Patent Grant
11453817
Described are compositions for use in wellbore fluids in well operations. More specifically, described are compositions with low crystallization temperatures and high densities for use in wellbore fluids in well operations.
When used in well operations, brines can crystallize if exposed to lower temperatures and/or higher pressures. As the density of a brine increases above the salt side of the eutectic point so does the true crystallization temperature (TCT) and pressure crystallization temperature (PCT), which can cause blockage to tubulars in a wellbore or in equipment on the surface if the fluid crystallizes. If crystallization occurs and the solid is filtered from the brine, this will lead to a decrease in fluid density and can cause wellbore stability issues or a blowout. Applying pressure to a brine at a density above the eutectic point will lead to an increase in density, which in turn can lead to crystallization.
Zinc salts, such as zinc bromide (ZnBr2), can be used to increase the density of brines to greater than 14.2 lb/gal while maintaining a low crystallization temperature. However, zinc is a marine pollutant and can cause issues in the processing stage if residual zinc is in the oil sent to the refinery. Addition of zinc brines can cause a sharp decrease in pH leading to high corrosion rates. Cesium formate (CHCsO2) can be used to increase the density of brines to greater than 13.1 lb/gal. Cesium formate is available only in limited supply making it cost-prohibitive for wellbore operations requiring significant volumes of fluid.
Iodide brines can be formulated with higher densities than brines containing chloride or bromide compounds. However, iodide brines are unstable and form iodine when exposed to oxygen or carbon dioxide in air. Brines can pick up carbon dioxide and oxygen from the air when being circulated through a wellbore. Oxygen can oxidize the iodide ion (I−) to iodine (I2). The conversion of iodide to iodine is detrimental to properties of the brine such as discoloration and precipitation. Additionally, the free iodine can destabilize additives present in the brine. Due to this instability, iodide brines have not been widely used in commercial wellbore activity applications.
Described are compositions for use in wellbore fluids in well operations. More specifically, described are compositions with low crystallization temperatures and high densities for use in wellbore fluids in well operations.
In a first aspect, a composition for use in a wellbore activity is provided. The composition includes an iodide brine. The iodide brine operable to be used in the wellbore activity. The iodide brine includes an iodide salt, an aqueous fluid, and an iodide protectant, the iodide protectant operable to prevent the presence of free iodine in the iodide brine, where the iodide protectant is present in the range between 0.001 v/v % and 5 v/v % of the iodide brine.
In certain aspects, the iodide salt is selected from the group consisting of lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, magnesium iodide, calcium iodide, strontium iodide, and combinations of the same. In certain aspects, the iodide brine further includes an additional halide. In certain aspects, the additional halide includes a monovalent halide selected from the group consisting of lithium chloride, lithium bromide, sodium chloride, sodium bromide, potassium chloride, potassium bromide, cesium chloride, cesium bromide, rubidium chloride, rubidium bromide, and combinations of the same. In certain aspects, the additional halide includes a divalent halide selected from the group consisting of calcium bromide, calcium chloride, magnesium bromide, magnesium chloride, strontium bromide, strontium chloride, and combinations of the same. In certain aspects, the iodide protectant is selected from the group consisting of amines, amino alcohols, hydroxylamines, hydrazines, erythorbic acid and derivative erythorbate salts, ascorbic acid and derivative ascorbate salts, citric acid and derivative citrate salts, and combinations of the same.
In a second aspect, a method of using an iodide brine during a wellbore activity is provided. The method includes the steps of introducing the iodide brine into a wellbore and completing the wellbore activity in the wellbore.
In certain aspects, the wellbore activity is selected from the group consisting of drilling, reservoir drilling, completion activities, workover activities, well intervention activities, or as a packer fluid.
While the scope will be described with several embodiments, it is understood that one of ordinary skill in the relevant art will appreciate that many examples, variations and alterations to the apparatus and methods described herein are within the scope and spirit. Accordingly, the exemplary embodiments described herein are set forth without any loss of generality, and without imposing limitations.
The compositions and methods described are directed to iodide brines containing an iodide-containing brine and an iodide protectant.
