WO2020220002A1 - Nanosilica dispersion for thermally insulating packer fluid - Google Patents
Nanosilica dispersion for thermally insulating packer fluid Download PDFInfo
- Publication number
- WO2020220002A1 WO2020220002A1 PCT/US2020/029982 US2020029982W WO2020220002A1 WO 2020220002 A1 WO2020220002 A1 WO 2020220002A1 US 2020029982 W US2020029982 W US 2020029982W WO 2020220002 A1 WO2020220002 A1 WO 2020220002A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nanosilica dispersion
- defined space
- polyamine
- thermally insulating
- packer fluid
- Prior art date
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 135
- 239000012530 fluid Substances 0.000 title claims abstract description 89
- 229920000768 polyamine Polymers 0.000 claims abstract description 65
- 230000002378 acidificating effect Effects 0.000 claims abstract description 53
- 239000007787 solid Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000012190 activator Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 230000015572 biosynthetic process Effects 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 15
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
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- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 8
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 8
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 claims description 5
- 230000017525 heat dissipation Effects 0.000 claims description 4
- KFUSXMDYOPXKKT-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OCC1OC1 KFUSXMDYOPXKKT-UHFFFAOYSA-N 0.000 claims description 3
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 238000005755 formation reaction Methods 0.000 description 25
- 239000000203 mixture Substances 0.000 description 14
- 230000003993 interaction Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000004148 curcumin Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 230000001687 destabilization Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010952 in-situ formation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000006187 pill Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000003180 well treatment fluid Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B36/00—Heating, cooling or insulating arrangements for boreholes or wells, e.g. for use in permafrost zones
- E21B36/003—Insulating arrangements
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/10—Nanoparticle-containing well treatment fluids
Definitions
- the present disclosure generally relates to controlling heat dispersion and heat loss within a wellbore or hydrocarbon-bearing formation. More specifically, embodiments of the disclosure relate to compositions of and methods for using thermally insulating packer fluids to place thermally insulating solid gels in situ.
- Insulating packer fluids are used in subterranean operations, and the fluid is generally placed into an annulus between a first tubing and a second tubing, or the walls of a wellbore.
- the insulating packer fluid acts to insulate hydrocarbon fluid that may be located within the first tubing from the environment surrounding the first tubing or the second tubing to enable optimum recovery of the hydrocarbon fluid. For instance, if the surrounding environment is cold, the insulating packer fluid protects the first fluid in the first tubing from the environment so that it can efficiently flow through the production tubing without cooling to a level hindering production. Preventing cooling is desirable because heat transfer can cause problems such as the precipitation of heavier hydrocarbons, severe reductions in flow rate, and in some cases, casing collapse.
- Such fluids also can be used for similar applications involving pipelines for similar purposes, or in other words to protect a fluid located within the pipeline from the surrounding environmental conditions so that the fluid can efficiently flow through the pipeline.
- Insulating fluids can be used in other insulating applications as well where it is desirable to control heat transfer.
- the present disclosure includes aqueous based thermally insulating packer fluids having low thermal conductivity that can be used in applications requiring an insulating fluid, such as pipeline applications and subterranean applications, including for example wellbores and hydrocarbon-bearing formations.
- the newly-developed thermally insulating packer fluid includes green and environmentally acceptable chemistry, which incorporates acidic nanosilica dispersions and one or more activators. Silica is considered environmentally benign.
- Activators for use in embodiments of the disclosure include a polyamine, for example a polyethylene polyamine.
- Polyethylene polyamines used in the present disclosure include, for example, diethylenetriamine, ethylenediamine, tetraethylenepentamine, triethylentetramine, pentaethylenehexamine, hexaethyleneheptamine, and combinations thereof.
- Beneficial insulating fluids of the present disclosure exhibit a low inherent thermal conductivity and can remain gelled or solidified to prevent, inter alia, convection currents that could carry heat away from a wellbore.
- the insulating fluids in some embodiments are aqueous-based, and easy to handle and use.
- the fluids tolerate greater temperatures (for example, temperatures of about 240 °F or greater) for long periods of time and at optimum performance.
- To produce nanosilica dispersions or colloidal silica sol one method is to remove sodium from sodium silicate via cation exchange. Without the sodium, polymerization takes place and particles begin to grow. After growth, the sol is stabilized and concentrated to the desired content.
