Controlled release solid scale inhibitors

1. A scale inhibitor composition for inhibiting scale in induced hydraulic fractures in hydraulic fracturing treatment of oil and/or gas wells comprising a polyphosphate glass component, the polyphosphate glass component comprising a reaction product of a mixture of components comprising from about 52 to about 75 wt. % of a phosphorus-containing compound, from about 6 to about 12 wt. % of a calcium-containing compound, from about 5 to about 10 wt. % of a magnesium-containing compound and from 1 to 20 wt. % of one or more controlled release additives comprising an aluminum-containing compound, a silicon-containing compound, or a zinc-containing compound, wherein:

the polyphosphate glass component being in the form of particles sized for insertion into fractures of hydraulically fractured wells and having a size of at least 100 mesh; and either;

the polyphosphate glass component comprises the aluminum-containing compound and dissolves at a rate of loss of less than 60% of the starting total mass over a 28 day period, when heated to 300° F. in deionized water at a concentration of 5 g polyphosphate glass per 300 mL deionized water; or

the polyphosphate glass component comprises the silicon- or zinc-containing compound and dissolves at a rate of loss less than 20% of the starting total mass over a 1 day period and greater than 20% of the starting total mass over a 28 day period, when heated to 150° F. in deionized water at a concentration of 5 g polyphosphate glass per 300 mL deionized water.

2. The composition of claim 1 , wherein the aluminum-containing compound comprises alumina, aluminum hydroxide, aluminium oxide hydroxide, a naturally occurring or synthetic alumina-containing mineral or polymorphs thereof, an aluminate salt or polymorphs thereof, an organic aluminum, or a combination thereof;

the silicon-containing compound comprises silica, a cyclic siloxane, a silicate salt, or a combination thereof; and

the zinc-containing compound comprises a zinc oxide, a zinc salt, or a combination thereof.

3. The composition of claim 2 , wherein the phosphorous-containing compound comprises phosphoric acid, polyphosphoric acid, a phosphate salt, a phosphate ester, or a phosphonate salt; the calcium-containing compound comprises calcium hydroxide, calcium oxide, calcium carbonate, or a combination thereof, and the magnesium-containing compound comprises magnesium hydroxide, magnesium oxide, magnesium carbonate, or a combination thereof; and the mixture further comprises a high-pH alkaline chemical comprising sodium carbonate, sodium hydroxide or a combination thereof.

4. The composition of claim 3 , wherein the aluminum-containing compound comprises alumina or aluminum hydroxide.

5. The composition of claim 4 , wherein the mixture comprises 2-10 wt % alumina or aluminum hydroxide.

6. The composition of claim 3 , wherein the silicon-containing compound comprises silica.

7. The composition of claim 6 , wherein the mixture comprises 2-10 wt % silica.

8. The composition of claim 1 , wherein the mixture consists essentially of the calcium-containing compound, the magnesium-containing compound, the phosphorous-containing compound, a high-pH alkaline compound and the one or more controlled release additives, wherein the polyphosphate glass component is a slowed release polyphosphate glass and the one or more controlled release additives is alumina or aluminum hydroxide; or the polyphosphate glass component is an accelerated release polyphosphate glass and the one or more controlled release additives is silica.

9. The composition of claim 3 , the polyphosphate glass component comprising a blend of a plurality of modified polyphosphate glasses, the plurality of modified polyphosphate glasses including at least one slowed release polyphosphate glass and at least one accelerated release polyphosphate glass, wherein the blend of a plurality of modified polyphosphate glasses exhibits a compound rate of dissolution.

10. The composition of claim 1 , wherein the mixture further comprises 5 to 10 wt. % of a high-pH alkaline compound; and the controlled release additive compound comprises either:

an aluminum-containing compound comprising aluminum hydroxide, alumina, aluminium oxide hydroxide, corundum, ruby, sapphire, bauxite, gibbsite, boehmite, diaspore, an aluminum halide, nitrate, phosphate or metaphosphate, a trialkylaluminum compound, or a combination thereof; or

a silicon-containing compound comprising silica, a cyclic siloxane, an orthosilicate salt, a metasilicate salt, or a combination thereof; or

a zinc-containing compound comprising a zinc oxide, a zinc salt, zinc carbonate, and combinations thereof.

11. The composition of claim 1 , wherein the polyphosphate glass component comprises the aluminum-containing compound and dissolves at the rate of loss of less than 60% of the starting total mass over the 28 day period, when heated to 300° F. in deionized water at the concentration of 5 g polyphosphate glass per 300 mL deionized water.

12. The composition of claim 1 , wherein the polyphosphate glass component comprises the silicon- or zinc-containing compound and dissolves at the rate of loss less than 20% of the starting total mass over the 1 day period and greater than 20% of the starting total mass over the 28 day period, when heated to 150° F. in deionized water at the concentration of 5 g polyphosphate glass per 300 mL deionized water.

13. A method of preparing the polyphosphate glass component of claim 1 , the method comprising:

mixing the phosphorous-containing compound, a high-pH alkaline compound, the calcium-containing compound, the magnesium-containing compound, and the one or more controlled release additives to form the mixture which undergoes a first reaction;

heating the mixture to a temperature of at least 1100° C. to form a glassy melt, the heated mixture undergoing a second reaction; and

cooling the glassy melt to form the polyphosphate glass component, wherein the polyphosphate glass component is a slow release polyphosphate glass if the one or more controlled release additives comprises the aluminum-containing compound, and the polyphosphate glass component is an accelerated release polyphosphate glass if the one or more controlled release additives comprises the silicon-containing compound or the zinc-containing compound.

14. The method of claim 13 , further comprising grinding the polyphosphate glass component into particles sized for insertion into fractures of hydraulically fractured wells and having a size of at least 100 mesh.

15. The method of claim 13 , the polyphosphate glass component comprising a blend of a plurality of modified polyphosphate glasses, the plurality of modified polyphosphate glasses including at least one slowed release polyphosphate glass and at least one accelerated release polyphosphate glass, and wherein the method further comprises blending at least one slowed release polyphosphate glass with at least one accelerated release polyphosphate glass to form the plurality of modified polyphosphate glasses, wherein the plurality of modified polyphosphate glasses exhibits a compound rate of dissolution.

16. A method of inhibiting scale formation in a subterranean formation, the method comprising mixing the composition of claim 1 with one or more proppants to form a mixture and injecting the mixture under pressure into hydraulically generated fractures of a wellbore.

17. A method of inhibiting scale formation in an industrial water system, the method comprising:

adding the scale inhibitor composition of claim 1 to an aqueous fluid within the system to inhibit scale formation on a surface of the system which is in contact with the fluid.

18. The method of claim 17 , wherein the surface is within a heat exchanger, a cooling tower, a pipeline, a water softener, a waste water treatment system, a paper mill, a mining system, a geothermal system, a fluid cooling system, a water treatment system, a water purification system, a wastewater treatment system, a reverse osmosis membrane, an ultrafiltration system, a water storage system, or an ion exchanger.

19. A method of inhibiting scale formation in a subterranean formation, the method comprising mixing the composition of claim 10 with one or more proppants to form a mixture and injecting the mixture under pressure into hydraulically generated fractures of a wellbore.

20. A method of inhibiting scale formation in an industrial water system, the method comprising:

adding the scale inhibitor composition of claim 10 to an aqueous fluid within the system to inhibit scale formation on a surface of the system which is in contact with the fluid.