Method of fracturing with gelled organic liquids

Claim 2

In the process of fracturing a subterranean formation wherein the viscosity of an organic liquid selected from the group consisting of aliphatic hydrocarbons, aliphatic halogenated hydrocarbons, xylene, and crude oil is first increased an effective amount above its normal viscosity by the addition of a thickening agent and then is introduced into and through a borehole which penetrates said subterranean formation at a sufficient pressure to fracture the formation the improvement which comprises: thickening said organic liquid by mixing therewith an effective quantity of both an aluminum activator compound selected from the group consisting of an alkali metal aluminate, aluminum isopropoxide and hydrated alumina, and an organic phosphate ester composition prepared by the process which comprises the reaction of: A. a pentavalent phosphorus compound selected from the group consisting of P 2 O 5 and a mixture of P 2 O 5 with polyphosphoric acid; B. a hydroxy ether of the formula ROR 1 OH wherein R is a C 1 to C 6 alkyl group, R 1 is a C 2 or C 3 alkylene group and the total carbon atoms of R and R 1 range from 3 to about 8; and C. when the total carbon atoms of R and R 1 is 3 or 4, a long chain substantially unsubstituted monohydric aliphatic alcohol containing at least 5 carbon atoms, but when the total carbon atoms of R and R 1 is 5 to 8, an alcohol selected from the group consisting of a long chain substantially unsubstituted monohydric aliphatic alcohol containing at least 5 carbon atoms, a short chain substantially unsubstituted monohydric aliphatic alcohol containing from 1 to 4 carbon atoms and a mixture of said alcohols, the individual mole ratios of the hydroxy ether, the long chain alcohol and the short chain alcohol to total P 2 O 5 being within the ranges of 0.4:1 to 4.5:1, 0:1 to 4.0:1 and 0:1 to 5.0:1 respectively, said reaction being conducted at temperature ranging from about 70° to about 90° C. for a period of time of from about 1.5 to about 6 hours, and said phosphorus compound, hydroxy ether, and alcohol or alcohols being provided in molar ratios and admixed in a sequence effective to provide a reaction product suitable for use in thickening said organic liquid.

Claim 3

The method of claim 1 wherein the total mole ratio of the hydroxy ether, the long chain alcohol and the short chain alcohol to total P 2 O 5 is about 3.64 to 1.

Claim 4

The method of claim 1 wherein the reaction temperature ranges from about 80° to about 90° C. and the reaction time ranges from about 1.5 to about 3 hours.

Claim 5

The method of claim 1 wherein the pentavalent phosphorus compound is P 2 O 5 .

Claim 6

The method of claim 1 wherein the aluminum compound is sodium aluminate.

Claim 7

The method of claim 1 wherein the organic liquid is an aliphatic hydrocarbon.

Claim 8

The method of claim 1 wherein from about 1 to about 25 gallons of the reaction product is employed per 1000 gallons of said organic liquid.

Claim 9

The method of claim 1 wherein each alcohol is unsubstituted.

Claim 10

The method of claim 8 wherein the individual mole ratios of the hydroxy ether, the long chain alcohol and the short chain alcohol to P 2 O 5 are within the ranges of 0.8:1 to 1.8:1; 0:1 to 1.4:1; and 0.9:1 to 2.0:1 respectively.

Claim 11

The method of claim 9 wherein the total mole ratio of the hydroxy ether, the long chain alcohol and the short chain alcohol to total P 2 O 5 ranges from about 2.8:1 to about 7.0:1.

Claim 12

The method of claim 10 wherein the aluminum compound is sodium aluminate.

Claim 13

The method of claim 1 wherein when the total carbon atoms of R and R 1 is 3 or 4 there is also reacted a short chain substantially unsubstituted monohydric aliphatic alcohol containing from 1 to 4 carbon atoms or a mixture of said alcohols.

Claim 14

The method of claim 1 wherein the long chain alcohol is unsubstituted and contains from 5 to 12 carbon atoms, and wherein the short chain alcohol is methanol, ethanol, or a mixture thereof.

Claim 15

The method of claim 13 wherein the aluminum compound is sodium aluminate.

Claim 16

The method of claim 14 wherein the organic liquid is an aliphatic hydrocarbon.

Claim 17

The method of claim 1 wherein the long chain monohydric alcohol contains from 5 to about 12 carbon atoms.

Claim 18

The method of claim 16 wherein the short chain alcohol is a primary, unsubstituted, straight chain, saturated alcohol.

Claim 19

The method of claim 17 wherein the short chain alcohol is ethanol, methanol, or a mixture thereof, and the long chain alcohol is unsubstituted.

Claim 20

The method of claim 17 wherein the short chain alcohol is methanol.

