Granted Patent B2

US 12,203,031 · App. 17/416,840 · Granted Jan 21, 2025

Inventors: Fatima Dugonjic-Bilic (Offenbach, DE); Benjamin Gerlach (Aschaffenburg, DE); Marita Neuber (Dreieich, DE)

Assignee: TouGas Oilfield Solutions GmbH

C09K8/584C08F20/56C09K8/54C09K8/588E21B43/16C09K2208/32

Abstract

Claims (104)

1. A method for treatment of subterranean oil and gas reservoirs comprising the steps of:

(i) providing a water-in-oil polymer emulsion containing water-soluble polymer in the aqueous phase, the aqueous phase finely dispersed in the continuous hydrophobic organic phase and the droplets stabilized by a surfactant package containing a first surfactant having a HLB-value between 3 and 9 and a second surfactant being an alkyl polyglycoside having a HLB-value of greater than 11 or a mixture of alkyl polyglycosides having a HLB-value of greater than 11, the water-soluble polymer is a synthetic copolymer or terpolymer, having an average molecular weight higher than 1,000,000 Dalton, and the water-in-oil polymer emulsion having a viscosity of less than 1000 mPas,

(ii) preparing an aqueous treatment fluid by inversion of said emulsion into water that may contains salts and optionally an inverter surfactant composition,

(iii) optionally adding additives, e.g. oxygen and/or radical scavenger and

(iv) introducing the aqueous treatment fluid into the subterranean oil and gas reservoir formation.

2. The method of claim 1 , wherein the aqueous phase which includes the water-soluble polymer is present in an amount from 40 to 90 wt. %, based on the total emulsion.

3. The method of claim 1 , wherein the polymer is a copolymer or terpolymer and the content of the water-in-oil emulsion is from 20 to 50 wt. %, based on the total emulsion.

4. The method of claim 1 , wherein the synthetic polymer comprises:

(I) at least structural units of formula (I)

wherein

R1, R2 and R3 independently are hydrogen or C 1 -C 6 -alkyl,

(II) from 0 to 95% by weight structural units of formula (II)

wherein

R4 is hydrogen or C 1 -C 6 -alkyl,

R5 is hydrogen, a cation of an alkaline metal, of an earth alkaline metal, of ammonia and/or of an organic amine,

A is a covalent C—S bond or a two-valent organic bridging group,

(III) from 0 to 30% by weight structural units of formula (III)

wherein

B is a covalent C—C bond or a two-valent organic bridging group

R6 and R7 are independently of one another hydrogen, C 1 -C 6 -alkyl, —COOR 9 or —CH 2 —COOR 9 , with R 9 being hydrogen, a cation of an alkaline metal, of an earth alkaline metal, of ammonia and/or of an organic amine,

R8 is hydrogen, a cation of an alkaline metal, of an earth alkaline metal, of ammonia and/or of an organic amine, or is C 1 -C 6 -alkyl, a group —C n H 2n —OH with n being an integer between 2 and 6, or is a group —C o H 2o —NR10R11, with o being an integer between 2 and 6, and

R10 and R11 are independently of one another hydrogen or C 1 -C 6 -alkyl,

(IV) from 0 to 50% by weight structural units of formula (IV)

wherein

R12 and R13 are independently of one another hydrogen, C 1 -C 6 -alkyl, —COOR16 or —CH 2 —COOR16, with

R16 being hydrogen, a cation of an alkaline metal, of an earth alkaline metal, of ammonia and/or of an organic amine,

R14 is hydrogen or, C 1 -C 6 -alkyl, and

R15 is —COH, —CO—C 1 -C 6 -alkyl or

R14 and R15 together with the nitrogen atom to which they are attached form a heterocyclic group with 4 to 6 ring atoms,

(V) from 0 to 20% by weight structural units of formula (V)

wherein

D is a covalent C—P bond or a two-valent organic bridging group

R17 is hydrogen or, C 1 -C 6 -alkyl, and

R18 and R19 are independently of one another hydrogen, a cation of an alkaline metal, of an earth alkaline metal, of ammonia and/or of an organic amine,

B is a covalent C—P bond or a two-valent organic bridging group,

(VI) optionally further copolymerisable monomers, such copolymerisable monomers being present from 0 to 20% by weight structural units,

with the proviso that the percentage of the structural units of formulae (I) to (VI), refer to the total mass of the copolymer and the percentage of the structural units of formulae (I) to (VI), amounts to 100%.

5. The method of claim 4 , wherein the synthetic copolymer is selected from the group consisting of polymers containing:

(I) 10 to 90% by weight of structural formula I,

(II) 0 to 95% by weight of structural formula II,

(III) 0 to 30% by weight of structural formula III,

(IV) 0 to 50% by weight of structural formula IV,

(V) 0 to 20% by weight of structural formula V,

referred to the total mass of the polymer, with the proviso that the percentage of the structural units of formulae (I) to (V) refer to the total mass of the copolymer and the percentage of the structural units of formulae (I) to (V) amounts to 100%.

6. The method of claim 1 , wherein the polymer is a copolymer having a K-value of higher than 180 determined as 0.1 wt.-% copolymer concentration in deionized water.

7. The method of claim 1 , wherein the alkyl polyglycoside(s) have a molecular weight of less than 950 g/mol.

8. The method of claim 1 , wherein the alkyl polyglycoside(s) consist of 1 to 5 glycoside units.

9. The method of claim 1 , wherein the alkyl side chain of the alkyl polyglycoside(s) consists of alkyl groups with an uniform number of up to 12 C-atoms or different length with up to 16 C-atoms.

10. The method of claim 1 , wherein the alkyl polyglycoside(s) are octyl- to dodecyl polyglucosides having 1 to 3 glucoside units and mixtures thereof.

