# US 7,608,571 B2 · Method for recovering crude oil from a subterranean formation utilizing a polyphosphate ester

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- Number: US 7,608,571 B2
- Document ID: US7608571B2
- Status: Granted
- Kind: B2
- Application number: 12/137,823
- Filed: 2008-06-12
- Published: 2009-01-22
- Granted: 2009-10-27
- Earliest claimed: 2007-07-20
- Assignees: Rhodia Inc.
- Inventors: Tobias Johannes Fütterer; Lawrence Alan Hough; Robert Lee Reierson
- Web page: https://patentgrep.com/patent/US7608571B2

## CPC

- C09K 8/58: Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K 8/584: characterised by the use of specific surfactants
- C09K 8/602: {containing surfactants}
- C09K 8/885: {obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds}
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

An aqueous fluid useful for the recovery of crude oil from a subterranean formation, including water and one or more organophosphorus materials and methods for using same.

## Claims

### Claim 1

A method for recovering crude oil from a subterranean formation, comprising introducing to the formation an aqueous fluid comprising:
(a) water or brine and
(b) an organophosphorus material selected from the group consisting of:
(b)(1) organophosphorus compounds according to structure (I):
wherein:
each R1 is and each R2 is independently absent or O, provided that at least one of R1 and R2 is O,
each R3 is independently alkyleneoxy, poly(alkyleneoxy), which may optionally, be substituted on one or more carbon atom of such alkyleneoxy, or poly(alkyleneoxy) group by alkyl, alkoxy, alkenyl, aryl, or aryloxy,
R5 is and each R4 is independently absent or alkyleneoxy, poly(alkyleneoxy), which may optionally, be substituted on one or more carbon atom of such alkyleneoxy, or poly(alkyleneoxy) group by alkyl, alkoxy, alkenyl, aryl, or aryloxy,-
R6 and R8 are each and each R7 is independently H, or (C1-C30)hydrocarbon, which hydrocarbon may optionally be substituted on one or more carbon atoms by fluorine, alkyl, alkenyl or aryl, on one carbon atom by hydroxyl, and/or interrupted at one or more sites by an O, N, or S heteroatom, or —POR9R10,
R9 and R10 are each independently alkoxy, aryloxy, or (C1-C30)hydrocarbon, which hydrocarbon may optionally be substituted on one or more carbon atoms by fluorine, alkyl, alkenyl or aryl and/or interrupted at one or more sites by an O, N, or S heteroatom, and
m is an integer of from 2 to 5,
(b)(2) salts of organophosphorus compounds according to structure (I),
(b)(3) condensation reaction products of two or more molecules of one or more organophosphorus compounds according to structure (I), and
(b)(4) mixtures comprising two or more of the compounds, salts, and/or reaction products of (b)(1), (b)(2), and (b)(3).

### Claim 2 (depends on 1)

The method of claim 1, wherein in the organophosphorus compounds, each R1 and each R2 is O, and the organophosphorus compound is selected from the group consisting of:
(II)(1) an organophosphate ester according to structure (II):
(II)(2) salts of organophosphorus compounds according to structure (II),
(II)(3) condensation reaction products of two or more molecules of one or more organophosphorus compounds according to structure (II), and
(II)(4) mixtures comprising two or more of the compounds, salts, and/or reaction products of (II)(1), (II)(2), and (II)(3).

### Claim 3 (depends on 1)

The method of claim 1, wherein in the organophosphorus compounds, each R1 is absent, each R2 is O, and the organophosphorus compound is selected from the group consisting of:
(III)(1)an organophosphonate ester according to structure (III):
(III)(2) salts of organophosphorus compounds according to structure (III),
(III)(3) condensation reaction products of two or more molecules of one or more organophosphorus compounds according to structure (III), and
(III)(4) mixtures comprising two or more of the compounds, salts, and/or reaction products of (III)(1), (III)(2), and (III)(3).

### Claim 4 (depends on 1)

The method of claim 1, wherein in the organophosphorus compounds, each R1 is O, each R2 is absent, and the organophosphorus compound is selected from the group consisting of:
(IV)(1) an organophosphonate ester according to structure (IV):
(IV)(2) salts of organophosphorus compounds according to structure (IV),
(IV)(3) condensation reaction products of two or more molecules of one or more organophosphorus compounds according to structure (IV), and
(IV)(4) mixtures comprising two or more of the compounds, salts, and/or reaction products of (IV)(1), (IV)(2), and (IV)(3).

