Method for recovering hydrocarbon fluids from a subterranean reservoir using alpha-glycol containing sulfonated epoxy resin compound

Abstract

Disclosed is a composition and use thereof for the recovery of hydrocarbon fluids from a subterranean reservoir. More particularly, this invention concerns -glycol containing sulfonated epoxy resin composition and method for preparing said composition. The -glycol containing sulfonated epoxy resin composition is made by forming a reaction product comprising an epoxide-containing compound, a primary amino sulfonate, and optionally one or more of a primary monoamine alkylene oxide oligomer, followed by converting any unreacted epoxide groups in the reaction product to -glycol groups by hydrolysis. Said -glycol containing sulfonated epoxy resin compositions demonstrate good solubility in aqueous solutions and are useful for modifying the permeability of subterranean formations and increasing the mobilization and/or recovery rate of hydrocarbon fluids present in the formations.

Claims

1. A method of modifying the permeability to water of a subterranean formation comprising the step of injecting into the subterranean formation an aqueous composition comprising from about 0.005 percent to about 2 percent, by weight, of an -glycol containing sulfonated epoxy resin composition wherein the -glycol containing sulfonated epoxy resin composition is made by: (A) forming a sulfonated epoxy resin polymer reaction product by reacting (i) an epoxide-containing compound having an average of more than one epoxide group per molecule, (ii) a primary amino sulfonate, (iii) optionally a primary monoamine alkylene oxide oligomer, and (iv) optionally an epoxide reactive compound selected from a primary monoamine, a secondary diamine, a monohydroxyalkyl primary monoamine, a dihydroxyalkyl primary monoamine, a trihydroxyalkyl primary monoamine, a monohydroxycycloalkyl primary monoamine, a dihydroxycycloalkyl primary monoamine, or a trihydroxycycloalkyl primary monoamine and (B) converting unreacted epoxy groups in the reaction product from step (A) to -glycol groups by hydrolysis.

2. The method of claim 1 wherein (i) the epoxide-containing compound is represented by a formula I, below: ##STR00010## where Q is selected from a divalent aromatic group Ar; Ar-L-Ar, wherein L is selected from a direct bond, C.sub.1 to C.sub.8 alkylene, SO.sub.2, S, >CO, or O; a divalent cycloaliphatic group K having from 4 carbons to 8 carbons, or R.sub.1KR.sub.2 where R.sub.1 and R.sub.2 are independently a C.sub.1 to C.sub.3 alkylene group; (ii) the primary amino sulfonate is represented by a formula II, below: ##STR00011## wherein Z is an aliphatic, cycloaliphatic, polycycloaliphatic, or aromatic hydrocarbon group optionally substituted with one or more alkyl groups and M is any monovalent cation; and (iii) if present, the primary monoamine alkylene oxide oligomer is represented by a formula III, below: ##STR00012## wherein R.sub.3 is H, C.sub.1 to C.sub.12 alkyl or cycloalkyl, R.sub.4 is a covalent bond, C.sub.1 to C.sub.12 alkyl or cycloalkyl, R.sub.5 and R.sub.6 are independently H, C.sub.1 to C.sub.12 alkyl or cycloalkyl, and x and y independently have a value from 0 to 400.

3. The method of claim 1 wherein an equivalent ratio of epoxide reactive groups in the primary monoamine sulfonate (ii), the optional primary monoamine alkylene oxide oligomer (iii), and the optional epoxide reactive compound (iv) to epoxy groups in the epoxide-containing compound (i) is 0.25:1 to 0.95:1.

4. The method of claim 1 wherein the -glycol containing sulfonated epoxy resin composition has an average molecular weight of from 300 to 100,000.

5. The method of claim 1 wherein the primary monoamine alkylene oxide oligomer is present in an amount of from 1 to 15 percent, of amine hydrogen equivalents for reaction with epoxide equivalents of component (i), the epoxide-containing compound.

6. The method of claim 1 wherein the epoxide-containing compound is selected from diglycidyl ether of 4,4-isopropylidenediphenol (bisphenol A); cis-1,3-cyclohexanedimethanol; trans-1,3-cyclohexanedimethanol; cis-1,4-cyclohexanedimethanol; or trans-1,4-cyclohexanedimethanol.

7. The method of claim 1 wherein the primary amino sulfonate is selected from sulfanilic acid, sodium salt; sulfanilic acid, potassium salt; aminomethanesulfonic acid, sodium salt; or aminomethanesulfonic acid, potassium salt.

