Patent US4177207A successfully refreshed from Google Patents.
US4177207A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Petroleum sulfonates
Assignee: Stepan Co
•
Filing: 1978-03-03
•
Granted: 1979-12-04
•
Expires: 1998-03-03
Abstract
Abstract Petroleum sulfonates yielding improved results in enhanced oil recovery processes are comprised of a reaction product obtained from a mixture of a major proportion of a petroleum oil feed stock, such as a crude or a portion thereof, and a minor proportion of an additive, such as an oxygenated hydrocarbon, i.e., an oxo-alcohol or the like, reacted with SO 3 under sulfonation conditions, mixed with about 0.5 to 20% (by reaction mixture weight) of water at the temperature in the range of about 50° to 150° C. for a relatively brief period of time and then neutralizing the resultant material with an base, such as NaOH. The neutralized petroleum sulfonated material thus obtained, which may or may not be extracted to remove unsulfonated organic material or salts, is then formulated into a slug for injection into an oil field for enhanced oil recovery.
Inventors
- 👤 Marvin L. Nussbaum
- 👤 Edward A. Knaggs
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 06:02
CPC Classifications
C; C07; C07C; C07C309/00; C07C309/01; C07C309/62; C09; C09K; C09K8/00; C09K8/58; C09K8/584; Y; Y10; Y10S; Y10S507/00; Y10S507/935; Y10S507/936
Claims Analysis
Total Claims: 51
Claim 1
Independent Claim
341 words
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 1 ) having an API gravity ranging from about 5° to 60° at 60° F., (a 2 ) having a boiling point (corrected atmospheric) ranging from about -20° to 1400° F., and (a 3 ) containing from about 10 to 95 weight percent (100 weight percent total stock basis) of sulfonatable components, said additive being characterized by (b 1 ) being comprised of unsulfonatable organic radical portions possessing an average molecular weight range from about 55 to 6000, (b 2 ) having a boiling point in the range from about 212° to 932° F. corrected atmospheric, and (b 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° to 392° 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° to about 150° C. for a period of time ranging from about one minute to about 60 minutes.
Claim 2
Independent Claim
341 words
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 1 ) having an API gravity ranging from about 5° to 60° at 60° F., (a 2 ) having a boiling point (corrected atmospheric) ranging from about -20° to 1400° F., and (a 3 ) containing from about 10 to 95 weight percent (100 weight percent total stock basis) of sulfonatable components, said additive being characterized by (b 1 ) being comprised of unsulfonatable organic radical portions possessing an average molecular weight range from about 55 to 6000, (b 2 ) having a boiling point in the range from about 212° to 932° F. corrected atmospheric, and (b 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° to 392° 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° to about 150° C. for a period of time ranging from about one minute to about 60 minutes.
Claim 3
Dependent Claim
39 words
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.
Claim 4
Dependent Claim
26 words
A method as defined in claim 1 wherein the crude acidic reaction mixture-water mixture is maintained at a temperature of about 80° to about 100° C.
Claim 5
Dependent Claim
32 words
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.
Claim 6
Dependent Claim
43 words
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.
Claim 7
Dependent Claim
41 words
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.
Claim 8
Dependent Claim
24 words
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.
Claim 9
Dependent Claim
20 words
A method as defined in claim 1 wherein said flowable liquid comprises a film and a continuous reaction takes place.
Claim 10
Dependent Claim
23 words
A method as defined in claim 1 wherein said flowable liquid is confined within a reaction vessel and a batch reaction takes place.
Claim 11
Dependent Claim
36 words
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.
Claim 12
Dependent Claim
30 words
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.
Claim 13
Dependent Claim
123 words
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° to about 392° 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° to 150° C. for a period of time ranging from about 2 to about 30 minutes.
Claim 14
Dependent Claim
39 words
A method as defined in claim 12 wherein said additive includes at least one C 2 to C 30 main hydrocarbon chain and is characterized as having a boiling point in the range of about 212° to 932° F.
Claim 15
Dependent Claim
46 words
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.
Claim 16
Dependent Claim
34 words
A method as defined in claim 12 wherein said additive is a C 4 to C 28 oxygen-containing compound characterized as having a boiling point in the range of about 212° to 932° F.
Claim 17
Dependent Claim
15 words
A method as defined in claim 15 wherein said oxygen-containing compound is a hydroxy-containing compound.
Claim 18
Dependent Claim
19 words
A method as defined in claim 16 wherein said hydroxy-containing compound is a C 6 to C 28 alcohol.
Claim 19
Dependent Claim
30 words
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.
Claim 20
Dependent Claim
17 words
A method as defined in claim 15 wherein said oxygen-containing compound is an oxo alcohol still bottom.
Claim 21
Dependent Claim
55 words
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.
Claim 22
Dependent Claim
53 words
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.
Claim 23
Dependent Claim
15 words
A method as defined in claim 15 wherein said oxygen-containing compound is a phenolic compound.
Claim 24
Dependent Claim
42 words
A method as defined in claim 22 wherein said phenolic compound is selected from the group consisting of phenol, C 1 to C 16 alkyl phenols, C 1 to C 16 alkyl C 1 to C 200 alkoxy phenols and mixtures thereof.
Claim 25
Dependent Claim
15 words
A method as defined in claim 15 wherein said oxygen-containing compound is a glycol compound.
Claim 26
Dependent Claim
33 words
A method as defined in claim 15 wherein said oxygen-containing compound is alkoxylated with about 1 to 200 mols of a C 2 to C 4 alkylene oxide per mole of oxygen-containing compound.
Claim 27
Dependent Claim
15 words
A method as defined in claim 15 wherein said oxygen-containing compound is a tallow alcohol.
Claim 28
Dependent Claim
34 words
A method as defined in claim 12 wherein said additive is a C 4 to C 40 olefinic hydrocarbon characterized as having a boiling point in the range of about 212° to 932° F.
Claim 29
Dependent Claim
18 words
A method as defined in claim 12 wherein said additive is a C 6 to C 40 aromatic.
Claim 30
Dependent Claim
33 words
A method as defined in claim 12 wherein said additive is a C 4 to C 6 ether characterized as having a boiling point in the range of about 212° to 932° F.
Claim 31
Dependent Claim
38 words
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.
Claim 32
Dependent Claim
35 words
A method as defined in claim 12 wherein said additive is a C 4 to C 6 hydrocarbon ether ester characterized as having a boiling point in the range of about 212° to 932° F.
Claim 33
Dependent Claim
42 words
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.
Claim 34
Dependent Claim
34 words
A method as defined in claim 12 wherein said additive is a C 7 to C 30 alkaryl compound characterized as having a boiling point in the range of about 212° to 932° F.
Claim 35
Dependent Claim
43 words
A method as defined in claim 12 wherein said additive is a C 1 to C 4 alkyl ester of a C 6 to C 20 aliphatic acid characterized as having a boiling point in the range of about 212° to 932° F.
Claim 36
Dependent Claim
25 words
A method as defined in claim 34 wherein said alkyl ester acid is a methyl ester of a C 12 to C 18 fatty acid.
Claim 37
Dependent Claim
25 words
A method as defined in claim 34 wherein said alkyl ester acid is a methyl ester of a C 8 to C 10 fatty acid.
Claim 38
Dependent Claim
25 words
A method as defined in claim 34 wherein said alkyl ester acid is a methyl ester of a C 14 to C 28 fatty acid.
Claim 39
Dependent Claim
43 words
A method as defined in claim 12 wherein said additive is a C 6 to C 28 alkyl ester of a C 6 to C 28 aliphatic alcohol characterized as having a boiling point in the range of about 212° to 932° F.
Claim 40
Dependent Claim
28 words
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.
Claim 41
Dependent Claim
31 words
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.
Claim 42
Dependent Claim
30 words
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.
Claim 43
Dependent Claim
231 words
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 4 to C 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 8 -C 10 alcohols, C 8 -C 10 fatty acid methyl esters, isopropyl palmitate, hydrogenated C 12 -C 16 fatty acid methyl esters, acetate ester of ethylene glycol monobutyl ether, C 8 to C 10 fatty acids, branched chain C 15 alkyl benzene, branched chain dodecylbenzenes, palmitic acid, C 14 -C 18 α-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° to about 392° 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° to 150° C. for a period of time ranging from about 2 to about 30 minutes.
Claim 44
Dependent Claim
154 words
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° F. to about 392° 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° to about 150° C. for a period of time ranging from about one minute to about 60 minutes.
Claim 45
Dependent Claim
66 words
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.
Claim 46
Dependent Claim
10 words
A sulfonation product produced by the method of claim 1.
Claim 47
Dependent Claim
10 words
A sulfonation product produced by the method of claim 12.
Claim 48
Dependent Claim
10 words
A sulfonation product produced by the method of claim 42.
Claim 49
Dependent Claim
64 words
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.
Claim 50
Dependent Claim
38 words
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 1 -C 5 alcohol, benzene and mixtures thereof with said base-treated resultant mixture.
Claim 51
Dependent Claim
51 words
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.
References Cited (Backward Citations)
US3887611A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1982-12-03 | 1983-06-04 | 1983-12-04 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-12-03 | 1987-06-04 | 1987-12-04 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-12-03 | 1991-06-04 | 1991-12-04 | $7700.00 | Window Closed / Lapsed |