### Claim 5 (depends on 1)

The method of claim 1, wherein in the organophosphorus compounds, each R3 is a divalent radical according to structure (V), (VI), or (VII):
wherein:
each R12 and each R13 is H, alkyl, alkoxy, alkenyl, aryl, aryloxy, or two R12 groups that are attached to the adjacent carbon atoms may be fused to form, together with the carbon atoms to which they are attached, a (C6-C8)hydrocarbon ring,
R20 is H,
p, p′, q, x and x′ are each independently integers of from 2 to 5,
each r, s, r′, r″, and y is independently a number of from 0 to 25, provided that at least one of r and s is not 0,
u is an integer of from 2 to 10,
v and w are each numbers of from 1 to 25, and
t, t′, and t″ are each numbers of from 1 to 25,
provided that the product of the quantity (r+s) multiplied times t is less than or equal to about 100, the product of the quantity (v+r′) multiplied times t′ is less than or equal to about 100, and the product of the quantity (w+r″) multiplied time t″ is less than or equal to about 100.

### Claim 6 (depends on 5)

The method of claim 5, wherein in the organophosphorus compounds, each R4 and each R5 is independently absent or a divalent radical according to structure (V) or (VI).

### Claim 7 (depends on 5)

The method of claim 5, wherein in the organophosphorus compounds, each R3 is independently a divalent radical according to structure (V) or (VI), wherein R4 and are each independently absent or R3.

### Claim 8 (depends on 5)

The method of claim 5, wherein in the organophosphorus compounds, each R3 is independently a divalent radical according to structure (V), wherein p is 2, 3, or 4, r is an integer from 1 to 25, s is 0, t is an integer of from 1 to 2, and R4 and R5 are each independently absent or R3.

### Claim 9 (depends on 5)

The method of claim 5, wherein in the organophosphorus compounds, each R3 is independently a divalent radical according to structure (VI), wherein the R12 groups are fused to form, including the carbon atoms to which they are attached, a (C6-C8) hydrocarbon ring, each R13 is H, p′ is 2 or 3, u is 2, v is an integer of from 1 to 3, r′ is an integer from 1 to 25, t′ is an integer of from 1 to 25, the product of the quantity (v+r′) multiplied times t″ is less than or equal to about 100, and R4 and R5 are each independently absent or R3.

### Claim 10 (depends on 5)

The method of claim 5, wherein in the organophosphorus compounds, each R1 and each R2 is O, and the organophosphorus compound is selected from:
(II)(1) an organophosphate ester according to structure (II):
(II)(2) salts of organophosphorus compounds according to structure (II), and
(II)(3) condensation reaction products of two or more molecules of one or more organophosphorus compounds according to structure (II), and
(II)(4) mixtures comprising two or more of the compounds, salts, and/or reaction products of (II)(1), and (II)(2), and (II)(3),
wherein in the organophosphorus compounds, according to structure (II)
R6 and R8 are each and each R7 is independently H or (C1-C30)hydrocarbon, which hydrocarbon may optionally be substituted on one or more carbon atoms by fluorine, alkyl, alkenyl or aryl, on one carbon atom by hydroxyl, and/or interrupted at one or more sites by an O, N, or S heteroatom, or —POR9R10,
R4 and R5 are each absent,
each R3 is independently a divalent radical according to structure (V), (VI), or (VII), and
m is an integer of from 2 to 5.

### Claim 11 (depends on 10)

The method of claim 10, wherein R6, R8 and each R7 are each H.

### Claim 12 (depends on 2)

The method of claim 2, wherein in the organophosphorus compounds, according to structure (II):
R8 and each R7 are each H,
R4 and R5 are each absent,
each R3 is independently a divalent radical according to structure (V),
each p, q is independently 2, 3, or 4,
each r is independently a number of from 1 to about 100,
each s is 0,
each t is 1, and
m is an integer of from 2 to 5.

### Claim 13 (depends on 1)

The method of claim 1, wherein the organophosphorus material is selected from:
(X)(1) organophosphorus compounds according to structure (IX):
wherein:
p is 2, 3,or 4,
r is a number of from 4 to about 50,
(IX)(2) salts of organophosphorus compounds according to structure (IX), and
(IX)(3) mixtures comprising two or more of the compounds and/or salts of (IX)(1) and (IX)(2).

### Claim 14 (depends on 5)

The method of claim 5, wherein in the organophosphorus compounds, each R1 and each R2 is O, and the organophosphorus compound is selected from:
(II)(1) an organophosphate ester according to structure (II):
(II)(2) salts of organophosphorus compounds according to structure (II), and
(II)(3) condensation reaction products of two or more molecules of one or more organophosphorus compounds according to structure (II), and
(II)(4) mixtures comprising two or more of the compounds, salts, and/or reaction products of (II)(1), (II)(2), and (II)(3),
wherein in the organophosphorus compounds, according to structure (II):
R6, R8 and each R7 are each H,
R4 and R5 are each absent,
each R3 is independently a divalent radical according to structure (VI),
the R12 groups are fused to form, including the carbon atoms to which they are attached, a (C6-C8)hydrocarbon ring,
each R13 is H
p′ is 2 or 3,
u is 2,
v is 1,
r′ is a number of from 1 to 25,
t′ is a number of from 1 to 25,
the product of the quantity (v+r′) multiplied times t′ is less than or equal to about 100, and
m is an integer of from 2 to 5.

