Claims
- 1. A method for preparing petroleum sulfonates comprising the sequential steps of
- (I) intimately contacting from about 5 to 40 parts by weight of sulfur trioxide with 100 parts by weight of a flowable liquid mixture, which comprises on a 100 weight percent total mixture basis:
- (A) from about 85 to 99.5 weight percent of a petroleum oil feed stock, and
- (B) from about 0.5 to 15 weight percent of an additive, said petroleum oil feed stock being characterized by
- (a.sub.1) having an API gravity ranging from about 5.degree. to 60.degree. at 60.degree. F.,
- (a.sub.2) having a boiling point (corrected atmospheric) ranging from about -20.degree. to 1400.degree. F., and
- (a.sub.3) containing from about 10 to 95 weight percent (100 weight percent total stock basis) of sulfonatable components,
- said additive being characterized by
- (b.sub.1) being comprised of unsulfonatable organic radical portions possessing an average molecular weight range from about 55 to 6000,
- (b.sub.2) having a boiling point in the range from about 212.degree. to 932.degree. F. corrected atmospheric, and
- (b.sub.3) a preponderance of such radicals each having attached at least one proton replaceable by a sulfo group and at least one moiety selected from the group consisting of an aromatic nucleus, an olefinic carbon pair, and an oxygen atom directly bonded to a carbon atom by at least one bond,
- said contacting being conducted at a temperature of from about 77.degree. to 392.degree. F., said contacting being continued for a time at least sufficient to sulfonate at least about 10 weight percent of the total sulfonatable components present in said petroleum oil feed stock so as to attain a crude acidic sulfonation reaction mixture; and
- (II) intimately contacting said crude acidic reaction mixture with about 0.5% to about 20% by weight, on a 100 weight percent total reaction mixture basis, of water and maintaining the so-attained mixture at a temperature of about 50.degree. to about 150.degree. C. for a period of time ranging from about one minute to about 60 minutes.
- 2. A method as defined in claim 1 wherein the amount of water brought into intimate contact with the crude acidic reaction mixture is about 2% to about 10% by weight, on a 100 weight percent total reaction mixture basis.
- 3. A method as defined in claim 1 wherein the crude acidic reaction mixture-water mixture is maintained at a temperature of about 80.degree. to about 100.degree. C.
- 4. A method as defined in claim 1 wherein the crude acidic reaction mixture-water mixture is maintained at said temperature for a period of time ranging from about 2 to about 30 minutes.
- 5. A method as defined in claim 1 including intimately contacting the crude acidic reaction mixture-water mixture attained after step II with a sufficient amount of a base to attain a pH within the resultant mixture in the range of about 3 to 12.
- 6. A method as defined in claim 5 wherein the amount of base brought into intimate contact with said crude acidic reaction mixture-water mixture is sufficient to attain a pH within the resultant mixture in the range of about 6 to 11.
- 7. A method as defined in claim 5 including extracting the base-treated crude acidic reaction mixture-water mixture so as to remove salts and free oil.
- 8. A method as defined in claim 1 wherein said flowable liquid comprises a film and a continuous reaction takes place.
- 9. A method as defined in claim 1 wherein said flowable liquid is confined within a reaction vessel and a batch reaction takes place.
- 10. A method as defined in claim 1 wherein said flowable liquid is confined within a reaction vessel and a continuous adding of reactants, and continuous removal of reaction products takes place to effect a quasi-continuous sulfonation.
- 11. A method as defined in claim 1 wherein said petroleum oil feed stock includes aromatic portions which have a molecular weight in the range of about 200 through about 1000.
- 12. The method of claim 1 wherein said contacting is continuously accomplished by the steps of
- forming a flowing liquid film of said mixture on a temperature-controlled reaction surface;
- impinging said liquid film with a mixture of gaseous sulfur trioxide and an inert gas so as to attain a sulfonation reaction between sulfonatable components in said film and sulfur trixode;
- controlling the reaction temperature so as to maintain said reaction temperature in the range of about 77.degree. to about 392.degree. F., and
- injecting about 2% to about 10% water into the so-attained reaction mixture while maintaining the temperature of the resultant mixture in the range of about 50.degree. to 150.degree. C. for a period of time ranging from about 2 to about 30 minutes.
- 13. A method as defined in claim 12 wherein said additive includes at least one C.sub.2 to C.sub.30 main hydrocarbon chain and is characterized as having a boiling point in the range of about 212.degree. to 932.degree. F.
- 14. A method as defined in claim 13 wherein said additive is selected from the group consisting of unsaturated aliphatic hydrocarbon compounds, substituted and unsubstituted aromatic compounds, olefinic compounds, oxygen-containing compounds, hydroxy-containing compounds, ester compounds, ether compounds, ester-ether compounds, ketone compounds, fatty acid compounds and mixtures thereof.
- 15. A method as defined in claim 12 wherein said additive is a C.sub.4 to C.sub.28 oxygen-containing compound characterized as having a boiling point in the range of about 212.degree. to 932.degree. F.
- 16. A method as defined in claim 15 wherein said oxygen-containing compound is a hydroxy-containing compound.
- 17. A method as defined in claim 16 wherein said hydroxy-containing compound is a C.sub.6 to C.sub.28 alcohol.
- 18. A method as defined in claim 17 wherein said alcohol is selected from the group consisting of hexanol, octanol, nonanol, decanol, octadecanol, dodecanol, lauryl, myristyl, palmityl, stearyl and mixtures thereof.
- 19. A method as defined in claim 15 wherein said oxygen-containing compound is an oxo alcohol still bottom.
- 20. A method as defined in claim 19 wherein said oxo alcohol still bottom is comprised of about 2 to 20% by weight of octyl alcohol; about 4 to 40% by weight of nonyl alcohol, about 25 to 90% by weight of decyl and higher boiling materials and about 20 to 80% by weight of esters.
- 21. A method as defined in claim 19 wherein said oxo alcohol still bottom is comprised of about 5% by weight of octyl alcohol, about 10% by weight of nonyl alcohol, about 35% by weight of decyl and higher boiling materials, about 45% by weight of esters and about 5% by weight of soaps.
- 22. A method as defined in claim 15 wherein said oxygen-containing compound is a phenolic compound.
- 23. A method as defined in claim 22 wherein said phenolic compound is selected from the group consisting of phenol, C.sub.1 to C.sub.16 alkyl phenols, C.sub.1 to C.sub.16 alkyl C.sub.1 to C.sub.200 alkoxy phenols and mixtures thereof.
- 24. A method as defined in claim 15 wherein said oxygen-containing compound is a glycol compound.
- 25. A method as defined in claim 15 wherein said oxygen-containing compound is alkoxylated with about 1 to 200 mols of a C.sub.2 to C.sub.4 alkylene oxide per mole of oxygen-containing compound.
- 26. A method as defined in claim 15 wherein said oxygen-containing compound is a tallow alcohol.
- 27. A method as defined in claim 12 wherein said additive is a C.sub.4 to C.sub.40 olefinic hydrocarbon characterized as having a boiling point in the range of about 212.degree. to 932.degree. F.
- 28. A method as defined in claim 12 wherein said additive is a C.sub.6 to C.sub.40 aromatic.
- 29. A method as defined in claim 12 wherein said additive is a C.sub.4 to C.sub.6 ether characterized as having a boiling point in the range of about 212.degree. to 932.degree. F.
- 30. A method as defined in claim 29 wherein said ether is selected from the group consisting of 4-methoxy butanol, 2-ethoxy ethanol, 2-propoxy ethanol, 2-butoxy ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol butyl ether and mixtures thereof.
- 31. A method as defined in claim 12 wherein said additive is a C.sub.4 to C.sub.6 hydrocarbon ether ester characterized as having a boiling point in the range of about 212.degree. to 932.degree. F.
- 32. A method as defined in claim 31 wherein said ether ester is selected from the group consisting of acetate ester of diethylene glycol monoethyl ether, acetate ester of ethylene glycol monoethyl ether, acetate ester of butylene glycol monoethyl ether and mixtures thereof.
- 33. A method as defined in claim 12 wherein said additive is a C.sub.7 to C.sub.30 alkaryl compound characterized as having a boiling point in the range of about 212.degree. to 932.degree. F.
- 34. A method as defined in claim 12 wherein said additive is a C.sub.1 to C.sub.4 alkyl ester of a C.sub.6 to C.sub.20 aliphatic acid characterized as having a boiling point in the range of about 212.degree. to 932.degree. F.
- 35. A method as defined in claim 34 wherein said alkyl ester acid is a methyl ester of a C.sub.12 to C.sub.18 fatty acid.
- 36. A method as defined in claim 34 wherein said alkyl ester acid is a methyl ester of a C.sub.8 to C.sub.10 fatty acid.
- 37. A method as defined in claim 34 wherein said alkyl ester acid is a methyl ester of a C.sub.14 to C.sub.28 fatty acid.
- 38. A method as defined in claim 12 wherein said additive is a C.sub.6 to C.sub.28 alkyl ester of a C.sub.6 to C.sub.28 aliphatic alcohol characterized as having a boiling point in the range of about 212.degree. to 932.degree. F.
- 39. A method as defined in claim 12 wherein said petroleum oil feed stock is selected from the group consisting of crude oil, topped crude oil and mixtures thereof.
- 40. A method as defined in claim 1 wherein said amount of the additive in said mixture ranges from about 0.5% to about 5% by weight of said petroleum oil feed stocks.