Advantageously, the addition of an iodide protectant described here demonstrates the ability to stabilize the iodide-containing brines by removing free iodine and protecting against further oxidation. Advantageously, the addition of an iodide protectant to the iodide-containing brines can immediately reduce the presence of iodine even at room temperature as compared to the use of glycerol or sorbitol which can reduce the free iodine, but requires an increase in temperature above ambient to increase the efficacy. Advantageously, the iodide brines have greater densities than conventional divalent and monovalent chloride and bromide brines without the addition of cesium formate or zinc bromide.
As used here, “iodide salt” refers to salts taking the form XI, where I is iodide and where X can be an alkali metal (Group 1), including lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs); or taking the form ZI2, where Z can be an alkaline earth metal (Group 2), including magnesium (Mg), calcium (Ca), and strontium (Sr).
As used here, “iodide protectant” refers to a compound that both scavenges free oxygen present in a brine to prevent further oxidation of the iodide to iodine and reacts with iodine present to produce iodide and stabilize the brine.
As used here, “divalent halide” refers to a salt compound containing an alkaline earth metal (Group 2), including magnesium (Mg), calcium (Ca), and strontium (Sr) and a halogen (Group 17) other than iodine. Examples of the divalent halide can include calcium bromide, calcium chloride, magnesium bromide, magnesium chloride, strontium bromide, strontium chloride, and combinations of the same.
As used here, “monovalent halide” refers to a salt compound containing an alkali metal (Group 1), including lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs) and a halogen (Group 17) other than iodine. Examples of the monovalent halide can include lithium chloride, lithium bromide, sodium chloride, sodium bromide, potassium chloride, potassium bromide, cesium chloride, cesium bromide, rubidium chloride, rubidium bromide, and combinations of the same.
As used here, “additional halide” refers to a monovalent halide, divalent halide, and combinations of the same.
As used here, “brine” refers a liquid fluid containing water and soluble salts.
The iodide brines described here include an iodide-containing brine and an iodide protectant. The iodide-containing brine can be any aqueous fluid containing an iodide salt. In at least one embodiment, the iodide salt can include lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, magnesium iodide, calcium iodide, strontium iodide, and combinations of the same. In at least one embodiment, the iodide salt can include sodium iodide, potassium iodide, calcium iodide, and combinations of the same. In at least one embodiment, the iodide salt can include lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, and combinations of the same. In at least one embodiment, the iodide salt can include magnesium iodide, calcium iodide, strontium iodide, and combinations of the same.
The aqueous fluid can be any water-containing fluid that can be used in wellbore activities. Examples of the aqueous fluid can include water, brine, water-based drilling fluids, and combinations of the same. In at least one embodiment, the aqueous fluid is water. In at least one embodiment, the aqueous fluid is brine.
In addition to the iodide salt, the iodide-containing brine can include an additional halide.
Examples of the iodide protectant can include amines, amino alcohols, hydroxylamines, hydrazines, erythorbic acid and derivative erythorbate salts, ascorbic acid and derivative ascorbate salts, and citric acid and derivative citrate salts, and combinations of the same. Examples of amines include ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), aminoethylpiperazine (AEP), hexaethyleneheptamine (HEHA), piperazine, methoxypropylamine (MOPA), morpholine, n-aminopropylmorpholine (APM), and combinations of the same. Examples of amino alcohols include monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), diethylaminoethanol (DEAE), dimethylethanolamine (DMEA), N-[3-aminopropyl]diethanolamine, aminoethylethanolamine (AEEA), 4-[2-hydroxyethyl]morpholine, diglycolamine, and combinations of the same. Examples of hydroxylamines include diethylhydroxylamine (DEHA), dimethylhydroxylamine (DMHA), hydroxylamine, and combinations of the same. Examples of erythorbate salts include sodium erythorbate. The iodide protectant can be designed to include iodide protectants that can begin to react immediately and those that react as activated, such that the iodide protectant provides both immediate scavenging of dissolved oxygen and long-term protection from oxidation of iodide to iodine.