- a method for placing thermal insulation in a wellbore or formation including the step of: introducing a thermally insulating packer fluid into the defined space such that the thermally insulating packer fluid forms a gelled solid and reduces a rate of heat transfer through the defined space as compared to a prior rate of heat transfer through the defined space before introducing the thermally insulating packer fluid, where the thermally insulating packer fluid comprises an acidic nanosilica dispersion and a polyamine.
- the polyamine comprises a polyethylene polyamine.
- the step of introducing the thermally insulating packer fluid into the defined space includes the steps of separately introducing the acidic nanosilica dispersion and introducing the polyamine. Still in other embodiments, the step of introducing the thermally insulating packer fluid into the defined space includes introducing the acidic nanosilica dispersion and the polyamine together.
- the acidic nanosilica dispersion comprises amorphous silicon dioxide in a range of about 5 weight percentage of the total weight of the acidic nanosilica dispersion (w/w%) to about 50 w/w% of the total weight of the acidic nanosilica dispersion.
- the acidic nanosilica dispersion comprises water in the range of about 50 w/w% to 95 w/w% of the total weight of the acidic nanosilica dispersion.
- the defined space has a temperature that is at or greater than about 100 °F.
- the defined space is selected from the group consisting of: a defined space in a wellbore, a defined space in a hydrocarbon-bearing formation, a defined space proximate a pipeline, an annulus, and combinations thereof.
- the reduction in the rate of heat transfer through the defined space causes heat dissipation through the defined space to take about 10 times as long as compared to heat dissipation at the prior rate of heat transfer through the defined space, where the defined space comprises water before introducing the thermally insulating packer fluid.
- the polyamine comprises a polyethylene polyamine selected from the group consisting of: diethylenetriamine, ethylenediamine, tetraethylenepentamine, triethylentetramine, pentaethylenehexamine, hexaethyleneheptamine, and combinations thereof.
- a solid gelled material useful for controlling the heat transfer profile through a defined space, where the solid gelled material forms by introducing an acidic nanosilica dispersion to the defined space, the acidic nanosilica dispersion including amorphous silicon dioxide in the range of about 5 weight percentage of the total weight (w/w%) of the acidic nanosilica dispersion to about 50 w/w% of the total weight of the acidic nanosilica dispersion; water in the range of 50 w/w% to 95 w/w% of the total weight of the acidic nanosilica dispersion; an acid; and a polyamine activator; where the acidic nanosilica dispersion forms the solid gelled material at an elevated temperature between about 100 °F and about 300 °F in the defined space.
- the acidic nanosilica dispersion has an initial pH that is acidic and where the acid comprises acetic acid.
- the initial pH is between about 2 and about 4.
- a volumetric ratio of the amorphous silicon dioxide, water, and acetic acid to the polyamine activator is between about 60:1 and 120: 1.
- at least one of the acid and the polyamine activator is consumed during formation of the solid gelled material.
- the polyamine comprises a polyethylene polyamine selected from the group consisting of: diethylenetriamine, ethylenediamine, tetraethylenepentamine, triethylentetramine, pentaethylenehexamine, hexaethyleneheptamine, and combinations thereof.
- FIGS. 1A and IB are photographs of a gelled solid formed by a mixture of an acidic nanosilica dispersion combined with a polyamine activator in accordance with an embodiment of the disclosure
- FIG. 2 is a diagram of an experiment described in this disclosure detailing the enhanced thermal insulating properties of gelled solids of the present disclosure versus water, for example;
- FIG. 3 is a chart showing slower heat loss for a gelled solid of the present disclosure, formed from a thermally insulating packer fluid, versus water.
- Embodiments of the disclosure include a nanosilica dispersion thermally insulating packer fluid optionally for use with pipelines, in wellbores, and in hydrocarbon-bearing formations.
- the nanosilica dispersion may include amorphous silicon dioxide in the range of about 5 weight percentage of the total weight (w/w%) of the nanosilica dispersion to about 50 w/w%, glycerin in the range of about 3 w/w% to about 5 w/w% total weight of the nanosilica dispersion, and water in the range of about 50 w/w% to about 95 w/w% total weight of the nanosilica dispersion. It should be appreciated that other suitable nanosilica dispersions may not include glycerin. The initial viscosity of a nanosilica dispersion readily allows for easy pumping and fluid flow.
