CA1232127A - Micellar slug for oil recovery - Google Patents
Micellar slug for oil recoveryInfo
- Publication number
- CA1232127A CA1232127A CA000449413A CA449413A CA1232127A CA 1232127 A CA1232127 A CA 1232127A CA 000449413 A CA000449413 A CA 000449413A CA 449413 A CA449413 A CA 449413A CA 1232127 A CA1232127 A CA 1232127A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Colloid Chemistry (AREA)
Abstract
MICELLAR SLUG FOR OIL RECOVERY
ABSTRACT OF THE DISCLOSURE
A micellar slug for use In the recovery of oil, the slug containing a hydrocarbon, an aqueous medium, a surfactant, and a cosurfactant. The surfactant contains as an essential component an internal olefin sulfonate having 10 to 26 carbon atoms and a disulfonate content of about 20% by weight or less. This micellar slug has an excellent capability for decreasing an interfacial tensions between oil and micro-emulsions and between water and micro-emulsions and an excellent salinity tolerance and hard-water resistance. Furthermore, the stable micro-emulsion from this micellar slug can be maintained during sweeping in subterranean reservoirs even when the salt concentration of the subterranean water is changed.
ABSTRACT OF THE DISCLOSURE
A micellar slug for use In the recovery of oil, the slug containing a hydrocarbon, an aqueous medium, a surfactant, and a cosurfactant. The surfactant contains as an essential component an internal olefin sulfonate having 10 to 26 carbon atoms and a disulfonate content of about 20% by weight or less. This micellar slug has an excellent capability for decreasing an interfacial tensions between oil and micro-emulsions and between water and micro-emulsions and an excellent salinity tolerance and hard-water resistance. Furthermore, the stable micro-emulsion from this micellar slug can be maintained during sweeping in subterranean reservoirs even when the salt concentration of the subterranean water is changed.
Description
MUZZLER SNUG FOR OIL RECOVERY
BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to a muzzler slug suitable for use in a muzzler drive for recovering oil from subterranean reservoirs. More specifically, it relates to a muzzler slug capable of recovering oil from subterranean reservoirs containing sub-terranean water having a very wide salt concentration at a high oil recovery efficiency.
Description of the Prior Art It is well known in the art that the so-called "primary recovery methods, including pumping methods, can recover only a portion of the petroleum or crude oil (referred to as "oil"
hereinafter) from subterranean reservoirs and leave substantial amounts of oil in the subterranean reservoirs.
In order -to recover the remaining large amounts of oil from the subterranean reservoirs, so-called "secondary recovery" methods have been proposed, wherein, for example, water or gas is injected into the subterranean reservoirs from an injection well at a pressure sufficient to increase the flyability of oil, steam is injected into subterranean reservoirs so as to effect I
the dispel cement of oil toward a E~oduction we l l, or oil in subterranean reservoirs is partially burned to heat the subterranean reservoirs so as to decrease the viscosity of thy oil and increase the flyability of the oil.
Furthermore, the so-called various 'Tertiary recovery" methods, including a combination of secondary recovery methods and Improved secondary recovery methods, have been proposed, wherein surfactants or water-soluble polymers are utilized. These methods æ e generally called "enhanced oil recovery" (ERR methods.
Of the surfac~ant ERR methods, the recent "muzzler drive" methods are to ye noted. According to these method, a muzzler slug, that is, a clear micro-emulsion derived from water and oil such as petroleum petroleum distillates, or fuel oil, is injected under pressure into the subterranean reservoirs for the recovery of oil in the subterranean reservoirs. These ERR methods are disclosed in, for example, So Patent Nos. 3506070, 3613786, 3740343, 3983940, 3990515, 4017405, and 4059154.
These prior arts disclose that various kinds of sun-fact ants including anionic-, non ionic , and cationic-type surfactants can be used alone or in any mixture thereof in the formation of muzzler slugs. Examples of such surfactants are petroleum sulfonates, alkylaryl sulfa-notes, dialkyl sulfosuccinates, Al Kane sulfonates, polyoxyethylene alkylether sulfates, alpha-olefin sulfonate, polyoxye~hylene alkylether3, polyoxyethylene I
alkylphenylethers, polyol fatty acid ester, alkyltri-methyl ammonia salts, and dialkyldimethyl ammonium salts.
The muzzler slugs should have the following kirk-teristics to recover oil from subterranean reservoirs at a high efficiency:
Sufficiently low m terfacial tensions between oil and the micro-emulsions and between formation water and the micro-emulsions; stability of the micro-emulsions and the small ah age in the interracial tensions during sweeping even when the salt concentration of the formation water is changed; salinity tolerance of the muzzler slugs at a wide salt concentration range, since the salt concentration range of the formation water extends widely from a low to high concentration;
and low cost availability of the muzzler slugs, since a large amount of a muzzler slug is necessary to recover oil from subterranean reservoirs.
SUMMARY OF TOE INVENTION
The object of the present invention is to provide, for the recovery of oil, a muzzler slug having an excellent oil-micro emulsion end formation water-micro--emulsion interracial tension decreasing capabilities and an excellent salinity tolerance at a wide salt concentration range and being capable of maintaining ye stability of the micro-emulsions during sweeping in eye subterranean reservoirs even when the salt concentration of the formation water is changed.
_ 4 ~23~
A further object of the present invention is to provide an oil recovery process using a muzzler slug.
Other objects and advantages of the present invent lion will be apparent from the following description.
In accordance with one embodiment of the present invention, there is provided a muzzler slug for use in the recovery of oil, the slug consisting essentially of a hydrocarbon, an aqueous medium, a surfactant, and a cosurfactant having an alcoholic hydroxyl group, the surfactant containing, as an essential component, an internal olefin sulfonate having 10 to 26 carbon atoms obtained by sulfonating internal olefins containing as a main constituent vinylene-type monoolefin having the general formula:
R - OH = OH - R' wherein R and R' are independently straight- or branched-chain saturated hydrocarbon radicals having 1 or more carbon atoms provided that the total carbon atom numbers of R and R', is 8 to 24, followed by neutralization.
In accordance with another embodiment of the present invention, there is provided a process -For producing oil from an oil-bearing subterranean reservoir penetrated by wells which comprises the steps of:
(1) injecting into the reservoir through an injection well a muzzler slug consisting essentially of a hydrocarbon, an aqueous medium, a surfactant, and a cosurfactant having an alcoholic hydroxyl group, the surfactan-t containing, as an essential component, an internal olefin sulfonate having 10 to 26 carbon atoms obtained by sulfonating internal olefins containing as a main constituent vinylene-type monoolefin hazing the general formula:
R - OH = OH I' I "'I
; $ I;
". "I ,., - pa - i23212~
wherein R and R' are independently straight- or branched-chain saturated hydrocarbon radicals having l or more carbon atoms provided that the total carbon atom numbers of R and R', is 8 to 24, followed by neutralization;
I injecting into the reservoir at least one driving fluid; and (3) recovering oil from the reservoir through a production well.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The muzzler slugs desirably used for the recovery of oil are transparent or translucent micro-emulsions containing about I to about 90% by weight of a hydrocarbon, about 4% to about 95% by weight of an aqueous medium, about 1% to about 30~ by weight of a surfactant containing, as an essential constituent, an internal olefin sulfonate having lo to 26 carbon atoms, and about 0.1% to about 20% by weight of a cosurfactant.