8. The method of claim 2 wherein for the primary monoamine alkylene oxide oligomer is present and R.sub.3 and R.sub.5 are CH.sub.3, R.sub.4 is CH.sub.2, R.sub.6 is H, and x and y independently have a value from 0 to 75 with the proviso that at least one of x or y is equal to or greater than 1.

9. The method of claim 1 wherein the aqueous composition further comprises about 1 to about 10 weight percent of one or more clay stabilization salts.

10. The method of claim 9 wherein the clay stabilization salts are selected from KCl, NaCl, NaBr, sodium acetate and NH.sub.4Cl.

Description

EXAMPLES

(1) In Examples 1 to 3 the following components are used:

(2) D.E.R. 332 Epoxy Resin is a high purity bisphenol A diglycidyl ether having a titrated epoxide equivalent weight of 171.2 available from The Dow Chemical Company;

(3) N,N-DMF is N,N-dimethylformamide which is 99.8% pure and is available anhydrous from Sigma-Aldrich Chemical;

(4) SURFONAMINE L-300 Amine is a hydrophilic polyether monoamine comprising propylene oxide and ethylene oxide in a ratio of 8:58 having a molecular weight of approximately 3000 daltons available from Huntsman Corp.;

(5) and

(6) Aminomethanesulfonic acid, sodium salt is 97% pure and is available from Sigma-Aldrich Chemical.

Example 1

Step A

(7) D.E.R. 332 (5.7067 grams, 0.033 epoxide equivalent) and anhydrous N,N-dimethylformamide (N,N-DMF) (50 milliliters) are charged to a 500 milliliter, three neck, round bottom, glass reactor containing a magnetic stirring bar, under overhead dynamic nitrogen (0.5 liter per minute). The reactor is additionally outfitted with a condenser maintained at room temperature, a thermometer and overhead nitrogen inlet. D.E.R. 332 having a titrated epoxide equivalent weight of 171.2 is the high purity epoxy resin of bisphenol A (4,4-isopropylidenediphenol) used. The reactants are weighed on a scale providing four decimal place accuracy. SURFONAMINE L-300 (4.7619 grams, 0.0033 amine hydrogen equivalent) solution in N,N-DMF (50 milliliters) is then added to the reactor followed by addition of dry aminomethanesulfonic acid, sodium salt (0.9982 grams, 0.0075 mole, 0.015 amine hydrogen equivalent) and N,N-DMF (250 milliliters). Heating of the resultant 25 C. stirred mixture commenced after placing a heating mantle under the reactor and activating the temperature controller. After 54 minutes 145 C. is attained and a hazy solution formed. Heating continued to 148 C. giving a boiling hazy solution. The reaction is held for the next 21 hours at 148 to 149 C. to provide an amber colored hazy solution. The hazy solution is removed from the reactor and rotary evaporated to a final temperature of 150 C. and a final vacuum of 2.0 mm Hg to give 11.54 grams of a tacky, viscous, amber colored, slightly hazy liquid at room temperature.

(8) The product is fully soluble at room temperature in the acetic acid and dichloromethane solvents employed for epoxide titration. Epoxide titration of a sample of the product gave an apparent epoxide equivalent weight (EEW) of 525.3.

Step B

(9) The bisphenol A epoxy resinaminomethanesulfonic acid (sodium salt)SURFONAMINE L-300 oligomeric product (11.20 grams) from A. above and DI water (400 milliliters) are charged to a 1 liter, single neck, round bottom, glass reactor containing a magnetic stirring bar. The reactor is additionally outfitted with a Claisen adaptor, a forced air cooled condenser, and a thermometer. Heating of the resultant 23 C. stirred mixture commenced after placing a heating mantle under the reactor and activating the temperature controller. After 14 minutes 66 C. is attained and an opaque brown colored solution formed. Heating continued and after a cumulative 16 minutes 75 C. is attained and a milky, opaque tan colored mixture formed. After a cumulative 32 minutes 100 C. is attained and an amber colored oil and water mixture formed. The reaction is held for 7 days at 100 C. The amber colored oil and water mixture is removed from the reactor and rotary evaporated to a final temperature of 150 C. and a final vacuum of 2.0 mm Hg to give a tacky, viscous, amber colored, liquid at room temperature. Epoxide titration of a sample of the product gave an apparent EEW of 2237 (note: the crystal violet indicator in the solution before titration gave a blue color instead of the usual violet color observed for titration of epoxy resin of bisphenol A). The product is dissolved in N,N-DMF (250 milliliters) then DI water (75 milliliters) is added to the stirred solution. The resultant solution is heated to 100 C. and held for 15 hours. The amber colored solution is removed from the reactor and rotary evaporated to a final temperature of 150 C. and a final vacuum of 2.0 mm Hg to give a tacky, viscous, amber colored, liquid at room temperature. A total of 11.16 grams of product is recovered (uncorrected for samples removed for analysis). Epoxide titration of a sample of the product demonstrated the EEW is unchanged (note: the crystal violet indicator in the solution before titration again gave a blue color instead of the usual violet color observed for titration of epoxy resin of bisphenol A).