- the nanosilica dispersion may be an acidic nanosilica dispersion and may have a pH of less than 7 before interaction with a formation, wellbore, or other area for its placement.
- the nanosilica dispersion thermally insulating packer fluid may be introduced into a space or annulus in a wellbore or formation, such that the nanosilica dispersion thermally insulating packer fluid forms into a solid gelled material and alters the heat transfer profile of the location of its placement.
- the nanosilica dispersion thermally insulating packer fluid can be allowed to interact with a zone where heat transfer profile alteration is desired for a period of time to enable the in-situ formation of a gelled solid as a result of the interaction between the nanosilica dispersion and the location of its placement.
- Embodiments of the disclosure also include a nanosilica dispersion and one or more polyamine activators.
- Polyamines used in the present disclosure include, for example, diethylenetriamine, ethylenediamine, tetraethylenepentamine, triethylentetramine, pentaethylenehexamine, hexaethyleneheptamine, and combinations thereof.
- the nanosilica dispersion may include amorphous silicon dioxide in the range of about 5 w/w% to about 50 w/w%, glycerin in the range of about 3 w/w% to about 5 w/w%, and water in the range of about 50 w/w% to about 95 w/w%.
- Polyamine is used as a chemical activator for converting an acidic nanosilica dispersion into a gelled solid.
- the polyamine reacts with the acid used to stabilize the acidic nanosilica dispersion. This raises the pH of the nanosilica dispersion from acidic to alkaline, which in turn destabilizes the dispersion thereby turning it into a gelled solid.
- either or both of the acid and polyamine are partially or fully consumed during destabilization of the dispersion to avoid damage to a wellbore or hydrocarbon bearing formation.
- the nanosilica dispersion may be an acidic nanosilica dispersion and may have a pH of less than 7 before interaction with the activator.
- Acetic acid for example, in addition to or alternative to other weak acids and strong acids can be used to lower the pH of a nanosilica dispersion and to stabilize the dispersion.
- the nanosilica dispersion and one or more polyamine activators can be introduced into a wellbore, formation, annulus or other defined or confined space, such that the nanosilica dispersion and one or more polyamine activators alter the heat transfer profile of the space.
- the nanosilica dispersion and one or more polyamine activators can be allowed to interact with a space for placement for a period of time to enable the in-situ formation of a gelled solid as a result of the interaction between the nanosilica dispersion and the one or more polyamine activator.
- the nanosilica dispersion while flowing as a fluid can quickly fill cracks and small spaces, and once formed into a gelled solid can alter the heat transfer profile of cracks and small spaces to, for example, reduce heat transfer through the cracks or small spaces.
- the nanosilica dispersion for use as a thermally insulating packer fluid can be an acidic nanosilica dispersion and can have a pH of less than 7 before interaction with a formation or space for placement.
- the nanosilica dispersion includes a stabilizer of acetic acid.
- the nanosilica dispersion has a pH in the range of about 2 to about 4 at 25 °C, a specific gravity of about 1.21 (g/ml), and a viscosity of about or less than about 30 cP at 25°C.
- the nanosilica dispersion may be obtained from Evonik Corporation of Parsippany, New Jersey, USA.
- the nanosilica dispersion for thermally insulating packer fluid can include additional materials.
- the nanosilica dispersion for a thermally insulating packer fluid can include calcium carbonate particles, fibers (such as polyester fibers, polypropylene fibers, starch fibers, polyketone fibers, ceramic fibers, glass fibers or nylon fibers), mica, graphite, or combinations thereof. Additional materials for inclusion into the nanosilica dispersion can be incorporated based on the results of the heat transfer profile of the gelled solid which forms from the thermally insulating packer fluid.
- the nanosilica dispersion and one or more polyamine activator acting as a packer fluid for thermal insulation can be allowed to interact with a space for placement, such as a zone within a wellbore or hydrocarbon-bearing formation, for a period of time.
- the period of time may be of sufficient duration to enable formation of a gelled solid as a result of the interaction between the nanosilica dispersion and the one or more polyamine activator causing destabilization of the dispersion.
- the formed gelled solid may alter the heat transfer profile in a zone of placement (for example, by entering and blocking porous and permeable paths, cracks, and fractures in a formation).