The aqueous medium usable in the formation of the muzzler slug of the present invention includes soft water, water containing inorganic salts, and brine. For example r rain water, river water, lake water, formation water, oil stratum water, and seawater can be freely used in the formation of the muzzler slug of the present invention.
The muzzler slugs of the present invention contain ~r~3 I
I
the internal olefin sulfonates having good salinity tolerance and hard-water resistance as an essential constituent of the surfactant. Therefore, brine having a salt concentration of up to about 10% by weight can be used in the formation of the muzzler slugs of the present invention. Further, brine having a salt concentration of up to about 15~ by weight can be used when other surfactants or cosurfactants are used together with the internal olefin sulfonate. Furthermore, the muzzler slugs of the present invention have an excellent hard--water resistance. For example, brine usable in the formation of the muzzler slugs of the present invention can contain a relatively large amount of multivalent metal ions, for example, about 5,000 Pam of a My ion (i.e., about 2.6~ by weight of McCoy). Thus, waxer or brine) usable in the formation of the muzzler slugs of the resent invention can contain 0% to about lo by weight, desirably about 0.5% to about 12% by weight and more desirably about 1% to about 10~ by weight, of inorganic salts Typical examples of the inorganic salts contained Lo the water (or brine) are Nail, Clue, Nazi , and K2S04. For instance, seawater contains about OWE% by weight of inorganic salts including about 1,600 Pam, in terms of a My ion, of diva lent metal ions.
25 This salt concentration is within the desirable salt concentration range of the present invention.
The internal olefin sulfonates Usable as an essential sur~actant in the present invention are those obtained by sulfonating internal olefins containing as a main constituent vinylene-type monoolefin having 10 to 26 carbon atoms, desirably 12 to 24 carbon atoms and having a general formula:
R -- OH = OH - R' wherein R and R' are independently straight- or branched-chain saturated hydrocarbon radicals having 1 or more carbon atoms provided that the total carbon atom numbers of R and R' is 8 to 24, desirably 10 to 22, and optionally 10 containing about 33% by weight (about one third of the olefins) or less of tri-substituted type monoolefins, followed by neutralizing the sulfonated products with appropriate bases and, then, optionally, hydrolyzing the neutralized products. The internal olefin sup donates thus prepared generally contain about 10~ to about 60~
by weight of alkenyl sulfonates having a double bond and about 90~ to about 40~ by weight of hydroxyalkane sulfa-notes and also contain about 80% by weight or more of monosulfonates and about 20% by weigh or less of dip sulfonates. It should be noted, however, that internal olefin sulfonates having the compositions different from the above-mentioned composition ratios can be prepared by appropriately selecting the sulfonation conditions and hydrolysis conditions. Generally speaking, the increase in the carbon atom number of the internal ole~ln tends to result in an increase in the composition ratio of the alkenylsulfonate. On the other hand, the increase in the mow ratio of the sulfonating agent to the internal ~32~
olefin during the sulfonation tends to result in an increase in the composition ratio of the disulfonate.
The content of the disulfonate in the internal olefin sulfonates usable in the present invention should be about 20% by weight or less. A disulfon~te content of more than 20~ by weight undesirably decreases the interfaclal tension decreasing capability of the internal olefin sulfonates and, therefore, decreases the oil recovery efficiency of the muzzler slugs. Thus, a small content of the disulfonate in the internal olefin sulfonates increases the salinity tolerance and the resistance against the change in the salt concentration of the brine, without impairing the interracial tension decreasing capability of the internal olefin sulfonates.
Accordingly, the content of the disulfonates in the internal olefin sulfonates is desirably about 0.5% to about 15~ by weight, more desirably about I to about 12~ by weight The internal olefin sulfonates usable in the present invention can be alkali metal salts, alkaline earth metal salts, ammonium salts, and organic amine salts thereof. The desirable counter cations are Nay K, go Cay NH4 , and alkanolammonium.
Examples of internal olefin sulfonates usable in the formation of the muzzler slugs of the present invention are: internal olefin sulfonate having 12, 14, 16, 18, 20, 22, 24, 12-16, 13-14, 13-16, 14 I 18, 15-18, 16-18, 16-20, 17-20, 18-20, and 20-24 carbon I
atoms. These sulfonates may be used alone or in any mixture thereof.
As mentioned above, the muzzler slugs of the present invention contain about 1% to about 30~ by weight of the surfactant. However, the muzzler slugs desirably contain about 3% to about 25~ by weight of the surfactant, taking into consideration both low interracial tensions and reasonable cost The amount of the higher internal olefin sulfonates having 10 to 26 carbon atoms should be lo at least 50% by weight, desirably 60~ by weight or more, based on the total amount of the surfactants contained in the muzzler slugs.
The hydrocarbons usable as an oil component in the present invention include, for example, petroleum, pique-fled petroleum gas, crude gasoline ~naphtha), kerosine,diesel oil, and fuel oil. The recovered petroleum it desirably used due to its low cost and availability as well as its composition, which is similar to that of the oil contained in subterranean reservoirs. As mentioned above, the muzzler slugs of the present invention can contain about I to about 90% by weight of hydrocarbons.
The desirable concentration of hydrocarbons is within the range of about 3% to about 40~ by weight whereby an oil-in-water (O/W) type emulsion is formed, since the 25 use of a large amount of hydrocarbons is not economical.
The cosurfactants used in the formation of the muzzler slugs of the present invention are an essential constituent for forming micro-emulsions associated with 2t7 _ 9 _ the surfactants. The cosurfactants usable in the present invention are those having an alcoholic hydroxyl group.
the desirable cosurfactants are alcohols having the general formula:
S Rescission wherein n is a number of from 0 to about 4 and R" is an alkyd or alkenyl group having 4 to 8 carbon atoms when n is zero and an alkyd or alkenyl group having 6 to lo carbon atoms, a phenol group, or an alkylphenyl group lo having 7 to 16 carbon atoms when n it not zero. The aliphatic groups of R" may be straight chain or branched--chain groups.
Examples of such alcohols are buttonless, pentanols, hexanols, 2-ethylhexanol or other octanols, polyoxy-lo ethylene hexylethers (n = lo, polyoxyethylene decylethers(n = 2), polyoxyethylene tridecylethers (n = 4), polyoxy~
ethylene butylphenylethers on = 2), polyoxyethylene nonylphenylethers (n = 3), and polyoxyethylene dodecyl-phenylethers (n = 4).
