight: principal agent-C18H35CON(CH2OH)(C2H4OH)10 parts, association agent-5 parts of alkylphenol polyoxyethylene ether sodium sulfate, synergist-2 parts of octadecyl sodium sulfate and 83 parts of water.
As shown in fig. 1, the oil-displacing agent composition is prepared by the following steps: add host C to 83 parts water at room temperature in parts by weight18H35CON(CH2OH)(C2H4OH)10 parts, stirring for 8 hours to obtain a main agent aqueous solution, heating to 40 ℃, adding 5 parts of alkylphenol polyoxyethylene ether sodium sulfate into the main agent aqueous solution, stirring for 3 hours, cooling to room temperature, adding 2 parts of synergist sodium dodecyl sulfate, stirring for 3 hours, and standing for 30 hours to obtain a clear transparent solution, namely the variable viscosity oil-displacing agent composition containing no macromolecules.
In order to illustrate the irreplaceability of the main agent, the association agent and the synergist in the oil displacement system, three comparative experiments are specially set, namely the main agent is cancelled, the association agent is cancelled and the synergist is cancelled on the basis of the compound system of the embodiment.
Control system 2-1: the raw materials comprise the following components in parts by weight: 5 parts of association agent-alkylphenol polyoxyethylene ether sodium sulfate, 2 parts of synergist-octadecyl sodium sulfate and 83 parts of water.
The oil-displacing agent composition of the control system 2-1 was prepared by the following steps: adding 5 parts by weight of alkylphenol polyoxyethylene ether sodium sulfate into 83 parts by weight of water at room temperature, stirring for 3 hours, adding 2 parts by weight of lauryl sodium sulfate, stirring for 3 hours, and standing for 30 hours to obtain a clear and transparent solution, namely the oil-displacing agent composition without the main agent.
Control systems 2-2: the raw materials comprise the following components in parts by weight: principal agent-C18H35CON(CH2OH)(C2H4OH)10 parts by weight of2 parts of sodium octadecyl sulfate and 83 parts of water as an effect agent.
The oil-displacing agent composition of the control system 2-2 was prepared by the following steps: add host C to 83 parts water at room temperature in parts by weight18H35CON(CH2OH)(C2H4OH)10 parts by weight, stirring for 8 hours to obtain a main agent aqueous solution, adding 2 parts by weight of sodium dodecyl sulfate into the main agent aqueous solution, stirring for 3 hours, and standing for 30 hours to obtain a clear and transparent solution, namely the oil-displacing agent composition containing no association agent.
Control systems 2-3: the raw materials comprise the following components in parts by weight: principal agent-C18H35CON(CH2OH)(C2H4OH)10 parts, an association agent-alkylphenol polyoxyethylene ether sodium sulfate 5 parts and water 83 parts.
The oil-displacing agent compositions of the control systems 2-3 were prepared by the following steps: add host C to 83 parts water at room temperature in parts by weight18H35CON(CH2OH)(C2H4OH)10 parts, stirring for 8 hours to obtain a main agent aqueous solution, heating to 40 ℃, adding 5 parts of alkylphenol polyoxyethylene ether sodium sulfate into the main agent aqueous solution, stirring for 3 hours, cooling to room temperature, and standing for 30 hours to obtain a clear transparent solution, namely the oil-displacing agent composition without the synergist.
The oil-water interfacial tension of the oil displacement agent composition at different salinity is measured according to the rotating drop method in SY/Y5370-1999, and the viscosity of the oil displacement agent composition at different salinity is measured according to the rotating method in GB/T10247-2008. Wherein the results obtained are measured at different salinity for the oil displacing agent composition without dilution (i.e. salinity is controlled by dosing salt to the oil displacing agent composition). The results are shown in Table 2.
As can be seen from Table 2, the viscosity of the oil-displacing agent composition of example 2 by itself can spontaneously develop up to 1X 10 in water environments of different salinity7The viscosity of the oil displacement agent composition changes along with the increase of salinity by a multiple change, namely, the viscosity is increased and the viscosity is reduced, and the two different trends change in different salinity ranges(ii) a And the oil-displacing agent composition reduces the oil-water interfacial tension from 18-24mN/m to 3.4-6.6 x 10 at different salinity-2mN/m, has the capability of reducing oil-water interfacial tension and emulsifying crude oil.
In the case of lack of any one of the main agent, the association agent and the synergist in the combined formula, as shown in the comparison systems 2-1, 2-2 and 2-3, the effect of greatly changing the viscosity in the examples cannot be realized, and the fact that the three components need to be matched with each other proves that the lack of one component is not necessary.
TABLE 2
Example 3
The embodiment provides an oil displacement agent composition with variable viscosity, which comprises the following raw materials in parts by weight: main agent-para-C7H6ClCON(CH2OH)22 parts of association agent-1 part of fatty alcohol-polyoxyethylene ether sodium sulfonate, 0.5 part of synergist-hexadecyl sodium sulfate and 96.5 parts of water.
As shown in fig. 1, the oil-displacing agent composition is prepared by the following steps: adding the main agent para-C to 96.5 parts of water at room temperature in parts by weight7H6ClCON(CH2OH)2Stirring for 4 hours after 2 parts of the mixture is finished to obtain a main agent aqueous solution, heating to 42 ℃, adding 1 part of sodium fatty alcohol-polyoxyethylene ether sulfonate into the main agent aqueous solution, stirring for 1 hour, cooling to room temperature, adding 0.5 part of synergist sodium cetyl sulfate, stirring for 1 hour, and standing for 18 hours to obtain a clear transparent solution, namely the variable-viscosity oil-displacing agent composition without macromolecules.
In order to illustrate the irreplaceability of the main agent, the association agent and the synergist in the oil displacement system, three comparative experiments are specially set, namely the main agent is cancelled, the association agent is cancelled and the synergist is cancelled on the basis of the compound system of the embodiment.
Control system 3-1: the raw materials comprise the following components in parts by weight: association agent-1 portion of sodium fatty alcohol-polyoxyethylene ether sulfonate, synergist-0.5 portion of sodium hexadecyl sulfate and 96.5 portions of water.
The oil-displacing agent composition of the control system 3-1 was prepared by the following steps: adding 1 part of sodium fatty alcohol-polyoxyethylene ether sulfonate into 96.5 parts of water at room temperature, stirring for 1 hour, adding 0.5 part of sodium hexadecyl sulfate, stirring for 1 hour, and standing for 18 hours to obtain a clear and transparent solution, namely the oil-displacing agent composition without the main agent.
Control system 3-2: the raw materials comprise the following components in parts by weight: main agent-para-C7H6ClCON(CH2OH)22 portions, synergist-hexadecyl sodium sulfate 0.5 portion and water 96.5 portions.
The oil-displacing agent composition of the control system 3-2 was prepared by the following steps: adding the main agent para-C to 96.5 parts of water at room temperature in parts by weight7H6ClCON(CH2OH)2Stirring for 4 hours after 2 parts to obtain a main agent aqueous solution, adding 0.5 part of sodium hexadecyl sulfate into the main agent aqueous solution, stirring for 1 hour, and standing for 18 hours to obtain a clear and transparent solution, namely the oil-displacing agent composition without the association agent.
Control systems 3-3: the raw materials comprise the following components in parts by weight: main agent-para-C7H6ClCON(CH2OH)22 parts of association agent-sodium fatty alcohol polyoxyethylene ether sulfonate 1 part and 96.5 parts of water.
The oil-displacing agent composition of the control system 3-3 was prepared by the following steps: adding the main agent para-C to 96.5 parts of water at room temperature in parts by weight7H6ClCON(CH2OH)2Stirring for 4 hours after 2 parts of the mixture is finished to obtain a main agent aqueous solution, heating to 42 ℃, adding 1 part of fatty alcohol-polyoxyethylene ether sodium sulfonate into the main agent aqueous solution, stirring for 1 hour, cooling to room temperature, and standing for 18 hours to obtain a clear transparent solution, namely the oil-displacing agent composition without the synergist.
The oil-water interfacial tension of the oil displacement agent composition at different salinity is measured according to the rotating drop method in SY/Y5370-1999, and the viscosity of the oil displacement agent composition at different salinity is measured according to the rotating method in GB/T10247-2008. Wherein the results obtained are measured at different salinity for the oil displacing agent composition without dilution (i.e. salinity is controlled by dosing salt to the oil displacing agent composition). The results are shown in Table 3.
As can be seen from Table 3, the viscosity of the oil-displacing agent composition of example 3 by itself can spontaneously develop up to 1X 10 in water environments of different salinity5The viscosity of the oil displacement agent composition changes along with the increase of salinity by a multiple of change, namely, the viscosity is increased and the viscosity is reduced, and the change of two different trends occurs in different salinity ranges; and the oil-displacing agent composition reduces the oil-water interfacial tension from 18-24mN/m to 4.9-7.2 x 10 at different salinity-2mN/m, has the capability of reducing oil-water interfacial tension and emulsifying crude oil.
In the case of lack of any one of the main agent, the association agent and the synergist in the combined formula, as shown in the comparison systems 3-1, 3-2 and 3-3, the effect of greatly changing the viscosity in the examples cannot be realized, and the fact that the three components need to be matched with each other proves that the lack of one component is not necessary.
TABLE 3
Example 4
The embodiment provides an oil displacement agent composition with variable viscosity, which comprises the following raw materials in parts by weight: principal agent-C12H25CON(C2H4OH)(C2H4OH)5 parts, association agent-fatty alcohol polyoxyethylene ether sodium sulfate 3 parts, synergist-lauryl sodium sulfate 1 part and water 91 parts.
As shown in fig. 1, the oil-displacing agent composition is prepared by the following steps: adding the main agent C into 91 parts of water at room temperature in parts by weight12H25CON(C2H4OH)(C2H4OH)5 parts, stirring for 6 hours to obtain a main agent aqueous solution, heating to 40 ℃, and adding fatty alcohol polyoxyethylene into the main agent aqueous solution3 parts of sodium vinyl ether sulfate, stirring for 2 hours, cooling to room temperature, adding 1 part of synergist sodium dodecyl sulfate, stirring for 2 hours, and standing for 24 hours to obtain a clear transparent solution, namely the variable-viscosity oil-displacing agent composition without macromolecules.
In order to illustrate that the chemical components of the main agent cannot be replaced for ensuring the viscosity characteristic of the oil displacement system, 6 comparison experiments are specially set, and the main agent is replaced by 6 types of other surfactants on the basis of the compound system of the embodiment.
Control system 4-1: the main agent is replaced by petroleum sulfonate, and the preparation mode and the formula proportion of the composition are unchanged.
Control system 4-2: the main agent is replaced by petroleum carboxylate, and the preparation mode and the formula proportion of the composition are unchanged.
Control systems 4-3: the main agent is replaced by sorbitol acetal derivatives, and the preparation mode and the formula proportion of the composition are unchanged.
Control systems 4-4: the main agent is replaced by N-amido carboxylic betaine, and the preparation mode and the formula proportion of the composition are unchanged.
Control systems 4-5: the main agent is replaced by nonylphenol polyoxyethylene ether, and the preparation mode and the formula proportion of the composition are unchanged.
Control systems 4-6: the main agent is replaced by hydroxyethyl cellulose, and the preparation mode and the formula proportion of the composition are unchanged.
The lowest and highest viscosities of the system prepared in example 4 and the 6 control systems described above were determined in the salinity range of 242-49517mg/L according to the methods described in examples 1-3, and the results are shown in Table 4. The data show that other types of surfactants can not replace the main agent of the invention and can not enable the viscosity of the oil displacement agent to generate 10 at different salinity2-1010The change in magnification.
TABLE 4
| Salinity (mg/L) | Minimum viscosity (mPa. s) | Highest viscosity (mPa. s) |
| Example 4 | 28 | 2.58×107 |
| Control System 4-1 | 12 | 26 |
| Control System 4-2 | 10 | 39 |
| Control System 4-3 | 7 | 12 |
| Control System 4-4 | 33 | 69 |
| Control systems 4-5 | 9 | 11 |
| Control systems 4-6 | 51 | 70 |
Example 5
This embodiment provides a glueThe oil displacement agent composition with variable degree comprises the following raw materials in parts by weight: principal agent-C12H25CON(C2H4OH)(C2H4OH)5 parts, association agent-fatty alcohol polyoxyethylene ether sodium sulfate 3 parts, synergist-lauryl sodium sulfate 1 part and water 91 parts.
As shown in fig. 1, the oil-displacing agent composition is prepared by the following steps: adding the main agent C into 91 parts of water at room temperature in parts by weight12H25CON(C2H4OH)(C2H4OH)5 parts and then stirring for 6 hours to obtain a main agent aqueous solution, heating to 40 ℃, then adding 3 parts of fatty alcohol-polyoxyethylene ether sodium sulfate into the main agent aqueous solution, stirring for 2 hours, cooling to room temperature, then adding 1 part of synergist sodium dodecyl sulfate, stirring for 2 hours, and standing for 24 hours to obtain a clear transparent solution, namely the variable viscosity oil-displacing agent composition containing no macromolecules.
In order to illustrate that the chemical components of the association agent in the invention can not be replaced for ensuring the viscosity characteristic of the oil displacement system, 6 comparative experiments are specially set, and the association agent is replaced by 6 types of other surfactants on the basis of the compound system of the embodiment.
Control system 5-1: the association agent is replaced by petroleum sulfonate, and the preparation mode and the formula proportion of the composition are not changed.
Control system 5-2: the association agent is replaced by the petroleum carboxylate, and the preparation mode and the formula proportion of the composition are not changed.
Control systems 5-3: the association agent is replaced by sorbitol acetal derivative, and the preparation mode and the formula proportion of the composition are not changed.
Control systems 5-4: the associative agent is replaced by N-amido carboxylic betaine, and the preparation mode and the formula proportion of the composition are not changed.
Control systems 5-5: the associative agent is replaced by the polyoxyethylene nonyl phenyl ether, and the preparation mode and the formula proportion of the composition are unchanged.
Control systems 5-6: the associative agent is replaced by the hydroxyethyl cellulose, and the preparation mode and the formula proportion of the composition are not changed.
The lowest and highest viscosities of the system prepared in example 5 and the above 6 control systems were determined in the salinity range of 242-49517mg/L according to the methods described in examples 1-3, and the results are shown in Table 5. The data show that other types of surfactants cannot replace the action of the association agent, and cannot enable the viscosity of the oil displacement agent to generate 10 degrees at different salinity2-1010The change in magnification.
TABLE 5
| Salinity (mg/L) | Minimum viscosity (mPa. s) | Highest viscosity (mPa. s) |
| Example 5 | 28 | 2.58×107 |
| Control System 5-1 | 14 | 16 |
| Control System 5-2 | 12 | 28 |
| Control System 5-3 | 9 | 14 |
| Control systems 5-4 | 26 | 37 |
| Control systems 5-5 | 11 | 18 |
| Control systems 5-6 | 34 | 42 |
Example 6
The embodiment provides an oil displacement agent composition with variable viscosity, which comprises the following raw materials in parts by weight: principal agent-C12H25CON(C2H4OH)(C2H4OH)5 parts, association agent-fatty alcohol polyoxyethylene ether sodium sulfate 3 parts, synergist-lauryl sodium sulfate 1 part and water 91 parts.
As shown in fig. 1, the oil-displacing agent composition is prepared by the following steps: adding the main agent C into 91 parts of water at room temperature in parts by weight12H25CON(C2H4OH)(C2H4OH)5 parts and then stirring for 6 hours to obtain a main agent aqueous solution, heating to 40 ℃, then adding 3 parts of fatty alcohol-polyoxyethylene ether sodium sulfate into the main agent aqueous solution, stirring for 2 hours, cooling to room temperature, then adding 1 part of synergist sodium dodecyl sulfate, stirring for 2 hours, and standing for 24 hours to obtain a clear transparent solution, namely the variable viscosity oil-displacing agent composition containing no macromolecules.
In order to illustrate that the chemical components of the synergist of the invention can not be replaced for ensuring the viscosity property of the oil displacement system, 6 comparative experiments are specially set, and the synergist is replaced by 6 types of other surfactants on the basis of the compound system of the embodiment respectively.
Control system 6-1: the synergist is replaced by petroleum sulfonate, and the preparation mode and the formula proportion of the composition are unchanged.
Control system 6-2: the synergist is replaced by petroleum carboxylate, and the preparation mode and the formula proportion of the composition are unchanged.
Control systems 6-3: the synergist is replaced by sorbitol acetal derivative, and the preparation mode and the formula proportion of the composition are unchanged.
Control systems 6-4: the synergist is replaced by N-amido carboxylic betaine, and the preparation mode and the formula proportion of the composition are unchanged.
Control systems 6-5: the synergist is replaced by the nonylphenol polyoxyethylene ether, and the preparation mode and the formula proportion of the composition are unchanged.
Control systems 6-6: the synergist is replaced by hydroxyethyl cellulose, and the preparation mode and the formula proportion of the composition are unchanged.
The lowest and highest viscosities of the system prepared in example 6 and the 6 control systems described above were determined in the salinity range of 242-49517mg/L according to the methods described in examples 1-3, and are shown in Table 6. The data show that other types of surfactants cannot replace the effect of the synergist, and cannot enable the viscosity of the oil displacement agent to generate 10 degrees at different salinity2-1010The change in magnification.
TABLE 6
Example 7
The embodiment provides an oil displacement agent composition with variable viscosity, which comprises the following raw materials in parts by weight: principal agent-C12H25CON(C2H4OH)(C2H4OH)5 parts, association agent-fatty alcohol polyoxyethylene ether sodium sulfate 3 parts, synergist-lauryl sodium sulfate 1 part and water 91 parts.
As shown in fig. 1, the oil-displacing agent composition is prepared by the following steps: adding the main agent C into 91 parts of water at room temperature in parts by weight12H25CON(C2H4OH)(C2H4OH)5 parts and then stirring for 6 hours to obtain a main agent aqueous solution, heating to 40 ℃, then adding 3 parts of fatty alcohol-polyoxyethylene ether sodium sulfate into the main agent aqueous solution, stirring for 2 hours, cooling to room temperature, then adding 1 part of synergist sodium dodecyl sulfate, stirring for 2 hours, and standing for 24 hours to obtain a clear transparent solution, namely the variable viscosity oil-displacing agent composition containing no macromolecules.
To demonstrate that the concentration ratios of the main agent, the association agent and the synergist in the present invention are not substitutable for ensuring the viscosity characteristics of the oil displacing system, 3 comparative experiments were set, and the concentration ratios of the main agent, the association agent and the synergist were respectively reduced on the basis of the compound system of the present example.
Control system 7-1: the addition amount of the main agent is replaced by 0.4 part by weight, and the preparation mode of the composition and the proportion of the rest formula are unchanged.
Control system 7-2: the addition amount of the association agent is replaced by 0.4 part by weight, and the preparation mode of the composition and the proportion of the rest formula are unchanged.
Control systems 7-3: the addition amount of the synergist is replaced by 0.4 part by weight, and the preparation mode of the composition and the proportion of the rest formula are unchanged.
The lowest and highest viscosities of the system prepared in example 7 and the above 3 control systems were measured in the salinity range of 242-49517mg/L according to the methods described in examples 1-3, and the results are shown in Table 7. The data show that the composition prepared by the main agent, the association agent, the synergist and the water, which belong to the chemical composition range of the invention but are lower than the concentration range of the invention, can not enable the viscosity of the oil displacement agent to generate 10 degrees of viscosity at different salinity2-1010The concentration ranges of the present invention are essential and non-substitutable.
TABLE 7
| Salinity (mg/L) | Minimum viscosity (mPa. s) | Highest viscosity (mPa. s) |
| Example 7 | 28 | 2.58×107 |
| Control System 7-1 | 15 | 166 |
| Control System 7-2 | 22 | 148 |
| Control System 7-3 | 24 | 71 |
It can be seen from the above examples that examples 1, 2 and 3 and the reference systems 1-1, 1-2, 1-3, 2-1, 2-2, 2-3, 3-1, 3-2 and 3-3 are illustrations of the necessity of combining the three types of components, i.e., the main agent, the associative agent and the synergistic agent, in the combined formulation, and that these three types of components need to be matched with each other and are not indispensable for achieving the object of the present invention. Examples 4 to 6 are illustrative of the necessity and irreplaceability of the ranges of the specific components of the main agent, the association agent and the synergist in the combined formula, and for the purpose of the present invention, the ranges of the chemical compositions of all three components need to be within the range defined by the present invention, and other chemical components cannot be replaced. Example 7 is an illustration of the necessity and irreplaceability of the concentration ranges of the main agent, the association agent and the synergist in the combined formula, and the concentration ranges of the three components are all required to be within the range defined by the invention for achieving the purpose of the invention, and the concentration outside the range cannot be replaced.
In conclusion, the macromolecule-free oil displacement composition can adapt to oil reservoirs with different salinity, particularly oil reservoirs with high salinity, which are the main parts of the found oil reservoirs, so that the oil displacement composition has a wide application range; the oil displacement composition has the capability of reducing oil-water interfacial tension and emulsifying crude oil on the premise of adapting to oil deposit performances with different salinity, can improve oil displacement efficiency and recovery ratio, and creates higher economic benefit and social benefit.