(10) Fourier transform infrared spectrophotometric (FTIR) analysis of a sample of the product as a film on a KCl plate is completed and compared against FTIR analysis results for D.E.R. 332 as a standard. The CO stretching of the epoxide group at 915.5 cm.sup.1 in the standard is completely gone in the product. The combined COC epoxide stretching and 1,4-substituted aromatic ring absorbance at 830.8 cm.sup.1 in the standard are reduced in relative intensity (830.4 cm.sup.1 in the product). The CH stretching of the epoxide ring at 3056.1 cm.sup.1 in the standard is completely gone in the product. A strong, broad OH stretching absorbance centered at 3390.5 cm.sup.1 appeared in the product but is not present in the standard. A broad CN stretch is observed in the product at 1106 cm.sup.1. A COC ether stretching absorbance is observed in the product at 1041 cm.sup.1 and in the standard at 1035 cm.sup.1. The product comprised the following nominal structural units:

(11) ##STR00007##

Example 2

Step A

(12) D.E.R. 332 (5.7067 grams, 0.033 epoxide equivalent) and anhydrous N,N-dimethylformamide (N,N-DMF) (50 milliliters) are charged to a 500 milliliter, three neck, round bottom, glass reactor containing a magnetic stirring bar, under overhead dynamic nitrogen (0.5 liter per minute). The reactor is additionally outfitted with a condenser maintained at room temperature, a thermometer and overhead nitrogen inlet. D.E.R. 332 having a titrated epoxide equivalent weight of 171.2 is the high purity epoxy resin of bisphenol A (4,4-isopropylidenediphenol) used. The reactants are weighed on a scale providing four decimal place accuracy. SURFONAMINE L-300 (4.7619 grams, 0.0033 amine hydrogen equivalent) solution in N,N-DMF (50 milliliters) is then added to the reactor followed by addition of dry aminomethanesulfonic acid, sodium salt (1.7302 grams, 0.013 mole, 0.026 amine hydrogen equivalent) and N,N-DMF (250 milliliters). Heating of the resultant 24 C. stirred mixture commenced after placing a heating mantle under the reactor and activating the temperature controller. After 31 minutes 145 C. is attained and a hazy solution formed. Heating continued to 148 C. giving a boiling slightly hazy solution. The reaction is held for the next 53.9 hours at 148 to 150 C. to provide an amber colored solution. The solution is removed from the reactor and rotary evaporated to a final temperature of 150 C. and a final vacuum of 1.0 mm Hg to give 11.51 grams of a tacky, viscous, amber colored, transparent, liquid at room temperature.

(13) The product is fully soluble at room temperature in the acetic acid and dichloromethane solvents employed for epoxide titration. Epoxide titration of a sample of the product gave an apparent epoxide equivalent weight (EEW) of 1422.

Step B

(14) The bisphenol A epoxy resinaminomethanesulfonic acid (sodium salt)SURFONAMINE L-300 oligomeric product (11.22 grams) from A above and DI water (400 milliliters) are charged to a 1 liter, single neck, round bottom, glass reactor containing a magnetic stirring bar. The reactor is additionally outfitted with a Claisen adaptor, a forced air cooled condenser, and a thermometer. Heating of the resultant 23 C. stirred mixture commenced after placing a heating mantle under the reactor and activating the temperature controller. After 55 minutes 100 C. is attained and an opaque, medium brown colored mixture formed. The reaction is held for 5 days at 100 C. The amber colored oil and water mixture is removed from the reactor and rotary evaporated to a final temperature of 150 C. and a final vacuum of 2.0 mm Hg to give a tacky, viscous, amber colored, liquid at room temperature. A total of 11.17 grams of product is recovered (uncorrected sample removed for FTIR analysis).