As mentioned above, the muzzler slugs of the present invention can contain about 0.1% to about I by weight of the cosurfactants. However, the desirable concern-traction of the cosurfactants is within the range of about 1% to about 15% by weight from the viewpoints of the stability of the micro emulsions and the decreasing capacity for the interracial tensions.
As mentioned above, the muzzler slugs of the present invention contain internal olefin sulfonates having lo Jo to 26 carbon atoms as an essential or major constituent of the surfactants. However, other auxiliary surfactants can alto key included, together with the internal olefln sulfonates.
Examples of such auxiliary suxfactants are anionic surfactants and non ionic surfactants such as petroleum sulfonates, alkylbenzene sulfonates, polyoxye~hylene alkylether sulfates, dialkyl sulfosuccinates, alpha--olefin sulfonates, paraffin gut ion ales, soaps, higher 10 alcohol ethoxylate~, alkylphenol ethoxylates, polyol Patty acid esters, fatty acid alkylol asides, and pow-oxyethylene fatty acid aside 5 .
The viscosity of the muzzler slugs of the present invention can be suitably adjusted by selecting the kinds and amounts of the component s of the micro emulsions However, when a muzzler slug having a high viscosity is desired, an appropriate known thickening agent such as a water-soluble polymer can be added to the mice far slugs .
Examples of thickening agents usable in the formation of the muzzler slugs are heteropolysaccharides produced by microbes, naphthalenesulfonic acid-formaldehyde condemn-sates, polyacrylamides, polyacrylates, hydroxyethyl-cellulose, and carboxymethylcelluloses The muzzler slugs of the present invention can be readily obtained by any known method of production. For example, the hydrocarbons, the surfactants, the aqueous medium, and the cosurfactants can be mixed in any mixing order by using conventional mixing devices, mixing Jo temperatures, and mixing pressures.
The recovery of oil from subterranean reservoirs can be carried out by means of any conventional muzzler drive method by using the muzzler slugs of the present invention. For instance, the muzzler slugs are injected under pressure into at least one injection well of the subterranean reservoirs. Then, at least one driving fluid such as flood water and/or aqueous solution of the above-mentioned thickening agent it Injected into the injection well so as to transfer or drive the remaining oil toward on oil production well and to recover the oil from the production well. The suitable amount of the muzzler slugs injected into the injection well is about I to about 25% by volume of the porosity of the subtler-reunion reservoirs.
The suitable salt concentration of the subterranean water in the subterranean reservoirs where the muzzler slugs of the present invention can be applied is 0% to about 15~ by weight, desirably about 0.1~ to about 12%
by weight and, more desirably, about 0.5~ to about lo by weight. Although the salt concentration of water used in the formation of the muzzler slugs is not necessarily the same as that of the subterranean water, they are desirably the same prom the viewpoints that the Walt concentration is changed during the sweeping.
As mentioned hereinabove, the muzzler slugs of the present invention contain the internal olefin sulfonates having a disulfonate content of about 20~ by weight or I
Lowe as an essential component of the surfactantO The resultant macular slugs thus haze an excellent salinity tolerance and hereditary resistance and can form micro--emulsions by using water having a very wide salt consign traction ox soft water to urine having a high salt concentration. Furthermore, the muzzler slugs of the present invention have very small interracial tensions between water and the micro emulsions and between oil and the micro-emulsions and have resistance against the change in the salt concentrations. As a result, the following remarkable advantageous features can be obtained:
1) Either soft water, seawater, or subtler-reunion water having a hush salt Concentration can be freely used;
BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to a muzzler slug suitable for use in a muzzler drive for recovering oil from subterranean reservoirs. More specifically, it relates to a muzzler slug capable of recovering oil from subterranean reservoirs containing sub-terranean water having a very wide salt concentration at a high oil recovery efficiency.
Description of the Prior Art It is well known in the art that the so-called "primary recovery methods, including pumping methods, can recover only a portion of the petroleum or crude oil (referred to as "oil"
hereinafter) from subterranean reservoirs and leave substantial amounts of oil in the subterranean reservoirs.
In order -to recover the remaining large amounts of oil from the subterranean reservoirs, so-called "secondary recovery" methods have been proposed, wherein, for example, water or gas is injected into the subterranean reservoirs from an injection well at a pressure sufficient to increase the flyability of oil, steam is injected into subterranean reservoirs so as to effect I
the dispel cement of oil toward a E~oduction we l l, or oil in subterranean reservoirs is partially burned to heat the subterranean reservoirs so as to decrease the viscosity of thy oil and increase the flyability of the oil.
Furthermore, the so-called various 'Tertiary recovery" methods, including a combination of secondary recovery methods and Improved secondary recovery methods, have been proposed, wherein surfactants or water-soluble polymers are utilized. These methods æ e generally called "enhanced oil recovery" (ERR methods.
Of the surfac~ant ERR methods, the recent "muzzler drive" methods are to ye noted. According to these method, a muzzler slug, that is, a clear micro-emulsion derived from water and oil such as petroleum petroleum distillates, or fuel oil, is injected under pressure into the subterranean reservoirs for the recovery of oil in the subterranean reservoirs. These ERR methods are disclosed in, for example, So Patent Nos. 3506070, 3613786, 3740343, 3983940, 3990515, 4017405, and 4059154.
These prior arts disclose that various kinds of sun-fact ants including anionic-, non ionic , and cationic-type surfactants can be used alone or in any mixture thereof in the formation of muzzler slugs. Examples of such surfactants are petroleum sulfonates, alkylaryl sulfa-notes, dialkyl sulfosuccinates, Al Kane sulfonates, polyoxyethylene alkylether sulfates, alpha-olefin sulfonate, polyoxye~hylene alkylether3, polyoxyethylene I
alkylphenylethers, polyol fatty acid ester, alkyltri-methyl ammonia salts, and dialkyldimethyl ammonium salts.
The muzzler slugs should have the following kirk-teristics to recover oil from subterranean reservoirs at a high efficiency:
Sufficiently low m terfacial tensions between oil and the micro-emulsions and between formation water and the micro-emulsions; stability of the micro-emulsions and the small ah age in the interracial tensions during sweeping even when the salt concentration of the formation water is changed; salinity tolerance of the muzzler slugs at a wide salt concentration range, since the salt concentration range of the formation water extends widely from a low to high concentration;
and low cost availability of the muzzler slugs, since a large amount of a muzzler slug is necessary to recover oil from subterranean reservoirs.
SUMMARY OF TOE INVENTION
The object of the present invention is to provide, for the recovery of oil, a muzzler slug having an excellent oil-micro emulsion end formation water-micro--emulsion interracial tension decreasing capabilities and an excellent salinity tolerance at a wide salt concentration range and being capable of maintaining ye stability of the micro-emulsions during sweeping in eye subterranean reservoirs even when the salt concentration of the formation water is changed.
_ 4 ~23~
A further object of the present invention is to provide an oil recovery process using a muzzler slug.
Other objects and advantages of the present invent lion will be apparent from the following description.
In accordance with one embodiment of the present invention, there is provided a muzzler slug for use in the recovery of oil, the slug consisting essentially of a hydrocarbon, an aqueous medium, a surfactant, and a cosurfactant having an alcoholic hydroxyl group, the surfactant containing, as an essential component, an internal olefin sulfonate having 10 to 26 carbon atoms obtained by sulfonating internal olefins containing as a main constituent vinylene-type monoolefin having the general formula:
R - OH = OH - R' wherein R and R' are independently straight- or branched-chain saturated hydrocarbon radicals having 1 or more carbon atoms provided that the total carbon atom numbers of R and R', is 8 to 24, followed by neutralization.
In accordance with another embodiment of the present invention, there is provided a process -For producing oil from an oil-bearing subterranean reservoir penetrated by wells which comprises the steps of:
(1) injecting into the reservoir through an injection well a muzzler slug consisting essentially of a hydrocarbon, an aqueous medium, a surfactant, and a cosurfactant having an alcoholic hydroxyl group, the surfactan-t containing, as an essential component, an internal olefin sulfonate having 10 to 26 carbon atoms obtained by sulfonating internal olefins containing as a main constituent vinylene-type monoolefin hazing the general formula:
R - OH = OH I' I "'I
; $ I;
". "I ,., - pa - i23212~
wherein R and R' are independently straight- or branched-chain saturated hydrocarbon radicals having l or more carbon atoms provided that the total carbon atom numbers of R and R', is 8 to 24, followed by neutralization;
I injecting into the reservoir at least one driving fluid; and (3) recovering oil from the reservoir through a production well.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The muzzler slugs desirably used for the recovery of oil are transparent or translucent micro-emulsions containing about I to about 90% by weight of a hydrocarbon, about 4% to about 95% by weight of an aqueous medium, about 1% to about 30~ by weight of a surfactant containing, as an essential constituent, an internal olefin sulfonate having lo to 26 carbon atoms, and about 0.1% to about 20% by weight of a cosurfactant.
The aqueous medium usable in the formation of the muzzler slug of the present invention includes soft water, water containing inorganic salts, and brine. For example r rain water, river water, lake water, formation water, oil stratum water, and seawater can be freely used in the formation of the muzzler slug of the present invention.
The muzzler slugs of the present invention contain ~r~3 I
I
the internal olefin sulfonates having good salinity tolerance and hard-water resistance as an essential constituent of the surfactant. Therefore, brine having a salt concentration of up to about 10% by weight can be used in the formation of the muzzler slugs of the present invention. Further, brine having a salt concentration of up to about 15~ by weight can be used when other surfactants or cosurfactants are used together with the internal olefin sulfonate. Furthermore, the muzzler slugs of the present invention have an excellent hard--water resistance. For example, brine usable in the formation of the muzzler slugs of the present invention can contain a relatively large amount of multivalent metal ions, for example, about 5,000 Pam of a My ion (i.e., about 2.6~ by weight of McCoy). Thus, waxer or brine) usable in the formation of the muzzler slugs of the resent invention can contain 0% to about lo by weight, desirably about 0.5% to about 12% by weight and more desirably about 1% to about 10~ by weight, of inorganic salts Typical examples of the inorganic salts contained Lo the water (or brine) are Nail, Clue, Nazi , and K2S04. For instance, seawater contains about OWE% by weight of inorganic salts including about 1,600 Pam, in terms of a My ion, of diva lent metal ions.
25 This salt concentration is within the desirable salt concentration range of the present invention.
The internal olefin sulfonates Usable as an essential sur~actant in the present invention are those obtained by sulfonating internal olefins containing as a main constituent vinylene-type monoolefin having 10 to 26 carbon atoms, desirably 12 to 24 carbon atoms and having a general formula:
R -- OH = OH - R' wherein R and R' are independently straight- or branched-chain saturated hydrocarbon radicals having 1 or more carbon atoms provided that the total carbon atom numbers of R and R' is 8 to 24, desirably 10 to 22, and optionally 10 containing about 33% by weight (about one third of the olefins) or less of tri-substituted type monoolefins, followed by neutralizing the sulfonated products with appropriate bases and, then, optionally, hydrolyzing the neutralized products. The internal olefin sup donates thus prepared generally contain about 10~ to about 60~
by weight of alkenyl sulfonates having a double bond and about 90~ to about 40~ by weight of hydroxyalkane sulfa-notes and also contain about 80% by weight or more of monosulfonates and about 20% by weigh or less of dip sulfonates. It should be noted, however, that internal olefin sulfonates having the compositions different from the above-mentioned composition ratios can be prepared by appropriately selecting the sulfonation conditions and hydrolysis conditions. Generally speaking, the increase in the carbon atom number of the internal ole~ln tends to result in an increase in the composition ratio of the alkenylsulfonate. On the other hand, the increase in the mow ratio of the sulfonating agent to the internal ~32~
olefin during the sulfonation tends to result in an increase in the composition ratio of the disulfonate.
The content of the disulfonate in the internal olefin sulfonates usable in the present invention should be about 20% by weight or less. A disulfon~te content of more than 20~ by weight undesirably decreases the interfaclal tension decreasing capability of the internal olefin sulfonates and, therefore, decreases the oil recovery efficiency of the muzzler slugs. Thus, a small content of the disulfonate in the internal olefin sulfonates increases the salinity tolerance and the resistance against the change in the salt concentration of the brine, without impairing the interracial tension decreasing capability of the internal olefin sulfonates.
Accordingly, the content of the disulfonates in the internal olefin sulfonates is desirably about 0.5% to about 15~ by weight, more desirably about I to about 12~ by weight The internal olefin sulfonates usable in the present invention can be alkali metal salts, alkaline earth metal salts, ammonium salts, and organic amine salts thereof. The desirable counter cations are Nay K, go Cay NH4 , and alkanolammonium.
Examples of internal olefin sulfonates usable in the formation of the muzzler slugs of the present invention are: internal olefin sulfonate having 12, 14, 16, 18, 20, 22, 24, 12-16, 13-14, 13-16, 14 I 18, 15-18, 16-18, 16-20, 17-20, 18-20, and 20-24 carbon I
atoms. These sulfonates may be used alone or in any mixture thereof.
As mentioned above, the muzzler slugs of the present invention contain about 1% to about 30~ by weight of the surfactant. However, the muzzler slugs desirably contain about 3% to about 25~ by weight of the surfactant, taking into consideration both low interracial tensions and reasonable cost The amount of the higher internal olefin sulfonates having 10 to 26 carbon atoms should be lo at least 50% by weight, desirably 60~ by weight or more, based on the total amount of the surfactants contained in the muzzler slugs.
The hydrocarbons usable as an oil component in the present invention include, for example, petroleum, pique-fled petroleum gas, crude gasoline ~naphtha), kerosine,diesel oil, and fuel oil. The recovered petroleum it desirably used due to its low cost and availability as well as its composition, which is similar to that of the oil contained in subterranean reservoirs. As mentioned above, the muzzler slugs of the present invention can contain about I to about 90% by weight of hydrocarbons.
The desirable concentration of hydrocarbons is within the range of about 3% to about 40~ by weight whereby an oil-in-water (O/W) type emulsion is formed, since the 25 use of a large amount of hydrocarbons is not economical.
The cosurfactants used in the formation of the muzzler slugs of the present invention are an essential constituent for forming micro-emulsions associated with 2t7 _ 9 _ the surfactants. The cosurfactants usable in the present invention are those having an alcoholic hydroxyl group.
the desirable cosurfactants are alcohols having the general formula:
S Rescission wherein n is a number of from 0 to about 4 and R" is an alkyd or alkenyl group having 4 to 8 carbon atoms when n is zero and an alkyd or alkenyl group having 6 to lo carbon atoms, a phenol group, or an alkylphenyl group lo having 7 to 16 carbon atoms when n it not zero. The aliphatic groups of R" may be straight chain or branched--chain groups.
Examples of such alcohols are buttonless, pentanols, hexanols, 2-ethylhexanol or other octanols, polyoxy-lo ethylene hexylethers (n = lo, polyoxyethylene decylethers(n = 2), polyoxyethylene tridecylethers (n = 4), polyoxy~
ethylene butylphenylethers on = 2), polyoxyethylene nonylphenylethers (n = 3), and polyoxyethylene dodecyl-phenylethers (n = 4).
As mentioned above, the muzzler slugs of the present invention can contain about 0.1% to about I by weight of the cosurfactants. However, the desirable concern-traction of the cosurfactants is within the range of about 1% to about 15% by weight from the viewpoints of the stability of the micro emulsions and the decreasing capacity for the interracial tensions.
As mentioned above, the muzzler slugs of the present invention contain internal olefin sulfonates having lo Jo to 26 carbon atoms as an essential or major constituent of the surfactants. However, other auxiliary surfactants can alto key included, together with the internal olefln sulfonates.
Examples of such auxiliary suxfactants are anionic surfactants and non ionic surfactants such as petroleum sulfonates, alkylbenzene sulfonates, polyoxye~hylene alkylether sulfates, dialkyl sulfosuccinates, alpha--olefin sulfonates, paraffin gut ion ales, soaps, higher 10 alcohol ethoxylate~, alkylphenol ethoxylates, polyol Patty acid esters, fatty acid alkylol asides, and pow-oxyethylene fatty acid aside 5 .
The viscosity of the muzzler slugs of the present invention can be suitably adjusted by selecting the kinds and amounts of the component s of the micro emulsions However, when a muzzler slug having a high viscosity is desired, an appropriate known thickening agent such as a water-soluble polymer can be added to the mice far slugs .
Examples of thickening agents usable in the formation of the muzzler slugs are heteropolysaccharides produced by microbes, naphthalenesulfonic acid-formaldehyde condemn-sates, polyacrylamides, polyacrylates, hydroxyethyl-cellulose, and carboxymethylcelluloses The muzzler slugs of the present invention can be readily obtained by any known method of production. For example, the hydrocarbons, the surfactants, the aqueous medium, and the cosurfactants can be mixed in any mixing order by using conventional mixing devices, mixing Jo temperatures, and mixing pressures.
The recovery of oil from subterranean reservoirs can be carried out by means of any conventional muzzler drive method by using the muzzler slugs of the present invention. For instance, the muzzler slugs are injected under pressure into at least one injection well of the subterranean reservoirs. Then, at least one driving fluid such as flood water and/or aqueous solution of the above-mentioned thickening agent it Injected into the injection well so as to transfer or drive the remaining oil toward on oil production well and to recover the oil from the production well. The suitable amount of the muzzler slugs injected into the injection well is about I to about 25% by volume of the porosity of the subtler-reunion reservoirs.
The suitable salt concentration of the subterranean water in the subterranean reservoirs where the muzzler slugs of the present invention can be applied is 0% to about 15~ by weight, desirably about 0.1~ to about 12%
by weight and, more desirably, about 0.5~ to about lo by weight. Although the salt concentration of water used in the formation of the muzzler slugs is not necessarily the same as that of the subterranean water, they are desirably the same prom the viewpoints that the Walt concentration is changed during the sweeping.
As mentioned hereinabove, the muzzler slugs of the present invention contain the internal olefin sulfonates having a disulfonate content of about 20~ by weight or I
Lowe as an essential component of the surfactantO The resultant macular slugs thus haze an excellent salinity tolerance and hereditary resistance and can form micro--emulsions by using water having a very wide salt consign traction ox soft water to urine having a high salt concentration. Furthermore, the muzzler slugs of the present invention have very small interracial tensions between water and the micro emulsions and between oil and the micro-emulsions and have resistance against the change in the salt concentrations. As a result, the following remarkable advantageous features can be obtained:
1) Either soft water, seawater, or subtler-reunion water having a hush salt Concentration can be freely used;
(2) The muzzler slugs injected into the subterranean reservoirs are subjected to no substantial adverse effects by inorganic salts present in the subtler-reunion reservoirs;
(3) Thy muzzler drive method can be readily applied in subterranean reservoirs containing oil having a low viscosity to a high viscosity; and
(4) A high oil recovery efficiency can be attained since stable micro-emulsions are maintained in the subterranean reservoirs until oil banks are formed.
EXAMPLES
The present invention now will ye ~Irther illustrated by, but is by no means limited to, the following examples, in which the component ratios or amounts of samples used are based on n % by weight" unless orioles specified.
Example 1 Micro-emulsions were prepared by weighing 10.5~ of sodium C14-C18 internal olefin sulfonates (C14-Cl~ IOS-Na) having various disulfonate contents or petroleum sulfonate TRACY (manufactured by Witch Chemical Corp.) as a sun-fact ant, 4.5~ of Amy alcohol as a cosurfactant, 17% of fuel oil (ASTM No. 2 oil) as a hydrocarbon, and 68% of an aqueous solution of 8% of sodium chloride dissolved in demineralized water as a brine in a beaker. The resultant mixture was stirred at 100 rum for 30 minutes at a temperature of 71C.
The IOS-Na samples having various disulfonate (DO) contents used as a surfactant were prepared by changing the molar ratio of the starting internal olefin and S03.
The samples having a small DO content were prepared by extracting the disulfonates from the reaction products by isobutyl alcohol to adjust the desired DO
contents.
The micro-emulsion forming capabili~les, the inter-facial tension decreasing capabilities, and the oil recovery efficiencies of the micro-emulsions thus prepared were evaluated as follows. The results are shown in Table 1.
The micro-emulslon forming capabilities were deter-mined from the visual appearance of the micro-emulslons according to the following:
o ...... A transparent or translucent and home-generous micro-emul~ion was formed x ...... An opaque suspend ion, rather than a micro-emulsion was formed.
The interracial tensions were measured by a spinning drop type tensiometer at 71C in an appropriately diluted system.
The oil recovery tests were carried out by using err sandstone core having a size of 3.8 cm diameter and 28 cm length and having a permeability of about 500 my and a porosity of about 20%. A core sufficiently saturated with brine was set Lo a core holder and, then, Lull oil was injected under pressure m to the core at a feed rate of 6 cumin until no brine was discharged.
Then, brine was injected under pressure at the same feed rate in a water drive method until the content of the fuel oil in the effluent became less than 0.1%. thus, the fuel oil was recovered. After the waxer drive method the core holder and the micro-emulsions were placed in a constant temperature bath at a temperature of 71C for a muzzler drive method. The micro-emulsions were first injected under pressure into the core in an amount of 10% by volume of the pore volumes, a polymer solution (i.e., Lowe pup of Xanthan gum solution m a brine solution) way when injected under pressure in an amount of 100% by volume of the pore volume, and, finally, brine was injected under pressure in an amount of Lowe .
by volume of the pore volume. Thus, the fuel oil was I
recovered. The injection rate under pressure was 2 feet/day. The oil recovery efficiency was determined by measuring the amount of water in the core after the test in a Tulane azeotropic method to convert the recovery amount of the fuel oil.
Table l A B C D E F G
Surfactant 14 18 Petroleum Disul*nabe ccnbent 0* 4 712l9 24 sulfcnate (% effective component) Micro-emulsion rang c~pabili~ O o x In racial tension 3.5 4.4 5.2 6~4 9.8 19.3 (x 10 dyne/cm) Oil recovery 93 92 91 82 72 * Diaphaneity content: less than 0.1 Example 2 Micro-emulsions were prepared by weighing 10.5% of Cluck IOS-Na containing 7% (based on the effective component) of the disulfonate as a surfac~ant, 4.5~ of Amy alcohol as a cosurfactant, 17% of fuel oil (ASSET
No. 2 oil) as a hydrocarbon, and 68~ of an aqueous solution of a given amount of sodium chloride dissolved in demineralized water, or an aqueous solution of a given amount of Coequal or Meekly dissolved in the above-I
-prepared aqueous sodium chloride solution in a beaker.
The resultant mixture was stirred at 100 rip for 30 minutes at a temperature of 71C.
The micro-emulsion forming capabilities, the inter-facial tensions, and the oil recovery efficiencies of the micro-emulsions were evaluated in the same manner as in Example 1. The results are shown in Table 2 below.
Table 2 .
Sample No H I J K L
S~riactant 14 18 a Ermine Nail 1 12 15 5 5 (%) Cook - - - 0.5 McCoy - - _ _ owe M~xo-emulsion no O O O O O
capability Interracial tension 6.2 5.1 4.8 4.6 4.6 (x 10 dyne/cm) Old wreck (~)90 91 91 91 91 . .
Example 3 Micro-emulsions were prepared by weighing Lowe of C -Clue IOS-Na, C18-C20 ITS My, or C20 22 a surfactant, 4.5~ of Amy alcohol as a cosurfactant, 17% of fuel oil (ASTM No. 2 oil), and 68% of an aqueous solution of 8% of sodium chloride dissolved in definer-alized water in a beaker The resultant mixture was I
stirred at 100 rum for 30 minutes at a temperature of 71C.
he micro-emulsion forming capabilities, the inter-facial tensions, and the oil recovery efficiencies of the mlcro-emulsions were evaluated in top same manner as in Example l. The results are shown in Table 3 below.
Table 3 _ .
_ Same No. M_ N JO
Surfactant C13 C14 IOS-Na C18-C20 IOS,M~ C20 C22 Disulfonate content (I For effective 6 8 7 camFonent) Micro~lsion arming capability In facial Zion 9 9 6.5 3.8 (x 10 3 dyne/cm) Oil recovery (~) 81 90 92 Example 4 Muzzler slug compositions containing anionic surfactants, cosurfactants, hydrocarbons, and aqueous media were prepared.
The anionic surfactna~ used was sodium C14-Cl~
IOS-Na ADS = 7%), C20-C2~ IOS-Na ADS = 9%), petroleum sulfonate TRACY (manufactured by Witch Chemical Corp.).
The cosurfactants used were Amy alcohol or isopropyl alcohol. The hydrocarbons used were kerosene or fuel Lo oil (ASTM No. 2 fuel oil). The aqueous media used were seawater having a saline content of about 3.5~ and an alkaline earth metal ion concentration of about 1,600 Pam, or soft water.
S The muzzler slugs were prepared by first mixing the surfactant and the aqueous medium and, then, adding the cosurfactant and the hydrocarbon to the mixture, while stirring it.
The compositions and properties ox the muzzler slugs thus obtained are shown in Table 4. Visual appearance was determined according Jo the following:
o ...... A micro-emulsion was formed x ...... A suspension, rather than a micro-emulsion was formed.
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I U , o us I I' x I o a D I X
us o I o Y ¦ I I JO I 0 1 1 O Us I I
I I , or I a I I o co _ Jo Ye ,,~ tl, '0 o I -. ....
~;~32~
. _ . _ r I O o r D I I O o O
I ', o I o Jo , x i o I
I
Example 5 Muzzler slug samples were prepared in the same manner as descried in Example 4 except that various brines obtained by dissolving sodium chloride in de-mineralized water to predetermined saline concentrations were used.
The compositions and the properties of the samples are shown in Table S.
Example 6 Muzzler slug samples were prepared in the same manner as described in Example 4 except that various brines were obtained by adding I by weight of sodium chloride and magnesium chloride and/or calcium chloride so as to provide the predetermined bivalent metal ion concentration to demineralized water.
The compositions and the properties of the samples are shown in Table 6.
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, o us I O N I
I our I I 1` I I I O I
Jo ¦ I I D I clue:) I I I I X
o D I I D I I I CO
D
a) I. g g 8 on x 2 8 b o 3 Ye to o s C _ I C\ E us o C -I
_ I o >
Jo I o I
o I ED
M i I I n I I o O
I r` I I I I I O r` JO
D I I I I I O I
Jo I I l l l O us I
I I I I I I I I x -Iv I! 5 TV
32~
I -Muzzler slug samples were prepared in the same manner as described in Example 4 except that the counter ion s o f the internal olefin sup ion a toes were changed.
The compositions and the properties of the samples are shown in Table PA (monovalent cations) and Table 73 diva lent cations).
Example 8 Muzzler slug samples were prepared in the same manner as described in Example 4 except that two or more internal olefin sulfonates were used together.
The compositions and the properties of the samples are shown in Table 8.
I o I
I I ' , us , o o owe I æ
I us ¢ I I O O O ED
a) o us Jo _ _. 10 O
O
O
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Jo o I Ion I I o us I o 1~7 O
1 ` I I
1 I- o o X -a) Jo O
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o Jo o Jo Ye y o Jo I
I
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Jo . - - Ox X -o 11 " ,. " "
Jo o 3 Us
EXAMPLES
The present invention now will ye ~Irther illustrated by, but is by no means limited to, the following examples, in which the component ratios or amounts of samples used are based on n % by weight" unless orioles specified.
Example 1 Micro-emulsions were prepared by weighing 10.5~ of sodium C14-C18 internal olefin sulfonates (C14-Cl~ IOS-Na) having various disulfonate contents or petroleum sulfonate TRACY (manufactured by Witch Chemical Corp.) as a sun-fact ant, 4.5~ of Amy alcohol as a cosurfactant, 17% of fuel oil (ASTM No. 2 oil) as a hydrocarbon, and 68% of an aqueous solution of 8% of sodium chloride dissolved in demineralized water as a brine in a beaker. The resultant mixture was stirred at 100 rum for 30 minutes at a temperature of 71C.
The IOS-Na samples having various disulfonate (DO) contents used as a surfactant were prepared by changing the molar ratio of the starting internal olefin and S03.
The samples having a small DO content were prepared by extracting the disulfonates from the reaction products by isobutyl alcohol to adjust the desired DO
contents.
The micro-emulsion forming capabili~les, the inter-facial tension decreasing capabilities, and the oil recovery efficiencies of the micro-emulsions thus prepared were evaluated as follows. The results are shown in Table 1.
The micro-emulslon forming capabilities were deter-mined from the visual appearance of the micro-emulslons according to the following:
o ...... A transparent or translucent and home-generous micro-emul~ion was formed x ...... An opaque suspend ion, rather than a micro-emulsion was formed.
The interracial tensions were measured by a spinning drop type tensiometer at 71C in an appropriately diluted system.
The oil recovery tests were carried out by using err sandstone core having a size of 3.8 cm diameter and 28 cm length and having a permeability of about 500 my and a porosity of about 20%. A core sufficiently saturated with brine was set Lo a core holder and, then, Lull oil was injected under pressure m to the core at a feed rate of 6 cumin until no brine was discharged.
Then, brine was injected under pressure at the same feed rate in a water drive method until the content of the fuel oil in the effluent became less than 0.1%. thus, the fuel oil was recovered. After the waxer drive method the core holder and the micro-emulsions were placed in a constant temperature bath at a temperature of 71C for a muzzler drive method. The micro-emulsions were first injected under pressure into the core in an amount of 10% by volume of the pore volumes, a polymer solution (i.e., Lowe pup of Xanthan gum solution m a brine solution) way when injected under pressure in an amount of 100% by volume of the pore volume, and, finally, brine was injected under pressure in an amount of Lowe .
by volume of the pore volume. Thus, the fuel oil was I
recovered. The injection rate under pressure was 2 feet/day. The oil recovery efficiency was determined by measuring the amount of water in the core after the test in a Tulane azeotropic method to convert the recovery amount of the fuel oil.
Table l A B C D E F G
Surfactant 14 18 Petroleum Disul*nabe ccnbent 0* 4 712l9 24 sulfcnate (% effective component) Micro-emulsion rang c~pabili~ O o x In racial tension 3.5 4.4 5.2 6~4 9.8 19.3 (x 10 dyne/cm) Oil recovery 93 92 91 82 72 * Diaphaneity content: less than 0.1 Example 2 Micro-emulsions were prepared by weighing 10.5% of Cluck IOS-Na containing 7% (based on the effective component) of the disulfonate as a surfac~ant, 4.5~ of Amy alcohol as a cosurfactant, 17% of fuel oil (ASSET
No. 2 oil) as a hydrocarbon, and 68~ of an aqueous solution of a given amount of sodium chloride dissolved in demineralized water, or an aqueous solution of a given amount of Coequal or Meekly dissolved in the above-I
-prepared aqueous sodium chloride solution in a beaker.
The resultant mixture was stirred at 100 rip for 30 minutes at a temperature of 71C.
The micro-emulsion forming capabilities, the inter-facial tensions, and the oil recovery efficiencies of the micro-emulsions were evaluated in the same manner as in Example 1. The results are shown in Table 2 below.
Table 2 .
Sample No H I J K L
S~riactant 14 18 a Ermine Nail 1 12 15 5 5 (%) Cook - - - 0.5 McCoy - - _ _ owe M~xo-emulsion no O O O O O
capability Interracial tension 6.2 5.1 4.8 4.6 4.6 (x 10 dyne/cm) Old wreck (~)90 91 91 91 91 . .
Example 3 Micro-emulsions were prepared by weighing Lowe of C -Clue IOS-Na, C18-C20 ITS My, or C20 22 a surfactant, 4.5~ of Amy alcohol as a cosurfactant, 17% of fuel oil (ASTM No. 2 oil), and 68% of an aqueous solution of 8% of sodium chloride dissolved in definer-alized water in a beaker The resultant mixture was I
stirred at 100 rum for 30 minutes at a temperature of 71C.
he micro-emulsion forming capabilities, the inter-facial tensions, and the oil recovery efficiencies of the mlcro-emulsions were evaluated in top same manner as in Example l. The results are shown in Table 3 below.
Table 3 _ .
_ Same No. M_ N JO
Surfactant C13 C14 IOS-Na C18-C20 IOS,M~ C20 C22 Disulfonate content (I For effective 6 8 7 camFonent) Micro~lsion arming capability In facial Zion 9 9 6.5 3.8 (x 10 3 dyne/cm) Oil recovery (~) 81 90 92 Example 4 Muzzler slug compositions containing anionic surfactants, cosurfactants, hydrocarbons, and aqueous media were prepared.
The anionic surfactna~ used was sodium C14-Cl~
IOS-Na ADS = 7%), C20-C2~ IOS-Na ADS = 9%), petroleum sulfonate TRACY (manufactured by Witch Chemical Corp.).
The cosurfactants used were Amy alcohol or isopropyl alcohol. The hydrocarbons used were kerosene or fuel Lo oil (ASTM No. 2 fuel oil). The aqueous media used were seawater having a saline content of about 3.5~ and an alkaline earth metal ion concentration of about 1,600 Pam, or soft water.
S The muzzler slugs were prepared by first mixing the surfactant and the aqueous medium and, then, adding the cosurfactant and the hydrocarbon to the mixture, while stirring it.
The compositions and properties ox the muzzler slugs thus obtained are shown in Table 4. Visual appearance was determined according Jo the following:
o ...... A micro-emulsion was formed x ...... A suspension, rather than a micro-emulsion was formed.
~3~7 I o I o a`
I I x I I
I U , o us I I' x I o a D I X
us o I o Y ¦ I I JO I 0 1 1 O Us I I
I I , or I a I I o co _ Jo Ye ,,~ tl, '0 o I -. ....
~;~32~
. _ . _ r I O o r D I I O o O
I ', o I o Jo , x i o I
I
Example 5 Muzzler slug samples were prepared in the same manner as descried in Example 4 except that various brines obtained by dissolving sodium chloride in de-mineralized water to predetermined saline concentrations were used.
The compositions and the properties of the samples are shown in Table S.
Example 6 Muzzler slug samples were prepared in the same manner as described in Example 4 except that various brines were obtained by adding I by weight of sodium chloride and magnesium chloride and/or calcium chloride so as to provide the predetermined bivalent metal ion concentration to demineralized water.
The compositions and the properties of the samples are shown in Table 6.
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, o us I O N I
I our I I 1` I I I O I
Jo ¦ I I D I clue:) I I I I X
o D I I D I I I CO
D
a) I. g g 8 on x 2 8 b o 3 Ye to o s C _ I C\ E us o C -I
_ I o >
Jo I o I
o I ED
M i I I n I I o O
I r` I I I I I O r` JO
D I I I I I O I
Jo I I l l l O us I
I I I I I I I I x -Iv I! 5 TV
32~
I -Muzzler slug samples were prepared in the same manner as described in Example 4 except that the counter ion s o f the internal olefin sup ion a toes were changed.
The compositions and the properties of the samples are shown in Table PA (monovalent cations) and Table 73 diva lent cations).
Example 8 Muzzler slug samples were prepared in the same manner as described in Example 4 except that two or more internal olefin sulfonates were used together.
The compositions and the properties of the samples are shown in Table 8.
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I us ¢ I I O O O ED
a) o us Jo _ _. 10 O
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Claims (7)
1. A micellar slug for use in the recovery of oil, said slug consisting essentially of a hydrocarbon, an aqueous medium, a surfactant, and a cosurfactant having an alcoholic hydroxyl group, said surfactant containing, as an essential component, an internal olefin sulfonate having 10 to 26 carbon atoms obtained by sulfonating internal olefins containing as a main constituent vinylene-type monoolefin having the general formula:
R - CH = CH - R' wherein R and R' are independently straight- or branched-chain saturated hydrocarbon radicals having 1 or more carbon atoms provided that the total carbon atom numbers of R and R', is 8 to 24, followed by neutralization.
R - CH = CH - R' wherein R and R' are independently straight- or branched-chain saturated hydrocarbon radicals having 1 or more carbon atoms provided that the total carbon atom numbers of R and R', is 8 to 24, followed by neutralization.
2. A micellar slug as claimed in claim 1, wherein said surfactant is an internal olefin sulfonate having 12 to 24 carbon atoms.
3. A micellar slug as claimed in claim 1, wherein said micellar slug consists essentially of about 2% to about 90% by weight of the hydrocarbon, about 4% to about 95% by weight of the aqueous medium, about 1% to about 30% by weight of the surfactant, and about 0.1% to about 20% by weight of the cosurfactant.
4. A micellar slug as claimed in claim 1, wherein said cosurfactant has the general formula:
R"O(CH2CH2O)nH
wherein n is a number of from 0 to about 4 and R" is an alkyl or alkenyl group having 4 to 8 carbon atoms when n is zero and an alkyl or alkenyl group having 6 to 15 carbon atoms, a phenyl group, or an alkylphenyl group having 7 to 16 carbon atoms when n is not zero.
R"O(CH2CH2O)nH
wherein n is a number of from 0 to about 4 and R" is an alkyl or alkenyl group having 4 to 8 carbon atoms when n is zero and an alkyl or alkenyl group having 6 to 15 carbon atoms, a phenyl group, or an alkylphenyl group having 7 to 16 carbon atoms when n is not zero.
5. A micellar slug as claimed in claim 1, wherein said internal olefin sulfonate has a disulfonate content of up to about 20% by weight.
6. A micellar slug as claimed in claim 5, wherein the disulfonate content is from about 0.5% to about 15%
by weight.
by weight.
7. A process for producing oil from an oil-bearing subterranean reservoir penetrated by wells which comprises the steps of:
1) injecting into said reservoir through an injection well a micellar slug consisting essentially of a hydrocarbon, an aqueous medium, a surfactant, and a cosurfactant having an alcoholic hydroxyl group, said surfactant containing, as an essential component, an internal olefin sulfonate having 10 to 26 carbon atoms obtained by sulfonating internal olefins containing as a main constituent vinylene-type monoolefin having the general formula:
R - CH = CH - R' wherein R and R' are independently straight- or branched-chain saturated hydrocarbon radicals having 1 or more carbon atoms provided that the total carbon atom numbers of R and R', is 8 to 24, followed by neutralization;
(2) injecting into said reservoir at least one driving fluid; and (3) recovering oil from said reservoir through a production well.
1) injecting into said reservoir through an injection well a micellar slug consisting essentially of a hydrocarbon, an aqueous medium, a surfactant, and a cosurfactant having an alcoholic hydroxyl group, said surfactant containing, as an essential component, an internal olefin sulfonate having 10 to 26 carbon atoms obtained by sulfonating internal olefins containing as a main constituent vinylene-type monoolefin having the general formula:
R - CH = CH - R' wherein R and R' are independently straight- or branched-chain saturated hydrocarbon radicals having 1 or more carbon atoms provided that the total carbon atom numbers of R and R', is 8 to 24, followed by neutralization;
(2) injecting into said reservoir at least one driving fluid; and (3) recovering oil from said reservoir through a production well.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58045291A JPS59173485A (en) | 1983-03-19 | 1983-03-19 | Micelle solution for recovering petroleum |
| JP58-45291 | 1983-03-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1232127A true CA1232127A (en) | 1988-02-02 |
Family
ID=12715204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000449413A Expired CA1232127A (en) | 1983-03-19 | 1984-03-12 | Micellar slug for oil recovery |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS59173485A (en) |
| CA (1) | CA1232127A (en) |
| GB (1) | GB2136855A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2032242B1 (en) | 2006-05-24 | 2014-10-01 | Marine 3 Technologies Holdings (Pty) Ltd | A surface active ingredient composition |
| CA2672632A1 (en) * | 2006-12-21 | 2008-07-03 | Shell Internationale Research Maatschappij B.V. | Method and composition for enhanced hydrocarbons recovery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5915185A (en) * | 1982-07-19 | 1984-01-26 | ライオン株式会社 | Miscelle solution for recovery of crude oil |
-
1983
- 1983-03-19 JP JP58045291A patent/JPS59173485A/en active Granted
-
1984
- 1984-03-07 GB GB08406012A patent/GB2136855A/en not_active Withdrawn
- 1984-03-12 CA CA000449413A patent/CA1232127A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2136855A (en) | 1984-09-26 |
| JPS59173485A (en) | 1984-10-01 |
| GB8406012D0 (en) | 1984-04-11 |
| JPH0331871B2 (en) | 1991-05-08 |
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|---|---|---|---|
| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 20050202 |