- the interaction period may be in the range of about 0.5 hours to about 24 hours.
- the nanosilica dispersion may form a gelled solid when in contact with calcium carbonate of a formation of a well, for example.
- the pH of the nanosilica dispersion may increase (due to reaction of an acid of the dispersion with the carbonate formation) and become alkaline by an increase in pH.
- the delayed and controlled gelling of the nanosilica dispersion for use as a thermally insulating packer fluid may provide for easier pumping of the nanosilica dispersion for use as a thermally insulating packer fluid.
- the nanosilica dispersion for use as a thermally insulating packer fluid may be used at elevated temperatures in a wellbore such as, for example, 100 °F or greater, such as 300 °F, or any temperature in between or thereabouts.
- the environmentally friendly properties of the nanosilica dispersion for use as a thermally insulating packer fluid can minimize or prevent any environmental impact and effect on ecosystems, habitats, population, crops, and plants at or surrounding the drilling site where the acidic nanosilica dispersion is used.
- the volumetric ratio of the nanosilica dispersion to the one or more polyamine activator is between about 60: 1 to about 120: 1.
- the concentration of the polyamine activator is between about 0.25% by volume and about 10% by volume of the volume of the nanosilica dispersion, or between about 1% by volume and about 5% by volume of the volume of the nanosilica dispersion.
- the one or more polyamine activator can increase the rate of gelation of the nanosilica dispersion as compared to using the nanosilica dispersion alone as a thermally insulating packer fluid.
- the gelling of the nanosilica dispersion may be controlled by varying the concentration of the one or more polyamine activator, and the gelling may be controlled by changing the pH of the nanosilica dispersion for use as a thermally insulating packer fluid.
- increasing concentrations of the one or more polyamine activator may increase the pH of the nanosilica dispersion and increase the rate of gelation of the nanosilica dispersion for use as a thermally insulating packer fluid.
- the one or more polyamine activator exhibits no precipitation with the nanosilica dispersion at elevated temperatures, thus enabling use of the nanosilica dispersion composition as a single fluid pill (that is, without staged mixing of each component). Consequently, the delayed and controlled gelling of the nanosilica dispersion for use as a thermally insulating packer fluid can provide for easier pumping downhole.
- the nanosilica dispersion and one or more polyamine activator can be applied at elevated temperatures in a wellbore such as, for example, 100 °F or greater, such as 300°F.
- the environmentally friendly properties of the nanosilica dispersion and one or more polyamine activator can minimize or prevent any environmental impact and effect on ecosystems, habitats, population, crops, and plants at or surrounding the drilling site where the nanosilica dispersion and polyamine activator is used as a thermally insulating packer fluid.
- the nanosilica dispersion treatment fluid may be introduced into a treatment zone in a well, such as during a well treatment operation.
- the nanosilica dispersion treatment fluid may be pumped through a wellhead at a pump rate sufficient to position the well treatment fluid at the treatment zone.
- the nanosilica dispersion treatment fluid may be introduced using coiled tubing, and can be introduced into an annulus.
- the nanosilica dispersion treatment fluid may be used in producing wells or injection wells.
- the treatment zone may be a zone in a producing well.
- the nanosilica dispersion treatment fluid may be used in combination with secondary and tertiary flooding operations, such as water flooding.
- the nanosilica dispersion treatment fluid may be used to reduce heat loss in wellbore operations where water flooding is used, or where there is other potential for heat loss.
- the nanosilica dispersion treatment fluid may be used with one or more additional treatment fluids.
- the nanosilica dispersion treatment fluid may form a gelled solid when in contact with calcium carbonate of a formation of a well, for example.
- the nanosilica dispersion and one or more polyamine activator may be mixed to form a treatment fluid before use in a wellbore or formation.
- the resulting treatment fluid may be introduced into a treatment zone in a well, such as during a well treatment operation.
- the nanosilica dispersion and one or more polyamine activator for use as a thermally insulating packer fluid may be pumped through a wellhead at a pump rate sufficient to position the well treatment fluid at the treatment zone for altering a heat transfer profile.
- the nanosilica dispersion and polyamine activator treatment fluid may be introduced using coiled tubing.