### Claim 15 (depends on 3)

The method of claim 3, wherein the organophosphorus compound is according to structure (III), each R3 is a divalent radical according to structure (V) with s =0 and t=1, R4 and R5 are each absent, and R6, R7, and R8 are each H.

### Claim 16 (depends on 4)

The method of claim 4, wherein in the organophosphorus compounds, the organophosphorus compound is according to structure (IV), wherein R3 and R5 are each according to structure (V), with s=0 and t=1, and R6 and R8 are each H.

### Claim 17 (depends on 1)

The method of claim 1, wherein the organophosphorus material (b)(I) comprises a condensation reaction product of two or more molecules according to structure (I).

### Claim 18 (depends on 1)

The method of claim 1, wherein the organophosphorus material (b)(I) comprises a condensation reaction product of two or more molecules according to structure (I) in the form of a linear molecule.

### Claim 19 (depends on 1)

The method of claim 1, wherein the organophosphorus material (b)(I) comprises a condensation reaction product of two or more molecules according to structure (I) in the form of a linear molecule, selected from the group consisting of a linear condensation reaction product according to structure (X),
wherein R4, R7, p, r;
formed by condensation of a molecule according to structure (II)
with a molecule according to structure (V):
wherein
each p, q is independently integers of from 2 to 5,
each r, s, is independently a number of from 0 to 25, provided that at least one of r and s is not 0, and
t is a number from 1 to 25,
provided that the product of the quantity (r+s) multiplied times t is less than or equal to about 100.

### Claim 20 (depends on 1)

The method of claim 1, wherein the organophosphorus material (b)(I) comprises a condensation reaction product of two or more molecules according to structure (I) in the form of a crosslinked network.

### Claim 21 (depends on 1)

The method of claim 1, further comprising an aliphatic material.

### Claim 22 (depends on 21)

The method of claim 21, wherein the aliphatic material is a surfactant.

### Claim 23 (depends on 1)

The method of claim 1, further comprising at least one member selected from the group consisting of a polymer and a surfactant for reducing interfacial tension in an oil well.

### Claim 24 (depends on 1)

The method of claim 1, wherein the aqueous fluid consists of:
(a) water or brine and
(b) the organophosphorus material; and
optionally at least one member selected from the group consisting of alcohols, ketones, an aliphatic nonionic additive having an average carbon number from 10 to 24, a long chain aliphatic alcohol having an average carbon number from 10 to 30, polymer, surfactant, clay stabilization material, sand stabilization material, corrosion inhibitors, oxygen scavengers, and bactericides.

### Claim 25 (depends on 24)

The method of claim 24, wherein:
the alcohol is selected from the group consisting of isopropyl or butyl alcohol plus methyl alcohol;
the surfactant is an aliphatic anionic surfactant, wherein an aliphatic portion of the aliphatic anionic surfactant has an average carbon number from 10 to 24;
the clay stabilization and sand stabilization materials are selected from the group consisting of epoxy resins, poly(N-acrylamidomethyltrimethyl ammonium chloride) and poly(vinylbenzyltrimethyl ammonium chloride); and
the polymers are selected from the group consisting of biopolysaccharides, cellulose ethers, and acrylamide-derived polymers.

### Claim 26 (depends on 1)

The method of claim 1, wherein the aqueous fluid consists of:
(a) water or brine and
(b) the organophosphorus material; and
at least one member of the group consisting of alcohols, ketones, an aliphatic nonionic additive having an average carbon number from 10 to 24, a long chain aliphatic alcohol having an average carbon number from 10 to 30, polymer, surfactant, clay stabilization material, sand stabilization material, corrosion inhibitors, oxygen scavengers, and bactericides.

### Claim 27 (depends on 26)

The method of claim 26, wherein:
the alcohol is selected from the group consisting of isopropyl or butyl alcohol plus methyl alcohol;
the surfactant is an aliphatic anionic surfactant, wherein an aliphatic portion of the aliphatic anionic surfactant has an average carbon number from 10 to 24;
the clay stabilization and sand stabilization materials are selected from the group consisting of epoxy resins, poly(N-acrylamidomethyltrimethyl ammonium chloride) and poly(vinylbenzyltrimethyl ammonium chloride); and
the polymers are selected from the group consisting of biopolysaccharides, cellulose ethers, acrylamide-derived polymers.

### Claim 28 (depends on 13)

The method of claim 13, wherein r is a number of from 4 to about 25.

### Claim 29 (depends on 1)

The method of claim 1, wherein the organophosphorus material is selected from:
(X)(1) organophosphorus compounds according to structure (IX):
wherein:
p is 2 or 3,
r is a number of from 4 to about 50,
(IX)(2) salts of organophosphorus compounds according to structure (IX), and
(IX)(3) mixtures comprising two or more of the compounds and/or salts of (IX)(1) and (IX)(2).

### Claim 30 (depends on 29)

The method of claim 29, wherein r is a number of from 4 to about 25.