(15) FTIR analysis of a sample of the product as a film on a KCl plate is completed and compared against FTIR analysis results for D.E.R. 332 as a standard. The CO stretching of the epoxide group at 915.5 cm.sup.1 in the standard is completely gone in the product. The combined COC epoxide stretching and 1,4-substituted aromatic ring absorbance at 830.8 cm.sup.1 in the standard are reduced in relative intensity (830.6 cm.sup.1 in the product). The CH stretching of the epoxide ring at 3056.1 cm.sup.1 in the standard is completely gone in the product. A strong, broad OH stretching absorbance centered at 3416.1 cm.sup.1 appeared in the product but is not present in the standard. A broad CN stretch is observed in the product at 1105.2 cm.sup.1. A COC ether stretching absorbance is observed in the product at 1041 cm.sup.1 and in the standard at 1035 cm.sup.1. The product comprised the following nominal structural units:

(16) ##STR00008##

Example 3

Step A

(17) D.E.R. 332 (5.7067 grams, 0.033 epoxide equivalent) and anhydrous N,N-dimethylformamide (N,N-DMF) (50 milliliters) are charged to a 500 milliliter, three neck, round bottom, glass reactor containing a magnetic stirring bar, under overhead dynamic nitrogen (0.5 liter per minute). The reactor is additionally outfitted with a condenser maintained at room temperature, a thermometer and overhead nitrogen inlet. D.E.R. 332 having a titrated epoxide equivalent weight of 171.2 is the high purity epoxy resin of bisphenol A (4,4-isopropylidenediphenol) used. The reactants are weighed on a scale providing four decimal place accuracy. SURFONAMINE L-300 (4.7619 grams, 0.0033 amine hydrogen equivalent) solution in N,N-DMF (50 milliliters) is then added to the reactor followed by addition of dry aminomethanesulfonic acid, sodium salt (1.4973 grams, 0.01125 mole, 0.0225 amine hydrogen equivalent) and N,N-DMF (250 milliliters). Heating of the resultant 25 C. stirred mixture commenced after placing a heating mantle under the reactor and activating the temperature controller. After 59 minutes 148 C. is attained and a boiling, slightly hazy solution formed. The reaction is held for the next 55.7 hours at 148 to 150 C. to provide an amber colored, slightly hazy solution. The slightly hazy solution is removed from the reactor and rotary evaporated to a final temperature of 150 C. and a final vacuum of 1.0 mm Hg to give 11.74 grams of a tacky, viscous, amber colored, transparent liquid at room temperature comprising the nominal structural units given in Example 2 Step B. The product is fully soluble at room temperature in the acetic acid and dichloromethane solvents employed for epoxide titration. Epoxide titration of a sample of the product gave an apparent EEW of 1192.

Step B

(18) The bisphenol A epoxy resinaminomethanesulfonic acid (sodium salt)SURFONAMINE L-300 oligomeric product (11.60 grams) from A above and DI water (400 milliliters) are charged to a 1 liter, single neck, round bottom, glass reactor containing a magnetic stirring bar. The reactor is additionally outfitted with a Claisen adaptor, a forced air cooled condenser, and a thermometer. Heating of the resultant 23 C. stirred mixture commenced after placing a heating mantle under the reactor and activating the temperature controller. After 125 minutes 100 C. is attained and an opaque, light brown colored mixture formed. The reaction is held for 5 days at 100 C. The amber colored oil and water mixture is removed from the reactor and rotary evaporated to a final temperature of 150 C. and a final vacuum of 2.0 mm Hg to give a tacky, viscous, amber colored, liquid at room temperature. A total of 12.10 grams of product is recovered.

(19) FTIR analysis of a sample of the product as a film on a KCl plate is completed and compared against FTIR analysis results for D.E.R. 332 as a standard. The CO stretching of the epoxide group at 915.5 cm.sup.1 in the standard is completely gone in the product. The combined COC epoxide stretching and 1,4-substituted aromatic ring absorbance at 830.8 cm.sup.1 in the standard are reduced in relative intensity (831.8 cm.sup.1 in the product). The CH stretching of the epoxide ring at 3056.1 cm.sup.1 in the standard is completely gone in the product. A strong, broad OH stretching absorbance centered at 3398.8 cm.sup.1 appeared in the product but is not present in the standard. A broad CN stretch is observed in the product at 1107.8 cm.sup.1. A COC ether stretching absorbance is observed in the product at 1039.3 cm.sup.1 and in the standard at 1035 cm.sup.1. The product comprised the following nominal structural units:

(20) ##STR00009##