The amount of iodide protectant in the iodide brine can be in the range between 0.001 percent volume/volume (v/v %) to 5 v/v % of the iodide brine and alternately in the range between 0.01 v/v % and 2.5 v/v %. The amount of iodide protectant can be added until discoloration of the iodide-containing brine disappears or is reduced. An excess amount of iodide protectant above the amount needed to remove the discoloration, but below 5 v/v % can continue to operate in the fluid. An amount of iodide protectant greater than 5 v/v % can negatively impact the pH, such as increasing the pH to a point where hydroxides precipitate, and can reduce the density of the iodide-containing brine.
The iodide brines can be prepared by mixing the iodide-containing brine and iodide protectant at the wellsite or at an offsite location. In an embodiment where the iodide brine is prepared at the wellsite, additional amounts of the components can be added after the initial preparation of the stabilized iodide brine. In an embodiment where the iodide brine is prepared offsite, additional amounts of the iodide salt and iodide protectant can be added at the wellsite to maintain the desired properties.
The iodide brines described here can be used in any wellbore activity during the drilling and completion phases of an oil and gas producing well that requires a brine-based fluid. Wellbore activities can include drilling, reservoir drilling, completion activities, workover activities, well intervention activities, or as a packer fluid.
Example. This example analyzed the use of an iodide protectant in an iodide brine. An iodide-containing brine contained 34.0 wt % water, 13.6 wt % NaBr, 42.4 wt % NaI, and 10 wt % sorbitol. The iodide-containing brine had a density of 15.0 lb/gal measured at a temperature of 60 deg F. and a TCT of 42 deg F. The iodide-containing brine was allowed to stand at ambient temperature for one month at which time the iodide-containing brine was a dark orange color. Sample 1 was maintained as a control sample. Samples 2-7 were created by adding varying amounts of the iodide protectant DEHA to the aged iodide-containing brine to produce iodide brines. The samples were then subjected to American Public Health Associate (APHA) color tests according to ASTM D1209 at times following addition of the DEHA, as indicated in Table 1. The AHPA color tests were conducted to determine the minimum treatment level.
The data in Table 1 demonstrate that a small amount of DEHA, less than 0.005 v/v % can remove free iodine. The data also show that the addition of DEHA can prevent the oxidation of iodide and the production of free iodine. The data also show the time to remove free iodine at ambient temperature based on scavenger concentration.
Although the present embodiments have been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereupon without departing from the principle and scope. Accordingly, the scope should be determined by the following claims and their appropriate legal equivalents.
The singular forms “a,” “an,” and “the” include plural referents, unless the context clearly dictates otherwise.
Optional or optionally means that the subsequently described event or circumstances can or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur.
Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range.
As used herein and in the appended claims, the words “comprise,” “has,” and “include” and all grammatical variations of the same are each intended to have an open, non-limiting meaning that does not exclude additional elements or steps.
As used herein, terms such as “first” and “second” are arbitrarily assigned and are merely intended to differentiate between two or more components of an apparatus. It is to be understood that the words “first” and “second” serve no other purpose and are not part of the name or description of the component, nor do they necessarily define a relative location or position of the component. Furthermore, it is to be understood that that the mere use of the term “first” and “second” does not require that there be any “third” component, although that possibility is contemplated under the scope of the embodiments.