- the interaction period of the nanosilica dispersion for use as a thermally insulating packer fluid in a space for alteration of a heat transfer profile can be in the range of about 0.5 hours to about 24 hours. In some embodiments, the period may be selected based on the formation type of the treatment zone. For example, in some embodiments the interaction period for a carbonate formation may be about 8 hours for a liquid, fluid nanosilica dispersion to form a gelled solid.
- the acidic nanosilica dispersion used was IDISIL® LPH 35 manufactured by Evonik Corporation of Parsippany, New Jersey, USA.
- the properties of the nanosilica dispersion are described in Table 1:
- the acidic nanosilica dispersion was a milky liquid that was completely miscible in water and had the same evaporation rate as water.
- destabilization, gelling, and solidification of an acidic nanosilica dispersion using a polyamine as an activator was carried out.
- 120 ml of acidic nanosilica dispersion was placed in a beaker.
- the initial pH of acidic nanosilica dispersion was measured to be 3.7.
- 1 ml of a polyamine, specifically Ethyleneamine E-100 was slowly added to the acidic nanosilica with constant stirring. The stirring was performed for 5 minutes. No gelation was observed after stirring.
- Ethyleneamine E-100 is a mixture of tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), hexaethyleneheptamine (HEHA), and greater molecular weight products.
- TEPA tetraethylenepentamine
- PEHA pentaethylenehexamine
- HEHA hexaethyleneheptamine
- E-100 is a complex mixture of various linear, cyclic, and branched products with a number- average molecular weight of 250-300 g/mole.
- Ethyleneamine E-100 is produced by Huntsman Corporation of the Woodlands, TX.
- the general structure of E-100 is represented by the following Formula 1 : H 2 NCH2CH2(NHCH 2 CH2)XN H2
- the resultant pH of the nanosilica dispersion after addition of 1 ml of polyamine was measured to be 9.7.
- This nanosilica dispersion was then placed in a pressurized high temperature high pressure (HTHP) aging cell, and the cell was then subsequently placed in an oven and was static aged at 300 °F for about 16 hours. After 16 hours of static aging at 300 °F, the nanosilica dispersion mixed with polyamine was converted into a gelled solid, shown in FIGS. 1A and IB.
- This gelled solid obtained after static aging at elevated temperature can act as an insulating packer for a hydrocarbon-bearing formation, wellbore, or pipeline and is formed from the acidic nanosilica thermally insulating packer fluid.
- the gelling is permanent, and the gelled solid cannot be solubilized back into liquid in the space into which it is disposed.
- the gel produced is in the form of rigid solid.
- Polyamine is used as a chemical activator for converting an acidic nanosilica dispersion into a gelled solid.
- the polyamine reacts with the acid used to stabilize the acidic nanosilica dispersion. This raises the pH of the nanosilica dispersion from acidic to alkaline. This destabilizes the dispersion thereby turning it into a gelled solid.
- FIG. 2 a heat transfer experiment was carried out to compare to water the heat transfer properties of the gelled solid formed from the acidic nanosilica dispersion with a polyamine activator.
- the thermal insulation property of the packer fluid was evaluated by performing an experiment where a comparison of the cool-down results of the gelled solid versus plain water was made (shown in FIG. 3 and discussed as follows).
- Experimental set-up 200 included two 400 ml glass beakers, one containing the gelled solid 202 formed from the acidic nanosilica dispersion using polyamine as an activator (as described previously), and one containing water 204.
- Two measuring cylinders 206, 208 were then placed in each of the glass beakers.
- plain water 204 was placed surrounding the measuring cylinder 206 while in the other glass beaker, the gelled packer fluid 202 was placed surrounding measuring cylinder 208.
- the gelled packer fluid used in the experiment included an acidic nanosilica dispersion gelled using polyamine as the activator.
- 150 ml of water was disposed in a beaker and was heated up to 110 °F, after which 20 ml of the hot water was poured immediately into the two measuring cylinders 206, 208.
- Two temperature indicators 210, 212 were then placed in each of the measuring cylinders 206, 208, respectively, and the cool-down effect was evaluated by measuring the time taken for the hot water placed in the measuring cylinders to reach 73.7 °F.
