Method and compositions for hydraulic fracturing and for tracing formation water

1. A tracer composite for use in tracing production of formation water comprising:

a solid carrier material which is substantially non-soluble in water, said solid carrier material being an activated or silanized carrier material, and

an exposed tracer on said solid carrier material,

wherein the tracer composite has no coating thereon over the exposed tracer and

said exposed tracer is held on the solid carrier material by an adsorption bond which (i) substantially prevents the exposed tracer from being eluted from said solid carrier material at a detectable level in water having a salinity level of less than 1 part per thousand by weight but (ii) permits the exposed tracer, at least when said salinity level of said water reaches a value of 5 parts per thousand by weight, to be eluted from said solid carrier material at detectable levels which increase as said salinity level of said water increases.

2. The tracer composite of claim 1 wherein said exposed tracer is, or has been formed from, a halogenated benzoic aldehyde or a halogenated benzoic acid.

3. The tracer composite of claim 2 wherein said exposed tracer is, or has been formed from, a halogenated benzoic aldehyde and wherein said halogenated benzoic aldehyde is:

2-fluorobenzaldehyde; 4-fluorobenzaldehyde; 2,3,4,5-tetrafluorobenzaldehyde; 2-(trifluoromethyl) benzaldehyde; 4-(trifluoromethyl) benzaldehyde; 2,5-difluorobenzaldehyde; 3-fluorobenzaldehyde; 2,6-difluorobenzaldehyde; pentafluorobenzaldehyde; 3,5-difluorobenzaldehyde; 2,4-difluorobenzaldehyde; 3,4-difluorobenzaldehyde; 3,4,5-trifluorobenzaldehyde; 2,3,4-trifluorobenaldehyde; 2,4,5-trifluorobenzaldehyde; 2,3-difluorobenzaldehyde; 3-(trifluoromethyl) benzaldehyde; 2-chlorobenzaldehyde; 4-chlorobenzaldehyde; 3-chlorobenzaldehyde; 2,5-dichlorobenzaldehyde; 3,5-dichlorobenzaldehyde; 2,6-dichlorobenzaldehyde; 3,4-dichlorobenzaldehyde; 2, 4-dichlorobenzaldehyde; 2-chloro-4-fluorobenzaldehyde; 5-chloro-2-fluorobenzaldehyde; 4-chloro-3-fluorobenzaldehyde; 3-chloro-4-fluorobenzaldehyde; 4-chloro-2-fluorobenzaldehyde; 5-bromo-2-chlorobenzaldehyde; 2-bromo-5-chlorobenzaldehyde; 2-bromo-4-fluorobenzaldehyde; 3-bromo-4-fluorobenzaldehyde; 2-bromo-5-fluorobenzaldehyde; 4-bromo-2-fluorobenzaldehyde; 4-bromo-3-fluorobenzaldehyde; 3-bromo-2-fluorobenzaldehyde; 3-bromo-2,5-difluorobenzaldehyde; or 2-bromo-4,5-difluorobenzaldehyde.

4. The tracer composite of claim 3 wherein said solid carrier material provides catalytic sites in the presence of water which convert at least 50% of said halogenated benzoic aldehyde adsorbed on said solid carrier material to a halogenated benzoic acid.

5. The tracer composite of claim 2 wherein said solid carrier material is a granular activated charcoal.

6. A method of producing a tracer composite for use in tracing formation water, said method comprising the step of adsorbing a halogenated benzoic aldehyde on a solid carrier material which provides catalytic sites in the presence of water which convert at least a portion of said halogenated benzoic aldehyde adsorbed on said solid carrier material to a halogenated benzoic acid.

7. The method of claim 6 wherein said halogenated benzoic aldehyde is adsorbed on said solid carrier material in an amount in a range of from about 5% to about 30% by weight of a total weight of said tracer composite.

8. The method of claim 7 wherein at least 50% of said halogenated benzoic aldehyde adsorbed on said solid carrier material is converted in the presence of water to said halogenated benzoic acid.

9. The method of claim 8 wherein said halogenated benzoic aldehyde is:

2-fluorobenzaldehyde; 4-fluorobenzaldehyde; 2,3,4,5-tetrafluorobenzaldehyde; 2-(trifluoromethyl) benzaldehyde; 4-(trifluoromethyl) benzaldehyde; 2,5-difluorobenzaldehyde; 3-fluorobenzaldehyde; 2,6-difluorobenzaldehyde; pentafluorobenzaldehyde; 3,5-difluorobenzaldehyde; 2,4-difluorobenzaldehyde; 3,4-difluorobenzaldehyde; 3,4,5-trifluorobenzaldehyde; 2,3,4-trifluorobenaldehyde; 2,4,5-trifluorobenzaldehyde; 2,3-difluorobenzaldehyde; 3-(trifluoromethyl) benzaldehyde; 2-chlorobenzaldehyde; 4-chlorobenzaldehyde; 3-chlorobenzaldehyde; 2,5-dichlorobenzaldehyde; 3,5-dichlorobenzaldehyde; 2,6-dichlorobenzaldehyde; 3,4-dichlorobenzaldehyde; 2,4-dichlorobenzaldehyde; 2-chloro-4-fluorobenzaldehyde; 5-chloro-2-fluorobenzaldehyde; 4-chloro-3-fluorobenzaldehyde; 3-chloro-4-fluorobenzaldehyde; 4-chloro-2-fluorobenzaldehyde; 5-bromo-2-chlorobenzaldehyde; 2-bromo-5-chlorobenzaldehyde; 2-bromo-4-fluorobenzaldehyde; 3-bromo-4-fluorobenzaldehyde; 2-bromo-5-fluorobenzaldehyde; 4-bromo-2-fluorobenzaldehyde; 4-bromo-3-fluorobenzaldehyde; 3-bromo-2-fluorobenzaldehyde; 3-bromo-2,5-difluorobenzaldehyde; or 2-bromo-4,5-difluorobenzaldehyde.

10. The method of claim 9 wherein said solid carrier material is a granular activated charcoal.

11. A method of fracturing and tracing production of formation water from a subterranean formation, said method comprising the steps of:

(a) injecting a fracturing fluid into a fracturing zone of a subterranean formation wherein: at least a portion of said fracturing fluid includes an amount of a tracer composite material, said tracer composite material comprises an exposed tracer on a solid carrier material wherein said exposed tracer is for tracing said formation water, said solid carrier material is substantially non-soluble in water, said solid carrier material is an activated or silanized carrier material, the tracer composite material has no coating thereon over the exposed tracer, said exposed tracer is or is formed from a halogenated benzoic aldehyde or a halogenated benzoic acid, and said exposed tracer is held on the solid carrier material by an adsorption bond which (i) substantially prevents the exposed tracer from being eluted from said solid carrier material at a detectable level in water having a salinity level of less than 1 part per thousand by weight but (ii) permits the exposed tracer, at least when said salinity level of said water reaches a value of 5 parts per thousand by weight, to be eluted from said solid carrier material at detectable levels which increase as said salinity level of said water increases, and

(b) analyzing a product recovered from a well associated with said subterranean formation for a presence of said exposed tracer to determine whether said product includes formation water produced from said fracturing zone.

12. The method of claim 11 wherein said tracer composite material is formed by adsorbing a halogenated benzoic aldehyde on said solid carrier material and wherein said solid carrier material provides catalytic sites in the presence of water which convert at least a portion of said halogenated benzoic aldehyde adsorbed on said solid carrier material to a halogenated benzoic acid.

13. The method of claim 12 wherein said halogenated benzoic aldehyde is:

2-fluorobenzaldehyde; 4-fluorobenzaldehyde; 2,3,4,5-tetrafluorobenzaldehyde; 2-(trifluoromethyl) benzaldehyde; 4-(trifluoromethyl) benzaldehyde; 2,5-difluorobenzaldehyde; 3-fluorobenzaldehyde; 2, 6-difluorobenzaldehyde; pentafluorobenzaldehyde; 3,5-difluorobenzaldehyde; 2,4-difluorobenzaldehyde; 3,4-difluorobenzaldehyde; 3,4,5-trifluorobenzaldehyde; 2,3,4-trifluorobenaldehyde; 2,4,5-trifluorobenzaldehyde; 2,3-difluorobenzaldehyde; 3-(trifluoromethyl) benzaldehyde; 2-chlorobenzaldehyde; 4-chlorobenzaldehyde; 3-chlorobenzaldehyde; 2,5-dichlorobenzaldehyde; 3,5-dichlorobenzaldehyde; 2,6-dichlorobenzaldehyde; 3,4-dichlorobenzaldehyde; 2,4-dichlorobenzaldehyde; 2-chloro-4-fluorobenzaldehyde; 5-chloro-2-fluorobenzaldehyde; 4-chloro-3-fluorobenzaldehyde; 3-chloro-4-fluorobenzaldehyde; 4-chloro-2-fluorobenzaldehyde; 5-bromo-2-chlorobenzaldehyde; 2-bromo-5-chlorobenzaldehyde; 2-bromo-4-fluorobenzaldehyde; 3-bromo-4-fluorobenzaldehyde; 2-bromo-5-fluorobenzaldehyde; 4-bromo-2-fluorobenzaldehyde; 4-bromo-3-fluorobenzaldehyde; 3-bromo-2-fluorobenzaldehyde; 3-bromo-2,5-difluorobenzaldehyde; or 2-bromo-4, 5-difluorobenzaldehyde.

14. The method of claim 11 wherein said solid carrier material is a granular activated charcoal.

15. The method of claim 11 wherein at least most of said fracturing fluid injected into said fracturing zone includes a proppant material and said tracer composite material is blended with not more than a final ⅔ portion of a total amount of said proppant material which is injected into said fracturing zone.

16. The method of claim 15 wherein said tracer composite material is blended with not more than a final ½ portion of said total amount of said proppant material which is injected into said fracturing zone.

17. The method of claim 15 wherein said tracer composite material is blended with not more than a final ¼ portion of said total amount of said proppant material which is injected into said fracturing zone.

18. The method of claim 11 wherein said fracturing zone is a first fracturing zone, said tracer composite material is a first tracer composite material, said exposed tracer is a first exposed tracer, and said method further comprises the steps of:

(c) injecting, prior to step (b), a fracturing fluid into a second fracturing zone in said subterranean formation wherein: at least a portion of said fracturing fluid injected into said second fracturing zone includes an amount of a second tracer composite material, said second tracer composite material comprises a second exposed tracer on a solid carrier material, said second exposed tracer is for tracing formation water, said solid carrier material of said second tracer composite material is substantially non-soluble in water, said solid carrier material is an active or silanized carrier material, the second tracer composite material has no coating thereon over the second exposed tracer, said second exposed tracer is different from said first exposed tracer, said second exposed tracer is or is formed from a halogenated benzoic aldehyde or a halogenated benzoic acid adsorbed on said solid carrier material of said second tracer composite material, and said second exposed tracer is held on the solid carrier material of the second tracer composite material by an adsorption bond which (i) substantially prevents the second exposed tracer from being eluted from said solid carrier material of said second tracer composite material at a detectable level in water having a salinity level of less than 1 part per thousand by weight but (ii) permits the second exposed tracer to be eluted from said solid carrier material of said second tracer composite material at a detectable level at least when exposed to formation water having any salinity value which is equal to or greater than 5 parts per thousand by weight, and

(d) analyzing said product recovered from said well for a presence of said second exposed tracer to determine whether said product includes formation water produced from said second fracturing zone.

19. The method of claim 11 further comprising the steps of:

adding, prior to step (b), a fracturing fluid tracer to said fracturing fluid for tracing a return of said fracturing fluid, said fracturing fluid tracer being different from said exposed tracer for tracing said formation water and

analyzing said product recovered from said well associated with said subterranean formation for a presence of said fracturing fluid tracer to determine whether said product includes a return of said fracturing fluid from said fracturing zone.