| Number | Name | Date | Kind |
|---|---|---|---|
| 1911195 | Kepfer | May 1933 | A |
| 2191312 | Cannon | Feb 1940 | A |
| 2898294 | Priest et al. | Aug 1959 | A |
| 3275552 | Kern et al. | Sep 1966 | A |
| 4292183 | Sanders | Sep 1981 | A |
| 4444668 | Walker | Apr 1984 | A |
| 4465601 | Pasztor, Jr. | Aug 1984 | A |
| 4486340 | Glass, Jr. | Dec 1984 | A |
| 4566976 | House et al. | Feb 1986 | A |
| 5076364 | Hale et al. | Dec 1991 | A |
| 5330683 | Sufrin | Jul 1994 | A |
| 5415230 | Fisk, Jr. et al. | May 1995 | A |
| 5728652 | Dobson, Jr. | Mar 1998 | A |
| 5846914 | Finkelstein et al. | Dec 1998 | A |
| 6080704 | Halliday et al. | Jun 2000 | A |
| 6100222 | Vollmer et al. | Aug 2000 | A |
| 6124244 | Murphey | Sep 2000 | A |
| 6489270 | Vollmer et al. | Dec 2002 | B1 |
| 6617285 | Crews | Sep 2003 | B2 |
| 6635604 | Halliday et al. | Oct 2003 | B1 |
| 6730234 | Symens et al. | May 2004 | B2 |
| 6843931 | Sapienza | Jan 2005 | B2 |
| 7048961 | Knauf | May 2006 | B2 |
| 7078370 | Crews | Jul 2006 | B2 |
| 7306039 | Wang et al. | Dec 2007 | B2 |
| 7825073 | Welton et al. | Nov 2010 | B2 |
| 7910524 | Welton et al. | Mar 2011 | B2 |
| 7960315 | Welton et al. | Jun 2011 | B2 |
| 8003578 | Monroe et al. | Aug 2011 | B2 |
| 8030254 | Phatak et al. | Oct 2011 | B2 |
| 8067342 | Lin et al. | Nov 2011 | B2 |
| 8071059 | Filippi et al. | Dec 2011 | B2 |
| 8381537 | Morita et al. | Feb 2013 | B2 |
| 8697611 | Zhang et al. | Apr 2014 | B2 |
| 8853135 | Phatak et al. | Oct 2014 | B2 |
| 8936111 | Maghrabi et al. | Jan 2015 | B2 |
| 8950492 | Maghrabi et al. | Feb 2015 | B2 |
| 9593276 | Livanec | Mar 2017 | B2 |
| 9868890 | Alleman | Jan 2018 | B2 |
| 20030092581 | Crews | May 2003 | A1 |
| 20040124013 | Wiesner et al. | Jul 2004 | A1 |
| 20050038199 | Wang et al. | Feb 2005 | A1 |
| 20050101491 | Vollmer | May 2005 | A1 |
| 20050253110 | Chauhan et al. | Nov 2005 | A1 |
| 20080093579 | Knauf | Apr 2008 | A1 |
| 20080269081 | Lin et al. | Oct 2008 | A1 |
| 20090048126 | Phatak et al. | Feb 2009 | A1 |
| 20100016180 | Scoggins et al. | Jan 2010 | A1 |
| 20100093565 | Phatak et al. | Apr 2010 | A1 |
| 20100130388 | Phatak et al. | May 2010 | A1 |
| 20100163255 | Horton et al. | Jul 2010 | A1 |
| 20100303737 | Hurtig | Dec 2010 | A1 |
| 20100311621 | Kesavan | Dec 2010 | A1 |
| 20120118569 | Deville | May 2012 | A1 |
| 20130098615 | Perez et al. | Apr 2013 | A1 |
| 20130168095 | Loveless et al. | Jul 2013 | A1 |
| 20130231268 | Ghosh et al. | Sep 2013 | A1 |
| 20140148366 | Reyes Bautista | May 2014 | A1 |
| 20140221256 | Holtsclaw | Aug 2014 | A1 |
| 20140262283 | Savari et al. | Sep 2014 | A1 |
| 20140352961 | Dobson, Jr. et al. | Dec 2014 | A1 |
| 20150096808 | Misino et al. | Apr 2015 | A1 |
| 20160177698 | Schultheiss et al. | Jun 2016 | A1 |
| 20160208158 | Monahan et al. | Jul 2016 | A1 |
| 20170088762 | Zhang et al. | Mar 2017 | A1 |
| 20170145284 | Davidson et al. | May 2017 | A1 |
| 20170158939 | Chen et al. | Jun 2017 | A1 |
| 20170158976 | O'Rear | Jun 2017 | A1 |
| 20170190954 | Schultheiss et al. | Jul 2017 | A1 |
| 20170292055 | Alleman | Oct 2017 | A1 |
| 20180016484 | