BORATE CROSSLINKER

Abstract

The present disclosure relates to a crosslinking composition for use in crosslinking an aqueous suspension of guar, for use as a well treatment fluid and/or proppant carrier fluid for natural gas extraction. The present crosslinking composition is an aqueous suspension of hydroboracite. The composition may also comprise varying amounts of borax, canola oil, xanthan, glycerol, and/or NaOH. The composition may be selected to effect a desired delay in the crosslinking reaction in order to customize the viscosity and reaction time to the method of use, thereby maximizing proppant delivery while minimizing pump pressure.

Claims

1. A crosslinking composition comprising an aqueous suspension of approximately equal parts hydroboracite and borax.

2. The crosslinking composition of claim 1 wherein the composition further comprises canola oil, xanthan, and glycerol.

3. The crosslinking composition of claim 1 wherein the composition further comprises NaOH.

4. The crosslinking composition of claim 1 wherein the composition comprises 10-12% hydroboracite, 10-12% borax, 0.15-0.18% xanthan, and 15-20% glycerol.

5. A crosslinking composition comprising an aqueous suspension of approximately 10-20% hydroboracite and approximately 1-12% borax.

6. The crosslinking composition of claim 5 wherein the composition comprises 10-12% hydroboracite, 10-12% borax, 0.10-0.15% of a lightweight oil, 0.15-0.18% of a thickening agent, and 15-20% glycerol.

7. The crosslinking composition of claim 6 wherein the lightweight oil is canola oil and the thickening agent is xanthan.

8. A crosslinkable proppant carrier fluid comprising an aqueous suspension of guar and a crosslinking composition, wherein the crosslinking composition comprises a suspension of approximately 10-20% hydroboracite, approximately 1-12% borax, and approximately 15-20% glycerol.

9. The crosslinkable proppant carrier fluid of claim 8 wherein the crosslinking composition further comprises up to 1% canola oil and up to 1% xanthan.

10. The crosslinking composition of claim 4 wherein the composition further comprises 0.10-0.15% canola oil.

11. A method of crosslinking a proppant carrier fluid comprising mixing a crosslinking composition with an aqueous suspension of guar in a just-in-time fashion as the proppant carrier fluid is introduced into a wellbore, the crosslinking composition comprising approximately 10-20% hydroboracite, approximately 1-12% borax, and approximately 1-12% glycerol.

12. The method of claim 11 wherein the balance between the amount of hydroboracite and the amount of borax in the crosslinking composition achieves maximum viscosity in the proppant carrier fluid 5-120 minutes after the crosslinking composition is mixed with the aqueous suspension of guar.

13. The method of claim 11 wherein the balance between the amount of hydroboracite and the amount of borax in the crosslinking composition creates a 0-40 minute crosslink delay after the crosslinking composition is mixed with the aqueous suspension of guar.

14. A method of customizing a delay with which a crosslinkable proppant fluid reaches a desired viscosity, the method comprising adjusting a balance between an amount of hydroboracite and an amount of borax in a crosslinking composition according to the respective rates of borate ion release in hydroboracite and borax in comparison with the expected time delay between mixing the crosslinking composition with a crosslinkable substrate to form a crosslinked proppant fluid and delivering the crosslinked proppant fluid to a wellbore fracture.

15. The method of claim 14 further comprising the steps of mixing the crosslinking composition with an aqueous suspension comprising the crosslinkable substrate, forming the crosslinked proppant fluid, and delivering the crosslinked proppant fluid to a wellbore fracture.

Description

DETAILED DESCRIPTION

[0011] The present composition is a crosslinking agent for use in crosslinking a guar-based proppant fluid. The present composition is designed to crosslink guar at a controlled rate, and is particularly suited to applications where the crosslinking agent and the guar-based proppant fluid are mixed on-site at the well formation shortly before the mixture is introduced into the hydraulic fracture. The crosslinking rate of the fluid mixture can thus be customized according to how much time is expected to elapse between when the crosslinking agent and the proppant fluid are mixed, and when the resulting mixture arrives at its intended destination within the hydraulic fracture. An objective of the present composition is therefore to maintain a relatively lower viscosity in the proppant during the earlier stages of the proppant delivery, in order to minimize the friction pressure associated with pumping a viscous fluid into a well formation, while maximizing the benefits of a fully-crosslinked and therefore relatively highly viscous fluid at the later stages of proppant delivery, when the viscosity of the fluid accommodates increased proppant suspension and reduced fluid loss within the fractures.