- 41. A method as defined in claim 1 wherein said amount of additive in said mixture ranges from about 2% to about 10% by weight of said petroleum oil feed stocks.
- 42. A method of claim 1 wherein said contacting is continuously accomplished by the steps of
- forming a flowing liquid film of said mixture on a temperature controlled reaction surface, said additive being selected from the group consisting of oxo alcohol still bottoms, C.sub.4 to C.sub.28 aliphatic alcohols, alkoxylated phenols, diethylene glycol monoethyl ether, alkoxylated nonyl phenols, alkoxylated tallow alcohol, 2-butoxy ethanol, acetate ester of diethylene glycol monoethyl ether, C.sub.8 -C.sub.10 alcohols, C.sub.8 -C.sub.10 fatty acid methyl esters, isopropyl palmitate, hydrogenated C.sub.12 -C.sub.16 fatty acid methyl esters, acetate ester of ethylene glycol monobutyl ether, C.sub.8 to C.sub.10 fatty acids, branched chain C.sub.15 alkyl benzene, branched chain dodecylbenzenes, palmitic acid, C.sub.14 -C.sub.18 .alpha.-olefins, mesityl oxide, acetate ester of ethylene glycol monoethyl ether, and mixtures thereof;
- impinging said liquid film with a mixture of gaseous sulfur trioxide and an inert gas so as to attain a sulfonation reaction between sulfonatable components in said film and sulfur trioxide;
- controlling the reaction temperature so as to maintain said reaction temperature in the range of about 77.degree. to about 392.degree. F.; and
- injecting about 2% to about 10% water into the so-attained reaction mixture while maintaining the temperature of the resultant mixture in the range of about 50.degree. to 150.degree. C. for a period of time ranging from about 2 to about 30 minutes.
- 43. A process of producing, as defined in claim 1, petroleum sulfonates having an average equivalent weight of from about 350 to 550 and being suitable for use in subterranean oil recovery processes, said contacting being accomplished by the steps comprising:
- forming a flowable liquid of said mixture on a temperature controlled reaction surface;
- contacting said liquid with a gaseous sulfur trioxide so as to attain a sulfonation reaction between sulfonatable components in said liquid and sulfur trioxide;
- controlling the reaction temperature so as to maintain said reaction temperature in the range of about 77.degree. F. to about 392.degree. F.; and
- (II) intimately contacting said crude acidic reaction mixture with about 0.5% to about 20% by weight, on a 100 weight percent total reaction mixture basis, and maintaining the so-attained mixture at a temperature of about 50.degree. to about 150.degree. C. for a period of time ranging from about one minute to about 60 minutes.
- 44. The process of claim 1 wherein said contacting is continued for a time at least sufficient to produce a sulfonated composition which comprises on a 100 organic weight percent total weight basis
- (A) from about 5 to 98 weight percent of monosulfonated hydrocarbon,
- (B) from about 0 to 50 weight percent of polysulfonated hydrocarbon, and
- (C) from about 2 to 90 weight percent of non-sulfonated petroleum.
- 45. A sulfonation product produced by the method of claim 1.
- 46. A sulfonation product produced by the method of claim 12.
- 47. A sulfonation product produced by the method of claim 42.
- 48. A method as defined in claim 1 including intimately contacting the crude acidic reaction mixture-water mixture attained after step II with a sufficient amount of a base to attain a pH within the resultant mixture in the range of about 3 to 12 and subjecting said resultant mixture to an extraction process so as to remove salts and free oil from said resultant mixture.
- 49. A method as defined in claim 48 wherein said extraction process comprises admixing a hydrophilic solvent selected from the group consisting of water, a C.sub.1 -C.sub.5 alcohol, benzene and mixtures thereof with said base-treated resultant mixture.
- 50. A sulfonation product produced by the method of claim 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 43 or 44.
CROSS-REFERENCE TO RELATED APPLICATIONS
This is a continuation-in-part application of our U.S. Ser. No. 676,470, filed Apr. 13, 1976 (now U.S. Pat. No. 4,148,821), which in turn is a continuation-in-part of our U.S. Pat. Ser. No. 515,013, filed Oct. 16, 1974 (now abandoned), which in turn is a continuation-in-part of our U.S. Ser. No. 432,439, filed Jan. 11, 1974 (now abandoned), which in turn is a continuation-in-part of our U.S. Ser. No. 9,065, filed Feb. 5, 1970 (now abandoned), all of which are incorporated herein by reference.
US Referenced Citations (1)
Number |
Name |
Date |
Kind |
3887611 |
Sweeney |
Jun 1975 |
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Continuation in Parts (4)
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Number |
Date |
Country |
Parent |
676470 |
Apr 1976 |
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Parent |
515013 |
Oct 1974 |
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Parent |
432439 |
Jan 1974 |
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Parent |
9065 |
Feb 1970 |
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