11. The method of claim 1 , wherein the water-soluble polymer in the aqueous phase has a solubility in distilled water of at least 0.5% by weight at 30° C.

12. The method of claim 1 , wherein the total amount of first and second surfactant(s) ranges from 0.6 to 10 wt. %, of the total emulsion.

13. The method of claim 1 , wherein the ratio of the first and the second surfactant may vary between 0.5 to 1 and 8 to 1.

14. The method of claim 1 , wherein the first surfactant is present in an amount in the range of from about 0.5 wt. % to about 6 wt. % of the total emulsion and the second surfactant is present in an amount in the range of from about 0.1 wt. % to about 4 wt. % of the total emulsion, the ratio of the first and the second surfactant is between 0.5 to 1 and 8 to 1.

15. The method of claim 1 , wherein the copolymer or terpolymer comprises:

(I) at least structural units of formula (I)

wherein

R1, R2 and R3 independently are hydrogen or C 1 -C 6 -alkyl,

(II) from 0 to 95% by weight structural units of formula (II)

wherein

R4 is hydrogen or C 1 -C 6 -alkyl,

R5 is hydrogen, a cation of an alkaline metal, of an earth alkaline metal, of ammonia and/or of an organic amine,

A is a covalent C—S bond or a two-valent organic bridging group,

(III) from 0 to 30% by weight structural units of formula (III)

wherein

B is a covalent C—C bond or a two-valent organic bridging group

R6 and R7 are independently of one another hydrogen, C 1 -C 6 -alkyl, —COOR 9 or —CH 2 —COOR 9 , with R 9 being hydrogen, a cation of an alkaline metal, of an earth alkaline metal, of ammonia and/or of an organic amine,

R8 is hydrogen, a cation of an alkaline metal, of an earth alkaline metal, of ammonia and/or of an organic amine, or is C 1 -C 6 -alkyl, a group —C n H 2n —OH with n being an integer between 2 and 6, or is a group —C o H 2o —NR10R11, with o being an integer between 2 and 6,

R10 and R11 are independently of one another hydrogen or C 1 -C 6 -alkyl,

(IV) from 0 to 50% by weight structural units of formula (IV)

wherein

R12 and R13 are independently of one another hydrogen, C 1 -C 6 -alkyl, —COOR16 or —CH 2 —COOR16, with

R16 being hydrogen, a cation of an alkaline metal, of an earth alkaline metal, of ammonia and/or of an organic amine,

R14 is hydrogen or, C 1 -C 6 -alkyl, and

R15 is —COH, —CO—C 1 -C 6 -alkyl or

R14 and R15 together with the nitrogen atom to which they are attached form a heterocyclic group with 4 to 6 ring atoms,

(V) from 0 to 20% by weight structural units of formula (V)

wherein

D is a covalent C—P bond or a two-valent organic bridging group

R17 is hydrogen or, C 1 -C 6 -alkyl, and

R18 and R19 are independently of one another hydrogen, a cation of an alkaline metal, of an earth alkaline metal, of ammonia and/or of an organic amine,

B is a covalent C—P bond or a two-valent organic bridging group,

(VI) optionally further copolymerisable monomers, such copolymerisable monomers being present from 0 to 20% by weight structural units, with the proviso that the percentage of the structural units of formulae (I) to (VI), refer to the total mass of the copolymer and the percentage of the structural units of formulae (I) to (VI), amounts to 100%

and is produced by an inverse emulsion polymerization method comprising the steps of:

(i) preparation of an aqueous monomer solution, if necessary, adjusting pH value of the aforementioned monomer solution,

(ii) preparation of an organic solution consisting of a water-immiscible organic liquid that does not interfere with the polymerization reaction, said organic solution containing a surfactant package,

(iii) addition of the aqueous phase of step (i) to the organic phase of step (ii) to prepare a water-in-oil emulsion,

(iv) removal of oxygen and initiation of the polymerization reaction by addition of one or more compounds that form radicals

(v) adjusting reaction temperature by cooling or heating to allow complete conversion of the monomers into a polymer,

(vi) optionally addition of an inverter surfactant for facilitated inversion or further additives,

wherein

the surfactant package containing a first surfactant having a HLB-value between 3 and 9 and a second surfactant having a HLB-value of greater than 11, said second surfactant is an alkyl polyglycoside or a mixture of alkyl polyglycosides.

16. The method of claim 1 , wherein the treatment of the subterranean oil and gas reservoir is for enhanced oil recovery.

17. The method of claim 4 , wherein the synthetic copolymer is selected from the group consisting of polymers containing:

(I) from 20 to 70% by weight,

(II) from 10 to 80% by weight,

(III) from 0 to 20% by weight,

(IV) from 0 to 20% by weight,

(V) from 0.1 to 10% by weight,

referred to the total mass of the polymer, with the proviso that the percentage of the structural units of formulae (I) to (V) refer to the total mass of the copolymer and the percentage of the structural units of formulae (I) to (V) amounts to 100%.

18. The method of claim 1 , wherein the average molecular weight of the co- or ter-polymer, is higher than 3,000,000 Dalton.

19. The method of claim 1 , wherein the polymer is a copolymer having a K-value of higher than 200 determined as 0.1 wt. % copolymer concentration in deionized water.

20. The method of claim 1 , wherein the alkyl polyglycoside(s) consist of 1 to 3 glycoside units.

21. The method of claim 1 , wherein the alkyl polyglycoside(s) consist of 1 or 2 glycoside units.

22. The method of claim 1 , wherein the ratio of the first and the second surfactant may vary between 1 to 1 and 4 to 1.

Assignments (2)

Priority Claims (1)

Continuity (1)

References Cited (10)