Claim 21

In the process of fracturing a subterranean formation wherein the viscosity of an organic liquid selected from the group consisting of aliphatic hydrocarbons, aliphatic halogenated hydrocarbons, xylene, and crude oil is first increased an effective amount above its normal viscosity by the addition of a thickening agent and then is introduced into and through a borehole which penetrates said subterranean formation at a sufficient pressure to fracture the formation the improvement which comprises: thickening said organic liquid by mixing therewith an effective quantity of both an aluminum activator compound selected from the group consisting of an alkali metal aluminate, aluminum isopropoxide, and hydrated alumina and an organic phosphate ester composition prepared by the process which comprises the reaction of: A. a pentavalent phosphorus compound, selected from the group consisting of P 2 O 5 and a mixture of P 2 O 5 with polyphosphoric acid; B. a hydroxy ether of the formula ROR 1 OH wherein R is a C 1 to C 6 alkyl group, R 1 is a C 2 or C 3 alkylene group and the total carbon atoms of R and R 1 range from 3 to about 8; and C. when the total carbon atoms of R and R 1 is 3 or 4 a long chain substantially unsubstituted monohydric aliphatic alcohol containing at least 5 carbon atoms and short chain substantially monohydric aliphatic alcohol containing from one to four carbon atoms; when the total carbon atoms of R and R 1 is five to eight a short chain substantially unsubstituted monohydric aliphatic alcohol containing from one to four carbon atoms; the individual mole ratios of the hydroxy ether, the long chain alcohol and the short chain alcohol to total P 2 O 5 being within the ranges of 0.4:1 to 4.5:1; 0:1 to 4.0:1 and 0:1 to 5:1 respectively, and the total mole ratio of said three components to total P 2 O 5 being from about 2.8:1 to about 7.0:1, said reaction being conducted by first reacting the phosphorus compound with the hydroxy ether, and when the total carbon atoms of R and R 1 is 3 or 4, also with the long chain alcohol for a period of time of from about 5 to about 30 minutes at a temperature of from about 70° to about 90° C., cooling the reaction mixture to below 70° C., adding the short chain alcohol to the reaction mixture and reacting the mixture at a temperature of from about 70° to about 90° C. for a period of time to provide a total reaction time of from about 1.5 to about 6 hours.

Claim 22

In the process of fracturing a subterranean formation wherein the viscosity of an organic liquid selected from the group consisting of aliphatic hydrocarbons, aliphatic halogenated hydrocarbons, xylene, and crude oil is first increased an effective amount above its normal viscosity by the addition of a thickening agent and then is introduced into and through a borehole which penetrates said subterranean formation at a sufficient pressure to fracture the formation the improvement which comprises: thickening said organic liquid by mixing therewith an effective quantity of both an aluminum activator compound selected from the group consisting of an alkali metal aluminate, aluminum isopropoxide, and hydrated alumina and an organic phosphate ester composition prepared by the process which comprises the reaction of: A. a pentavalent phosphorus compound, selected from the group consisting of P 2 O 5 and a mixture of P 2 O 5 with polyphosphoric acid; B. a hydroxy ether of the formula ROR 1 OH wherein R is a C 1 to C 6 alkyl group, R 1 is a C 2 or C 3 alkylene group and the total carbon atoms of R and R 1 range from 3 to about 8; and C. when the total carbon atoms of R and R 1 is 3 or 4 a long chain substantially unsubstituted monohydric aliphatic alcohol containing at least 5 carbon atoms and short chain substantially monohydric aliphatic alcohol containing from one to four carbon atoms; when the total carbon atoms of R and R 1 is five to eight a short chain substantially unsubstituted monohydric aliphatic alcohol containing from one to four carbon atoms; the individual mole ratios of the hydroxy ether, the long chain alcohol and the short chain alcohol to total P 2 O 5 being within the ranges of 0.4:1 to 4.5:1; 0:1 to 4.0:1 and 0:1 to 5:1 respectively, and the total mole ratio of said three components to total P 2 O 5 being from about 2.8:1 to about 7.0:1, said reaction being conducted by first reacting the phosphorus compound with the hydroxy ether, and when the total carbon atoms of R and R 1 is 3 or 4, also with the long chain alcohol for a period of time of from about 5 to about 30 minutes at a temperature of from about 70° to about 90° C., cooling the reaction mixture to below 70° C., adding the short chain alcohol to the reaction mixture and reacting the mixture at a temperature of from about 70° to about 90° C. for a period of time to provide a total reaction time of from about 1.5 to about 6 hours.

Claim 23

The method of claim 20 wherein when the total carbon atoms of R and R 1 is five to eight there is also reacted with the pentavalent phosphorus compound and the hydroxy ether a long chain monohydric alcohol containing at least 5 carbon atoms prior to reacting the short chain alcohol.

Claim 24

The method of claim 20 wherein the long chain alcohol has 5 to 12 carbon atoms.

Claim 25

The method of claim 20 wherein the pentavalent phosphorus compound is P 2 O 5 .

Claim 26

The method of claim 20 wherein the short chain alcohol is a primary, unsubstituted, straight chain, saturated alcohol.

Claim 27

The method of claim 24 wherein the short chain alcohol is ethanol, methanol, or a mixture thereof, and the long chain alcohol is unsubstituted.

Claim 28

The method of claim 25 wherein the short chain alcohol is methanol.

Claim 29

The method of claim 25 wherein the short chain alcohol is ethanol.

Claim 30

The method of claim 20 wherein each alcohol is unsubstituted.

Claim 31

The method of claim 28 wherein the long chain alcohol has 5 to 12 carbon atoms; the pentavalent phosphorus compound is P 2 O 5 ; and the short chain alcohol is primary, straight chain, and saturated.

Claim 32

The method of claim 29 wherein the aluminum compound is sodium aluminate.

Claim 33

The method of claim 30 wherein the organic liquid is an aliphatic hydrocarbon.

Claim 34

The method of claim 31 wherein from about 1 to about 25 gallon of the reaction product is employed per 1000 gallons of organic liquid.

Claim 35

The method of claim 29 wherein said hydroxy ether is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, propylene glycol monoisobutyl ether, propylene glycol monomethyl ether and mixtures thereof.

Claim 36

The method of claim 33 wherein the individual mole ratios of the hydroxy ether, the long chain alcohol and the short chain alcohol to P 2 O 5 are within the ranges of 0.8:1 to 1.8:1; 0:1 to 1.4:1; and 0.9:1 to 2.0:1 respectively.

Claim 37

The method of claim 34 wherein the short chain alcohol is methanol, ethanol, or a mixture thereof.

Claim 38

The method of claim 35 wherein the total mole ratio of the short chain alcohol, hydroxy ether and long chain alcohol to P 2 O 5 is about 3.64:1.

Claim 39

The method of claim 36 wherein the short chain alcohol is methanol.