[0012] The present composition comprises water, hydroboracite, and borax. Hydroboracite is a compound that releases borate ions relatively slowly when suspended in aqueous solutions such as proppant fluids under the conditions typically associated with fracking formations. Borax is a compound that releases borate ions relatively quickly when suspended in aqueous solutions like proppant fluids under the conditions typically associated with fracking formations. By customizing the balance between the amount of borax and the amount of hydroboracite in the present composition, one of skill in the art can customize the resulting crosslinking reaction to fit the needs of any particular hydraulic fracturing operation. The inventors have determined that many hydraulic fracturing systems will be desirably served by providing approximately equal amounts of borax and hydroboracite in the present composition.

[0013] Alternate embodiments that deviate from this balance include differing the relative amounts of hydroboracite or borax, or including other known sources of borate ions that have different rates of borate ion release. For instance, each of the borate compounds ulexite, colemanite, probertite, nobleite, gowerite, frolovite, meyerhofferite, inyoite, priceite, tertschite, ginorite, and inderborite release borate ions at different rates. By accounting for the rate of ion release of the source of the borate ion, one of skill in the art could optimize a reaction rate using the concepts and methods disclosed herein to mix and balance different borate ion sources to support a desired reaction speed. The inventors have found that hydroboracite balanced with borax is one way to provide a well-timed crosslinking reaction for most on-the-fly well delivery applications.

[0014] In preferred embodiments, the present composition further comprises canola oil (or a similar lightweight oil), xanthan (or a similar thickening agent), and/or glycerol (or a similar polyol). Canola oil improves the dispersion of the hydroboracite powder in the aqueous diluent. Xanthan slightly increases the viscosity of the present composition (prior to mixing it with a guar-based proppant fluid) which helps to suspend the hydroboracite. Glycerol also modifies the viscosity of the present composition and enhances the performance of the present composition (and any proppant fluid into which it is mixed) at temperatures that are on the lower end of what would be expected in hydraulic fracturing environments.

[0015] In one preferred embodiment, the present composition consists of:

TABLE-US-00001 water 58.36% hydroboracite 11.37% borax 11.37% canola oil  0.13% xanthan  0.16% glycerol (99%) 18.61%

[0016] This embodiment typically provides a cross-link delay of 1 to 5 minutes in guar gels depending on the temperature conditions of the environment in which it is used. In general, carrier fluid pH effects delay time, and modification of the pH of the carrier fluid provides yet another way to control the crosslink time. The pH of the carrier fluid also influences the stability of the gel at the higher end of the temperature range.

[0017] Guar gels crosslinked with the present composition are stable from 80° F. to 325° F. The 1 to 5 minute delay associated with the embodiment detailed above occurs at a pH of about 9 to 12. This embodiment provides a stable, aqueous-based, delayed borate crosslinker that yields high quality viscous guar gels upon delivery. One advantage of this embodiment is that it provides a stable, aqueous-based, delayed borate crosslinker without the use of ulexite, colemanite, or other sources of borate ions, and without the need for crosslink modifying agents or other external means for regulating the crosslink reaction. By avoiding the use of boron sources such as ulexite, and avoiding the need for crosslink modifying or regulating agents, this embodiment of the present composition provides increased delay capabilities, increased customization of reaction rate, simplified customization calculations, and lower cost.

[0018] The present composition is well-suited for uses in which it is mixed with the proppant carrier fluid continuously and delivered to the well formation on the fly during the treatment at 1-3 GPT (L/m3). On-the-fly delivery involves mixing the proppant carrier fluid and the crosslinking composition on site and pumping the resulting fluid into the well formation in a just-in-time or continuous fashion, as opposed to mixing the proppant carrier and crosslinking composition off site or in advance and storing or transporting the resulting fluid before pumping it into the wellbore.

[0019] One of skill in the art will fully appreciate how to determine the optimum concentration of the crosslinking composition within the proppant fluid to suit the desired application. The present composition can also be used with gel breakers. One of skill in the art will appreciate how to determine the optimal gel breaker concentration and identify the type of gel breaker to use for the desired fluid properties.

[0020] Preferred embodiments of the present composition have a specific gravity at 68° F. of about 1.11-1.16. Preferred embodiments have a freezing point of about 11° F.

[0021] Additional exemplary embodiments, and their respective viscosities are provided in the following examples.

Example 1

[0022] The table below shows the formulation (first table) and corresponding viscosity delay at 160° F. (second table) for example embodiments 1-6. Measurements for embodiment 1 were taken using a F 50 Unit 2 rheometer, and measurements for embodiments 2-6 were taken using an F 50 Unit 1 rheometer.

[0023] Formulation:

TABLE-US-00002 x-Linker loading, CrossLink Water HB Borax Glycerol gpt pH 1 58.36% 11.37% 11.37% 18.61% 1 11.01 2 67.34% 11.37% 11.37%  9.63% 1.5 11.09 3 71.82% 15.00%  7.74%  5.16% 1.5 10.85 4 74.37% 13.82%  6.91%  4.61% 1.5 11.01 5 78.08% 17.08%  4.55%  0.00% 1 11.3 6 58.36% 19.37%  0.00% 18.61% 1.5 11.26

[0024] Viscosity (in cP) Over Time (in Minutes):

TABLE-US-00003 1.5 2 2.5 3 3.5 4 5 10 20 25 30 35 40 50 60 90 120 1 71 80 100 110 131 151 186 201 178 171 182 199 218 232 240 249 257 2 45 119 155 164 201 206 196 209 301 313 318 330 331 342 342 345 340 3 10 14 30 50 72 88 138 150 213 240 250 267 289 310 318 338 341 4 24 27 36 53 70 93 134 164 211 230 250 266 280 295 300 312 342 5 10 9 8 9 8 7 6 6 Fail 6 54 51 51 51 50 50 50 49 48 50 53 61 63 102 150 196 212

Example 2

[0025] The table below shows the formulation (first table) and corresponding viscosity delay at 200° F. (second table) for example embodiments 7-11. Measurements for embodiments 7-11 were taken using an F50 Unit 2 rheometer.

[0026] Formulation:

TABLE-US-00004 x-Linker loading, CrossLink Water HB Borax Glycerol gpt pH  7 58.36% 11.37% 11.37% 18.61% 1.5 11.26  8 67.34% 11.37% 11.37%  9.63% 1.5 11.23  9 71.82% 15.00%  7.74%  5.16% 1.5 11.32 10 74.37% 13.82%  6.91%  4.61% 1.5 11.4 11 78.08% 17.08%  4.55%  0.00% 1.5 11.5

[0027] Viscosity (in cP) Over Time (in Minutes):

TABLE-US-00005 1.5 2 2.5 3 3.5 4 5 10 20 25 30 35 40 50 60 90 120 7 77 95 126 175 202 237 234 250 255 267 260 264 260 262 259 232 204 8 30 35 61 106 137 172 191 220 181 191 178 173 176 174 170 154 134 9 25 23 24 30 45 67 100 112 128 137 123 121 130 133 132 128 119 10 17 27 40 53 68 85 110 84 83 89 65 76 94 97 97 77 59 11 24 23 21 20 20 21 20 20 Fail

Example 3

[0028] In an alternate embodiment, the present composition further comprises NaOH. NaOH modifies the pH under which the crosslinking reaction takes place, thus moderating the rate at which hydroboracite releases borate ions. The rate at which hydroboracite releases borate ions, in turn, further influences the rate at which the crosslinking reaction progresses.

Formulation 12:

[0029]

TABLE-US-00006 Lab Lab Lab Sp. Blend Blend Blend % by Volume Volume Component State Gravity gms ml lbs Gallon gals lbs. Water Liquid 1  45.58% 2161.54 4.7653065  57% 0.570930541 4.7653065 Hydroboracite Solid 2.2  11.05% 238.19 1.1552575  6% 0.062914182 1.155257499 Borax Liquid 1.73  11.41% 312.77 1.19289485  8% 0.08261302 1.192894848 Canola Oil Liquid 0.916  0.13% 6.73 0.01359126  0% 0.001777693 0.013591265 Xanthan Solid 1.49  0.16% 5.09 0.01672771  0% 0.001345063 0.01672771 Glycerol 99% Liquid 1.26  11.84% 445.63 1.23785057  12% 0.117703699 1.23785057 NaOH 50% Liquid 1.529  19.83% 615.04 2.07319061  16% 0.162451671 2.073190608 Total 100.00% 3785.00 10.4456077 100% 0.999735869 10.44560771 Theoretical 1.25292098 Specific Gravity Desired 1 Volume in gallons:

Example 4

Formulation 1 at 200° F. Measured with Fann 50 Unit 2 Rheometer in DI Water, with Polymer Loading 20 ppt, 1.5 gpt Formulation 1, Poolystim CS 1 gpt

[0030] Formulation 13: Formulation 1 without Canola Oil

TABLE-US-00007 Linear pH Gel Visc Linear Adjust 20 CrossLink Viscosity (in cP) over time (cP) Gel pH (gpt) pH 1 min 1.5 min 2 min 2.5 min 3 min 3.5 min 4 min 5 min 10 min 15 7.6 1 11.6 52 69 83 90 87 87 84 85 121 15 7.6 1 11.6 32 38 50 56 69 70 77 74 104 15 7.6 0.5 10.86 175 163 155 146 136 122 112 106 88 20 min 25 min 30 min 35 min 40 min 50 min 60 min 90 min 120 min 79 100 95 98 95 97 76 95 83 80 86 83 34 29 22

As Compared to Formulation 1:

[0031]

TABLE-US-00008 Linear Gel PfP pH Visc Linear Adjust 20 CrossLink Viscosity (in cP) over time (cP) Gel pH (gpt) pH 1 min 1.5 min 2 min 2.5 min 3 min 3.5 min 4 min 5 min 15.4 7.1 1 11.26 70 77 95 126 175 202 237 234 15.4 7.1 1 11.3 68 70 80 100 140 149 190 210 15.4 7.1 1 11.08 67 69 93 100 100 112 123 199 10 min 20 min 25 min 30 min 35 min 40 min 50 min 60 min 90 min 120 min 250 255 267 260 264 260 262 259 232 204 167 230 265 261 242 255 266 260 260 202 281 293 296 258 261 282 274 270 250 216

Example 5

[0032]

TABLE-US-00009 Linear Cross- Slurry Gel Linear Polystim PfP pH Polystim Linker Cross- Con- Load-ing Visc Gel CS Adjust 20 HTS Formu- loading Link dition (° F.) (gpt) (cP) pH (gpt) (gpt) (gpt) lation (gpt) pH A 270 35 37 7.2 1 2.8 4 1 2.5 12.21 B 280 40 46 7.4 1 2.8 4 1 2.5 12.01 C 300 40 46 7.5 1 3 4 1 3 12.1 D 300 40 46 7.5 1 3.75 5 1 3 12.1

Crosslinked Gel Viscosity in cP Over Time:

[0033]

TABLE-US-00010 Condition 1.5 min 2 min 2.5 min 3 min 3.5 min 4 min 5 min 10 min A 136 195 387 496 560 581 541 548 B 231 407 740 880 862 719 674 781 C 203 244 392 589 714 782 751 982 D 216 393 674 792 797 752 586 781 Condition 20 min 30 min 35 min 40 min 50 min 60 min 90 min 120 min A 257 379 369 404 368 360 272 204 B 659 946 827 826 763 648 479 274 C 342 179 175 160 132 111 84 72 D 320 170 362 206 156 145 86 70

Example 6

Formulation 1

Table Top Crosslinking at Various pH Gel Formulation: 20 ppt PolyFrac Plus M-4.0+1 gpt PolyStim (CS)+See table below Linear Gel Viscosity: 15.4 cP--->Gel pH: 7.20

[0034]

TABLE-US-00011 x-linked gel 9.25 9.54 9.92 10.50 11.2 pH pH Adjust 20 0.12 gpt 0.16 gpt 0.2 gpt 0.4 gpt 0.8 gpt Gel pH 10.3  10.5  10.7  11.05 11.5 Vortex 7 sec 11 sec 11 sec 24 sec 1 min 28 sec Closure Crown 10 sec 14 sec 15 sec 29 sec 1 min 50 sec Lip Instant Instant Instant 41 sec 2 min 11 sec

Example 7

Crosslinking Formulations 1 and 6 at Varying Temperatures

[0035]

TABLE-US-00012 Test pH 1.5 min 2 min 2.5 min 3 min 4 min Temp Formu- Adjust 20 Crosslinker Crosslink Viscocity Viscocity Viscocity Viscocity Viscocity (° F.) lation (gpt) (gpt) pH (cP) (cP) (cP) (cP) (cP) 200 1 0.6 2 10.52 225 240 239 236 213 160 F. 1 0.6 1.5 11.09 45 119 155 164 206 200 1 1 1.5 11.26 77 95 126 175 237 160 F. 1 1 1 11.44 39 49 62 71 104 160 1 1 1 11.03 53 50 51 57 81 160 6 1 1.5 11.26 54 51 51 51 50 160 6 0.16 1.5 9.7 54 51 51 51 50 Test 5 min 10 min 20 min 30 min 35 min 40 min 60 min 90 min 120 min Formu- Temp Viscocity Viscocity Viscocity Viscocity Viscocity Viscocity Viscocity Viscocity Viscocity lation (° F.) (cP) (cP) (cP) (cP) (cP) (cP) (cP) (cP) (cP) 1 200 187 278 285 225 241 246 236 212 211 1 160 F. 196 209 301 318 331 342 342 345 340 1 200 234 250 255 260 264 260 259 232 204 1 160 F. 130 164 213 246 251 262 264 273 275 1 160 110 173 210 235 220 217 231 243 245 6 160 50 50 48 61 63 102 150 196 212 6 160 49 50 48 53 61 75 125 216 210

Example 8

Gel Formulation: PolyFrac Plus+1 gpt PolyStim (CS)+2.0 gpt Hydroboracite x-Linker+See Table Below Linear Gel pH: 7.20

[0036]

TABLE-US-00013 Cross-linked Gel Viscosity, cP @ 100 sec-1 over time in minutes Condition 1.5 2.0 2.5 3.0 3.5 4.0 5.0 10 20 30 40 50 60 90 120 E 96 120 129 140 147 166 200 241 212 178 145 128 130 133 103 F 594 601 605 617 604 583 556 469 310 213 148 108 126 146 147 G 45 119 155 164 201 206 196 209 301 318 331 342 342 345 340 H 39 49 62 71 90 104 130 164 213 246 251 262 264 273 275 I 225 240 239 236 223 213 187 278 285 225 241 246 236 212 211 Test pH X-linker Temp Gel Hydration Adjust20, HTS, Loading, X-linked Condition (° F.) loading Visc, cP gpt gpt Formulation gpt gel pH E  80 F. 20# 15.4 0.4 0 1 1.5 10.61 F  80 F. 20# 15.4 0.6 0 1 2.0 10.2 G 160 F. 20# 15.2 0.6 0 1 1.5 11.09 H 160 F. 20# 15.2 1 0 1 1.0 11.44 I 200 20# 15.4 0.6 0 1 2.0 10.52

Example 9

Formulations 1-12 with Canola Oil and Xanthan

[0037]

TABLE-US-00014 50% Canola NaOH Oil Xanthan Form. # Water % Glycerol HB Borax % % Total  1 58.36% 18.61% 11.37% 11.37% 0.13% 0.16% 100.00%  2 67.34%  9.63% 11.37% 11.37% 0.13% 0.16% 100.00%  3 71.82%  5.16% 15.00%  7.74% 0.13% 0.16% 100.01%  4 74.37%  4.61% 13.82%  6.91% 0.13% 0.16% 100.00%  5 78.08%  0.00% 17.08%  4.55% 0.13% 0.16% 100.00%  6 58.36% 18.61% 22.74%  0.00% 0.13% 0.16% 100.00%  7 29.72% 17.42% 30.84% 22.02% 100.00%  8 32.56% 19.83% 35.09% 12.52% 100.00%  9 50.10% 19.83% 17.55% 12.52% 100.00% 10 65.18% 11.80% 11.37% 11.37% 0.13% 0.16% 100.01% 11 45.42% 19.76% 11.80% 11.37% 11.37% 0.13% 0.16% 100.01% 12 52.03% 17.97% 10.73% 19.03% 0.12% 0.12% 100.00% 50% Canola Water NaOH Glycerol, HB Borax Oil, Xanthan % % % % % % % All 29-79% 17-20% 0-36% 10-23% 0-12% 0-0.13% 0-0.16% formulation Range

[0038] The embodiments disclosed above are various species of the larger genus that is the presently disclosed composition, and methods of making and using that composition that collectively constitute the present disclosure. From this disclosure one of skill in the art can appreciate the relationships among borate ion sources, crosslink reactions, time, an temperature and will be able to readily extrapolate other desired reaction times and the borate ion source balances for achieving those reaction times through routine optimization. One of skill in the art would readily appreciate that further optimization of the formulation of the presently disclosed composition, the proppant fluid into which it is mixed, and the fracking systems and methods in which it is used can vary without departing from the scope of the present disclosure.