- the chart shows that for the gelled insulating packer fluid of the exemplified embodiment, the time required by the hot water to cool from 110 °F to 73.7 °F is about 50 minutes (min), while with plain water, the time required by hot water to cool from 110 °F to 73.7 °F is about 4.5 min.
- the time difference of 45.5 minutes shows that the heat loss in the case of the gelled solid formed from insulating packer fluid is much less than in the case of plain water.
- Some advantages of using such a combination as a thermally insulating packer fluid include: A) Utilizing network structures formed from acidic nanosilica and activators like one or more polyamine to provide a gelled solid from thermally insulating packer fluid; B) The nanosilica gelling time can be controlled by varying the concentration of the activator; C) The packer fluid utilizes environmentally friendly ingredients, as either or both of acid and polyamine are consumed during destabilization of the nanosilica dispersion; D) The gelling tendency of the system can be accelerated by changing the pH of the system from acidic to basic (in other words, the more basic the system, the faster is the gel formation); E) The activator shows no precipitation with nanosilica after mixing or at elevated temperatures (thus the composition can be pumped as a single pill); F) Delayed and controlled gelling of the fluid results in ease of pumping of the fluid; and G) Embodiments can be used at elevated temperatures.
- thermally insulating packer fluid compositions include a nanosilica dispersion at between about 5 w/w% to about 95 w/w% of the composition; an epoxy resin at between about 95 w/w% to about 5 w/w% of the composition; an acid, for example acetic acid in addition to or alternative to other weak or strong acids, to adjust the initial pH of the nanosilica dispersion to between about pH 1 to about pH 5, especially between about pH 2 to about pH 4; and a polyamine at between about 0.5 w/w% to about 10 w/w% of the composition, the polyamine operable to act as an activator or gelling initiator.
- suitable epoxy resins include for example a resin with bisphenol A, epichlorohydrin polymer (between about 60 w/w% to about 100 w/w%), optionally further including phenol, polymer with formaldehyde, glycidyl ether (between about 5 w/w% to about 10 w/w%), optionally further including oxirane, mono[(C12-14-alkyloxy) methyl] derivatives (between about 5 w/w% to about 10 w/w%), optionally further including 1,3-propanediol, 2-ethyl- 2- (hydroxymethyl)-, polymer with (chloromethyl) oxirane (between about 1 w/w% to about 5 w/w%).
- Such an epoxy offers low viscosity, non-crystallization properties, and good chemical and mechanical resistance downhole.
- Another suitable epoxy resin includes 2,3 -epoxypropyl o-tolyl ether, which offers low viscosity and good solvent resistance.
- Another suitable epoxy resin includes C 12-04 alkyl glycidyl ether, which offers low viscosity, flexibility, and low toxicity.
- An additional suitable resin for use in disclosed compositions is 1,6-hexanediol diglycidyl ether, which offers useful mechanical properties for in situ use, and advantageous reactivity with the present compositions.
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WO2023192472A1 (en) * | 2022-03-31 | 2023-10-05 | Saudi Arabian Oil Company | Systems and methods in which colloidal silica gel is used to seal a leak in or near a packer disposed in a tubing-casing annulus |
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WO2014085317A1 (en) * | 2012-11-29 | 2014-06-05 | M-I L.L.C. | High temperature viscosifier for insulating packer fluids |
WO2014085770A1 (en) * | 2012-11-29 | 2014-06-05 | M-I L.L.C. | Colloidal silica and polymer system for insulating packer fluids |
WO2019051014A1 (en) * | 2017-09-11 | 2019-03-14 | Saudi Arabian Oil Company | Nanosilica dispersion for thermally insulating packer fluid |
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WO2014085317A1 (en) * | 2012-11-29 | 2014-06-05 | M-I L.L.C. | High temperature viscosifier for insulating packer fluids |
WO2014085770A1 (en) * | 2012-11-29 | 2014-06-05 | M-I L.L.C. | Colloidal silica and polymer system for insulating packer fluids |
WO2019051014A1 (en) * | 2017-09-11 | 2019-03-14 | Saudi Arabian Oil Company | Nanosilica dispersion for thermally insulating packer fluid |
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WO2023192472A1 (en) * | 2022-03-31 | 2023-10-05 | Saudi Arabian Oil Company | Systems and methods in which colloidal silica gel is used to seal a leak in or near a packer disposed in a tubing-casing annulus |
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