CA2354789C

CA2354789C - Fracturing method using aqueous or acid based fluids

Info

Publication number: CA2354789C
Application number: CA 2354789
Authority: CA
Inventors: Travis L. Allan; Junad Amin; Alan K. Olson; Ronald G. Pierce
Original assignee: CHEMERGY Ltd; Calfrac Well Services Ltd
Current assignee: Calfrac Well Services Ltd
Priority date: 2000-08-08
Filing date: 2001-08-07
Publication date: 2006-05-23
Anticipated expiration: 2021-08-07
Also published as: CA2354789A1

Abstract

An improved method .and fracturing fluid for hydraulic fracturing of a subterranean formation, the fracturing fluid comprising a surfactant, a water soluble or dispersible anionic organic salt, an acid and a low molecular weight organic solvent.

Description

FRACTURING METHOD USING AQUEOUS OR ACID BASED FLUIDS
Field of the Invention The present invention relates to the field of fracturing fluids, in particular, surfactant based fracturing fluids.
Background of the Invention A fracturing fluid is a fluid that is pumped into a hydrocarbon-bearing reservoir in a geological formation under high pressure to open fractures in the formation, thereby to facilitate the flow of hydrocarbons from the formation. Fracturing fluids are preferably viscous, so as to be able to carry proppants into the fractures that are forced open in the formation.
Conventional fracturing fluids contain high molecular weight polysaccharides based polymers, as gelling agents. These polymers are associated with build-up of filter cake on the fracture face. If the filter cake is not completely removed, it will impede flow of reservoir fluid and hence reduce the effectiveness of the fracture.
Control and limiting of residual filter cake becomes extremely important when dealing with problematic formations. Alternative to the conventional polymeric system is the novel development of the present invention.
The present invention is ~~ non-polymeric visco-elastic system. The system is based on surfactant chemistry. Although surfactant based systems have been employed in gravel packing operations since the early 1980s (SPE 17168), further development and refinement of surfactant chemistry has yielded surfactant based fracturing fluids. Some of these techniques are discussed and revealed in Canadian Patent No. 1,298,697 and U.S. Patent No. 5,964,295.
The advantage of a surfactant based fracturing fluid over a polymeric gel based fluid is that micelle formation in surfactant fluids is virtually instantaneous, but does not alter the actual chemical composition of the fluid. That is, once a critical concentration of surfactant molecules is reached, they will aggregate as micelles, thereby increasing the viscosity of the fluid, but without changing the chemical composition. Therefore, no chemical initiator is required, and viscosity increase occurs uniformly throughout the fluid.
The key to the present invention therefore is the novel use of amphoteric glycinate surfactant, as an additive. In acidic conditions, the glycinate exhibits cationic properties. When the glycinate is combined in proper ratio with anionic salt such as Sodium Xylene Sulfonate in a neutral to acidic environment of an aqueous stimulation fluid (water or acid) it is believed to form highly structured three dimensional micelles. The interference/interaction of the micelles imparts the desired viscoelastic properties to the stimulation fluid. The required cationic activity of the glycinate is ensured by utilization of an organic acid in the formulation of the additive.
The purpose of a low molecular alcohol used in the system is to serve as a dispersability agent for making the system field friendly.
The viscoelastic properties imparted to stimulation fluid are controlled by three mechanisms:
1. By varying total additive added to the stimulation fluid (0.1-5.0% by volume);

2. By controlling the ratio between the organic/inorganic salt and the glycinate (0.15-0.6% of glycinate); and 3. By controlling or adjusting the pH of the fracturing fluid system.
Another novel use of amphoteric surfactant is the utilization of change in its ionic properties with pH to control the break viscosity lowering mechanism of the gel.
As the pH of the system is increased above 6.5 the ionic properties of the glycinate change from cationic to anionic. This change de-stabilizes the micellar structure, hence, resulting in the break of the gel, allowing for easy post frac cleanup.
In the earlier technologies, to attain a break the system had to encounter formation fluids (oil andlor water) in order to de-stabilize the gel structure. Simple adjustment in pH did not break the gel in the earlier inventions. This limited the use of the system to those wells that contained oil or those that produced condensate. In the present invention the pH of the system can be increased easily by utilization of alkaline compounds such as carbonates, oxides, amines and etc.
As the temperature of the system increases the interaction between the ion weakens, resulting in decrease in stability of the micelles. The upper limit of the gel appears to be around 65°C. The upper temperature range may be further increased by utilization with alternative salts or using a surfactant with different length of the alkyl group.
In a broad aspect, then, the present invention relates to a fracturing fluid comprising:
(i) a surfactant having the general formula R, R3N+CH2C00-where R,-R2 are each an aliphatic group of C1-C4, branched or straight chained, saturated or unsaturated, R3 is a group of C12-22, branched, straight or cyclic, saturated or unsaturated;
(ii) a water soluble or dispersible anionic organic or inorganic salt;
(iii) an acid; and (iv) a low molecular weight organic solvent wherein the viscosity of the fluid is lowered by raising the pH thereof.

According to a further aspect of the present invention, there is also provided a visco-elastic fluid for fracturing a subterranean formation, the viscosity of the fluid being breakable subsequent to fracturing, said visco-elastic fluid comprising:
(i) a surfactant having the general formula R, R3N+CH2C00-RZ
where R,-R2 are each an aliphatic group of C1-C4, branched or straight chained, saturated or unsaturated, R3 is a group of C12-22, branched, straight or cyclic, saturated or unsaturated;
(ii) a water soluble or dispersible anionic organic or inorganic salt;
(iii) an acid; and (iv) a low molecular weight organic solvent.
According to yet another aspect of the present invention, there is also provided a method of fracturing a subterranean formation comprising the steps of:
providing a visco-elastic surfactant based hydraulic fracturing fluid comprising:
(i) a surfactant having the general formula R, R3N+CHZCOO-where R,-R2 are each an aliphatic group of C1-C4, branched or straight chained, saturated or unsaturated, R3 is a group of C12-22, branched, straight or cyclic, saturated or unsaturated;
(ii) a water soluble or dispersible anionic organic or inorganic salt;
-3a-(iii) an acid; and (iv) a low molecular weight organic solvent, pumping said fracturing fluid through a well bore and into a subterranean formation at a sufficient pressure to cause fracturing of said formation; and lowering the viscosity of said fluid subsequent to said fracturing to facilitate formation clean-up.
According to yet another aspect of the present invention, there is also provided a fluid for fracturing a subterranean formation and for use with a breaker system, said fluid comprising:
(i) a surfactant having the general formula R~
R3N+CH2C00-where R,-R2 are each an aliphatic group of C1-C4, branched or straight chained, saturated or unsaturated, R3 is a group of C12-22, branched, straight or cyclic, saturated or unsaturated;
(ii) a water soluble or dispersible anionic organic or inorganic salt; and (iii) an acid.
According to yet a further aspect of the present invention, there is also provided a method of fracturing a subterranean formation comprising the steps of:
providing a visco-elastic surfactant based hydraulic fracturing fluid comprising:
(i) a surfactant having the general formula -3b-R, R3N+CH2C00-wherein R,-R2 are each an aliphatic group of C1-C4, branched or straight chained, saturated or unsaturated, R3 is a group of C12-22, branched, straight chained or cyclic, saturated or unsaturated;
(ii) a water soluble or dispersible anionic organic or inorganic salt; and (iii) an acid; and (iv) a low molecular weight organic solvent, and;
pumping said fracturing fluid through a well bore and into a subterranean formation at a sufficient pressure to cause fracturing of said formation including the further step of lowering the viscosity of said fluid by raising the pH thereof.
The attached drawing is a graph of viscosity % against pH.
It will be observed, then, that the present invention is a four component system, although the four components are typically combined into a single component prior to addition to the fluid being viscosified. The primary component, the surfactant, is preferably a dihydroxyethyl tallow glycinate having the structure:
-3c-C~,6_,B~IN+CH2C00-The second component, the salt is preferably sodium xylene sulfonate.
However, other similar salts may be used, such as potassium, zinc, ammonium, magnesium (etc.) xylene or toluene sulfonate. In addition, other naphthalene backboned sulfonate salts may be used. Inorganic salts such as sodium chloride or potassium chloride (KCL) can also be used.
As to the acid component, any organic or mineral acid may be used to lower the pH below 6.5. Acids that have been found to be useful include formic acid, citric acid, hydrochloric acid, and so on. The preferred acid is acetic acid because it is universally available, low cost, and safe to handle.
The final component, the alcohol solvent is used to modify the viscosity of the solvent, usually water, by altering its polarity, which will result in reduced viscosity of the miscellar formations.
In an aqueous fluid, the surfactant composition of the present invention is added in a concentration of from about 0.1 % wt to about 5.0% wt. The actual composition in a preferred composition will be, for example:
Glycinate 0.65 Organic salt0.20 Acid 0.025 Solvent 0.125 Some variations, up to about 50% per component, are possible.
Unfoamed, the upper temperature limit of the present invention is about 65°C.
However, formulation of the present invention is also compatible with CO2, NZ
and C02, N2, air and low molecular weight hydrocarbon gas foams, over a temperature range of 5°C - 80°C.
The addition of Nitrogen (N2) or Carbon Dioxide (C02) as either a liquid or gas can dramatically improved the flow back characteristics of fracture fluids especially in under pressured reservoirs. Not only is the amount of fluid required for the job reduced, the hydrostatic head of the well bore fluid is lowered and the well can flow on its own. High pumping pressures will compress Nitrogen bubbles during placement of the stimulation treatment only to expand when pressures are bled off and the treatment is flowed back. The fluid contains 10-200 standard cubic metres of Nitrogen or Carbon Dioxide per cubic metre of fluid.
Liquid or gaseous C02 can also be used to act as the energizing phase, although it is pumped as a liquid and returns to surfaces as a gas. The thermodynamic properties of liquid/gaseous C02 make it a unique fluid for fracturing.
The fluid is pumped at low temperatures of typically - 5 to -25° C and it remains as a critical fluid (single phase) while the fracture is created and the proppant placed.
Liquid C02 that leaks off from the fracture quickly rises to reservoir temperature, increasing its specific volume and becoming more like a gas. When the pressure is dropped and the well is flowed the single phase fluid returns to surface as C02 vapor.
Treatment design for N2 energized fluid systems typically utilizes N2 pumped at ratios of 40 - 60 scm/m3, which means standard cubic meters of Nitrogen gas per cubic meter of fluid (water). This is normally sufficient to allow the well to flow unassisted with reservoir pressure gradients of 6 kPa/m or higher. For energized C02 systems, liquid C02 is added at equivalent ratios, once the conversion from liquid to gas is made (543 scm/m3). Combined down hole fracturing pump rates are approximately 3.5m3/min.
Foam Fracturin4 When liquid C02 is used as the energizing medium, the resulting mixture is often referred to as an emulsion, since both phases are liquids. However, herein the term foam is used for describing both N2 or Liquid or gaseous C02 foamed systems.

A foam fracture treatment consists of nitrogen (typically 75%) dispersed as small bubbles throughout a continuous liquid phase. In traditional foams, the liquid phase contains surfactants and gellants to prevent coalescence and resulting phase separation. Foam quality (N2 or Liquid C02) should range from 52 - 95% (ratio of gas volume to foam volume). Above 95% the mixture can be defined as a mist with the gas becoming the continuous phase. Below 52% there is no bubble to bubble interference and therefore a stable foam does not exist. Above 52% the gas concentration is high enough for the bubbles to interfere and deform, thereby imparting resistance to shear and increasing the viscosity of the fluid system.
Unlike conventional foams that utilize long-chained polymers to viscosify the external phase, the present invE;ntion, foamed, uses a combination of surfactants to impart viscosity to the water phase. The chemical structure that is formed produces a three-dimensional matrix of molecules that interfere with each other and raise the apparent viscosity of the base fluid system. Combined with either N2 or Liquid C02, foam viscosities are generated as a function of foam quality and the fluid system develops all of the properties desired for a fracture fluid system. The use of surfactants also produces a fluid with strong foaming tendencies that aids the return of fluids from the reservoir when foamed with the producing hydrocarbon gas.
Field Trials With depths ranging from 450 - 1600 m, trial stimulation treatments have focussed on Cretaceous sandstones that range in reservoir pressure from 2 - 7 kPa/m. Fracture fluid cleanup has been reported as superior to conventional foams utilizing polymer base gels. Some of the stimulated reservoirs include Glauconite, Dinosaur Park, Bad Heart, Viking, Belly River, Colony, Sunburst, Bluesky, Dunvegan, Mannville, and Bow Island. Long term production data is not available at this time, but comments from trial operations are very positive on fast clean-up and initial production. Also, these reservoirs represent trial stimulation work to date and do not suggest any limitations on the potential for usage on other gas-bearing reservoirs.

Tyra~ical Treatments JOB TYPE LOCATION FORMATION AVERAGE RATEPROPPANT
VOL.

FRAC GRADIENT'DEPTH AVE. PRESSUREMAX CONC.

N2 Energized 69-22W5 Bad Heart 2.8 m3/min 25 tonne CWS 400 22 kPa/m 625 m 9.5 Mpa 1070 kg/m3 C02 Energized17-24W4 Ostracod 2.8 m3/min 10 tonne CWS 400 18 kPa/m 1668 m 27.0 Mpa 1012 kg/m3 Nz Foamed 33-5W4 Colony 3.4 m3/min 15 tonne CWS 400 22 kPa/m 858 m 18.3 Mpa 743 kg/m' COz Foamed 20-26W4 Belly River 4.2 m'/min 5 tonne CWS 400 17 kPa/m 969 m 12.0 Mpa 560 kg/m3 Note: CWS 400 is the fluid of the present invention.
Post Fracture Flow Rate Comparison JOB TYPE LOCATION MEDICINE L. MILK RIVERU. MILK RIVER
HAT FLOW RATE FLOW RATE
FLOW RATE

Nz Energized 21-17W4 11,680 m'Iday2,650 m3/day1,200 m3/day Borate NZ energized 21-17W4 10,860 m'/day4,610 m3/day2,700 m3/day Lab Test Data The following examples are used to illustrate viscosifying properties of the fluid of the present invention.
Example #1 Following additives were added to the water while stirring:
Glycinate 0.520 volume Sodium Xylene Sulfonate 0.152 volume Glacial Acetic Acid 0.040 volume Isopropyl Alcohol 0.088 volume Results:
Upon completion of addition of the additives. Viscoelastic gel was observed to be present in the container. The rheological properties of the gel were measured using Brookfield LVT viscometer with spindle #1 and the guard leg attached.
Speed~,RPM~ Viscosit cP
100 10.9 60 14.T
50 16.4.
30 23.2' 29.4 12 39.5~
Example #2 Following additives were added to the water while stirring.
15 Glycinate 1.30 volume Sodium Xylene Sulfonate 0.32 volume Glacial Acetic Acid 0.10 volume Isopropyl Alcohol 0.22 volume Results:
20 Upon completion of addition of the additives. Viscoelastic gel was observed to be present in the container. The rheological properties of the gel were measured using Brookfield t_VT viscometer with spindle #1 and the guard leg attached.
Speed ~RPM~ Viscosit cP
60 71.T
50 83.5~
127.4 20 178..8 12 267. 0 1.5 592 0.6 670 0.3 740 _g_ Conclusion:
The two examples clearly demonstrate viscosifying properties of surfactants.
These viscosities are deemed sufficient for fracturing.
The novel surfactant based system of the present invention can not only be used for viscosifying water but also can be used for viscosifying mineral, organic and/or inorganic acids. The rheological properties imparted by the system will be dictated by type of acid and strength of acid being used. Typical acid used are HC1 (10-34%, Acetic Acid, Formic Acid, Sulfamic Acid, HC1/HF acid mixture etc.) Typically, viscosified acids are used in stimulation of: hydrocarbon bearing formation, water injection wells, and disposal wells to improve production or injectivity of the reservoir. Viscosified acids have an advantage over non-viscosified acid, as the reaction rate of the acid to the formation rock is proportional to viscosity of acid mixture. By retarding the acid reactivity through the gellation process, deeper acid penetration in more controlled fashion is accomplished. This typically creates better flow channels between reservoir and the well.
The viscosifying acid with surfactant alternative embodiments of the present invention has an additional advantage compared to the conventional polymer methods of viscosifying acid. That is, as the acid reaction proceeds with the formation, product from this reaction produce salts that act as a breaker to viscosified acid. This allows to cleanup-spent acid more easily.
It will also be understood by one skilled in the art that altering the ratio of additives in either embodiment of the present invention can control the rheological properties.
In order to lower the viscosity of the surfactant based fracturing fluid of the present invention, the pH of the fluid is raised by the addition of an alkaline substance such as magnesium oxide or sodium hydroxide. This effectively raises the critical micelle concentration of the fluid, resulting in disassociation of the micelles that have _g_ been formed. Accordingly, it will be understood that formation clean-up is quickly accomplished, without caking or clogging.

Claims

1. A fluid for fracturing a subterranean formation comprising:
(i) a surfactant having the general formula where R1-R2 are each an aliphatic group of C1-C4, branched or straight chained, saturated or unsaturated, R3 is a group of C12-22, branched, straight or cyclic, saturated or unsaturated;
(ii) a water soluble or dispersible anionic organic or inorganic salt;
(iii) an acid; and (iv) a low molecular weight organic solvent wherein the viscosity of the fluid is lowered by raising the pH thereof.

2. A fluid as claimed in claim 1 wherein said pH is raised by the addition of an alkaline compound selected from the group consisting of carbonates, oxides and amines.

3. A fluid as claimed in claims 1 or 2, wherein the ratio of said salt to said surfactant is in the range of 1:4 to 1:2.

4. A fluid as claimed in claims 1, 2 or 3, wherein said salt is selected from the group consisting of potassium xylene sulfonate, sodium xylene sulfonate, ammonium xylene sulfonate, zinc xylene sulfonate, magnesium xylene sulfonate, sodium toluene sulfonate, potassium toluene sulfonate, zinc toluene sulfonate, ammonium toluene sulfonate, magnesium toluene sulfonate, NaCl and KCl.

5. A fluid as claimed in any of claims 1 to 4, wherein said acid is selected from the group consisting of formic acid, citric acid, hydrochloric acid and acetic acid.

6. A fluid as claimed in any of claims 1 to 5, wherein said organic solvent is a low molecular weight alcohol.

7. A fluid as claimed in any of claims 1 to 6, wherein said surfactant is present in a quantity of about 0.1 % (wt) to about 5.0% (wt).

8. A fluid as claimed in any of claims 1 to 7, in the form of a foam including about 52 to about 95% gas selected from the group consisting of CO2, N2, air and low molecular weight hydrocarbons.

9. A fluid as claimed in claim 8 containing 10-200 standard cubic metres of N2 per cubic metre of fluid.

10. A fluid as claimed in claim 8 containing 10-200 standard cubic metres of gaseous CO2 per cubic metre of fluid or the liquid equivalent.

11. A visco-elastic fluid for fracturing a subterranean formation, the viscosity of the fluid being breakable subsequent to fracturing, said visco-elastic fluid comprising:
(i) a surfactant having the general formula where R1-R2 are each an aliphatic group of C1-C4, branched or straight chained, saturated or unsaturated, R3 is a group of C12-22, branched, straight or cyclic, saturated or unsaturated;
(ii) a water soluble or dispersible anionic organic or inorganic salt;
(iii) an acid; and (iv) a low molecular weight organic solvent.

12. A fluid as claimed in claim 11, wherein the ratio of said salt to said surfactant is in the range of 1:4 to 1:2.

13. A fluid as claimed in claims 11 or 12, wherein said salt is selected from the group consisting of potassium xylene sulfonate, sodium xylene sulfonate, ammonium xylene sulfonate, zinc xylene sulfonate, magnesium xylene sulfonate, sodium toluene sulfonate, potassium toluene sulfonate, zinc toluene sulfonate, ammonium toluene sulfonate, magnesium toluene sulfonate, NaCl and KCl.

14. A fluid as claimed in claims 11, 12 or 13, wherein said acid is selected from the group consisting of formic acid, citric acid, hydrochloric acid and acetic acid.

15. A fluid as claimed in claims 11, 12, 13 or 14, wherein said organic solvent is a low molecular weight alcohol.

16. A fluid as claimed in any of claims 11 to 15, wherein said surfactant is present in a quantity of about 0.1 % (wt) to about 5.0% (wt).

17. A fluid as claimed in any of claims 11 to 16, in the form of a foam including about 52 to about 95% gas selected from the group consisting of CO2, N2, air and low molecular weight hydrocarbons.

18. A fluid as claimed in claim 17 containing 10-200 standard cubic metres of per cubic metre of fluid.

19. A fluid as claimed in claim 17 containing 10-200 standard cubic metres of gaseous CO2 per cubic metre of fluid or the liquid equivalent.

20. A fluid as claimed in any of claims 11 to 19 additionally comprising an alkaline compound selected from the group consisting of carbonates, oxides and amines added subsequent to fracturing for breaking said fluid's viscosity.

21. A method of fracturing a subterranean formation comprising the steps of:
providing a visco-elastic surfactant based hydraulic fracturing fluid comprising:
(i) a surfactant having the general formula where R1-R2 are each an aliphatic group of C1-C4, branched or straight chained, saturated or unsaturated, R3 is a group of C12-22, branched, straight or cyclic, saturated or unsaturated;
(ii) a water soluble or dispersible anionic organic or inorganic salt;
(iii) an acid; and (iv) a low molecular weight organic solvent, pumping said fracturing fluid through a well bore and into a subterranean formation at a sufficient pressure to cause fracturing of said formation; and lowering the viscosity of said fluid subsequent to said fracturing to facilitate formation clean-up.

22. A method as claimed in claim 21, wherein the ratio of said salt to said surfactant is in the range of 1:4 to 1:2.

23. A method as claimed in claims 21 or 22, wherein said salt is selected from the group consisting of of potassium xylene sulfonate, sodium xylene sulfonate, ammonium xylene sulfonate, zinc xylene sulfonate, magnesium xylene sulfonate, sodium toluene sulfonate, potassium toluene sulfonate, zinc toluene sulfonate, ammonium toluene sulfonate, magnesium toluene sulfonate, NaCl and KCl.

24. A method as claimed in claims 21, 22 or 23 wherein said acid is selected from the group consisting of formic acid, citric acid, hydrochloric acid and acetic acid.

25. A method as claimed in claims 21, 22, 23 or 24 wherein said organic solvent is a low molecular weight alcohol.

26. A method as claimed in any of claims 21 to 25, wherein said surfactant is present in a quantity of about 0.1 % (wt) to about 5.0% (wt).

27. A method as claimed in any of claims 21 to 26, in the form of a foam including about 52 to about 95% liquified gas selected from the group consisting of CO2, N2, air and low molecular weight hydrocarbons.

28. A method as claimed in any of claims 21 to 27 containing 10-200 standard cubic metres of N2 per cubic metre of fluid.

29. A method as claimed in any of claims 21 to 27 containing 10-200 standard cubic metres of gaseous C02 per cubic metre of fluid or the liquid equivalent.

30. A method as claimed in any of claims 21 to 29 wherein the step of lowering the viscosity of said fluid comprises the addition to said fluid of an alkaline compound selected from the group consisting of carbonates, oxides and amines.

31. A fluid for fracturing a subterranean formation and for use with a breaker system, said fluid comprising:
(i) a surfactant having the general formula where R1-R2 are each an aliphatic group of C1-C4, branched or straight chained, saturated or unsaturated, R3 is a group of C12-22, branched, straight or cyclic, saturated or unsaturated;
(ii) a water soluble or dispersible anionic organic or inorganic salt; and (iii) an acid.

32. A fluid as claimed in claim 29, wherein said acid is a strong acid selected from the group consisting of hydrochloric acid, hydrofluoric acid, formic acid, sulfamic acid, acetic acid, and mixtures thereof.

33. A method of fracturing a subterranean formation comprising the steps of:
providing a visco-elastic surfactant based hydraulic fracturing fluid comprising:
(i) a surfactant having the general formula wherein R1-R2 are each an aliphatic group of C1-C4, branched or straight chained, saturated or unsaturated, R3 is a group of C12-22, branched, straight chained or cyclic, saturated or unsaturated;
(ii) a water soluble or dispersible anionic organic or inorganic salt; and (iii) an acid; and (iv) a low molecular weight organic solvent, and;
pumping said fracturing fluid through a well bore and into a subterranean formation at a sufficient pressure to cause fracturing of said formation including the further step of lowering the viscosity of said fluid by raising the pH thereof.

34. A method as claimed in claim 33, wherein said pH is raised by the addition of an alkaline compound selected from the group consisting of carbonates, oxides, and amines.

35. A method as claimed in claims 33 or 34, wherein said ratio of said salt to said surfactant is in the range of 1:4 to 1:2.

36. A method as claimed in claims 33, 34 or 35, wherein said salt is selected from the group consisting of potassium xylene sulfonate, sodium xylene sulfonate, ammonium xylene sulfonate, zinc xylene sulfonate, magnesium xylene sulfonate, sodium toluene sulfonate, potassium toluene sulfonate, zinc toluene sulfonate, ammonium toluene sulfonate, magnesium toluene sulfonate, NaCl and KCl.

37. A method as claimed in claims 33, 34, 35 or 36, wherein said acid is selected from the group consisting of formic acid, citric acid, hydrochloric acid and acetic acid.

38. A method as claimed in any of claims 33 to 37, wherein said organic solvent is a low molecular weight alcohol.

39. A method as claimed in any of claims 33 to 38, wherein said surfactant is present in a quantity of about 0.1 % (wt) to about 5.0% (wt).

40. A method as claimed in any of claims 33 to 39, wherein said hydraulic fracturing fluid is in the form of a foam including about 52 to about 95% gas selected from the group consisting of CO2, N2, air and low molecular weight hydrocarbons.

41. A method as claimed in claim 40, wherein said hydraulic fracturing fluid contains 10-200 standard cubic metres of N2 per cubic metre of fluid.

42. A method as claimed in claim 40, wherein said hydraulic fracturing fluid contains 10-200 standard cubic metres of gaseous CO2 per cubic metre of fluid or the liquid equivalent.