Claims (7)
1. The oil displacement agent composition with variable viscosity comprises the following raw materials in parts by weight:
0.5-10 parts of a main agent;
0.5-5 parts of an association agent;
0.5-2 parts of a synergist; and
83 to 98.5 portions of water to make up to 100 portions,
wherein the main agent is represented by the general formula R1CON(R2OH)(R3OH) amide type nonionic surfactant, wherein R is1Is a linear alkyl group with a carbon number of 12 or 18, or a branched alkyl group with a carbon number of 12 or 18; or the main agent is para-C7H6ClCON(CH2OH)2；
R2OH and R3The hydroxyalkyl groups represented by OH are each independently selected from linear hydroxyalkyl groups having 1 to 2 carbon atoms;
the associative agent is substituted polyoxyethylene ether sulfate and/or substituted polyoxyethylene ether sulfonate, and the substituted polyoxyethylene ether sulfate and the substituted polyoxyethylene ether sulfonate are one of fatty alcohol-polyoxyethylene ether sulfate, fatty alcohol-polyoxyethylene ether sulfonate or alkylphenol polyoxyethylene ether sulfate;
the synergist is alkyl sulfate with carbon number of 12 or 18.
2. The variable viscosity oil-displacing agent composition according to claim 1, which is prepared by: adding 0.5-10 parts of main agent into 83-98.5 parts of water at room temperature, stirring for 4-8 hours to obtain a main agent aqueous solution, heating to 38-42 ℃, adding 0.5-5 parts of association agent into the main agent aqueous solution, stirring for 1-3 hours, cooling to room temperature, adding 0.5-2 parts of synergist, stirring for 1-3 hours, and standing for 18-30 hours to obtain the oil-displacing agent composition with variable viscosity.
3. The variable viscosity oil-displacing agent composition according to claim 1, having its own viscosity occurring at different salinity of 102-1010The change in magnification.
4. The variable viscosity oil-displacing agent composition according to claim 3, wherein the viscosity of the variable viscosity oil-displacing agent composition itself varies in a range of 0.1 mPa-s to 2 x 10 at different salinity8mPa·s。
5. A method of preparing a variable viscosity oil-displacing agent composition as claimed in any one of claims 1 to 4 comprising the steps of: adding 0.5-10 parts of main agent into 83-98.5 parts of water at room temperature, stirring for 4-8 hours to obtain a main agent aqueous solution, heating to 38-42 ℃, adding 0.5-5 parts of association agent into the main agent aqueous solution, stirring for 1-3 hours, cooling to room temperature, adding 0.5-2 parts of synergist, stirring for 1-3 hours, and standing for 18-30 hours to obtain the oil-displacing agent composition with variable viscosity.
6. Use of a variable viscosity oil displacement agent composition according to any one of claims 1 to 4 for the recovery of crude oil remaining in an oil field that has passed through a water flooding development stage.
7. The use of claim 6, wherein the oil field is a sandstone reservoir or a carbonate reservoir;
the permeability range of the oil field after water flooding development is 1 mu m2To 10000 μm2；
The viscosity range of the crude oil of the oil field after water flooding development is 0.1mPa & s to 1 x 103mPa·s；
The salinity of the formation water of the oil field after water drive development is 5 multiplied by 102mg/L to 2X 105mg/L；
The salinity of the formation water after water flooding development of the oil field varies in different regions.
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| US4042030A (en) * | 1976-05-24 | 1977-08-16 | Mobil Oil Corporation | Oil recovery by viscous waterflooding |
| US4181178A (en) * | 1977-12-12 | 1980-01-01 | Mobil Oil Corporation | Oil recovery by waterflooding with thickened surfactant solutions |
| CA2349234C (en) * | 2001-05-31 | 2004-12-14 | Imperial Oil Resources Limited | Cyclic solvent process for in-situ bitumen and heavy oil production |
| US7461694B2 (en) * | 2005-11-16 | 2008-12-09 | Rhodia Inc. | Methods for recovering oil from an oil reservoir |
| WO2013142789A1 (en) * | 2012-03-23 | 2013-09-26 | Saudi Arabian Oil Company | In-situ self diverting wag process |
| CN102952531B (en) * | 2012-11-09 | 2014-12-10 | 天津亿利科能源科技发展股份有限公司 | Surfactant for displacing oil of offshore oilfield and preparation method thereof |
| CN103421481A (en) * | 2013-09-04 | 2013-12-04 | 上海海瑰化工科技有限公司 | Glycine betaine surfactant composition system and purpose thereof |
| CN103468235A (en) * | 2013-09-26 | 2013-12-25 | 东北石油大学 | Chemical assistant for thermal recovery of thick oil and application thereof |
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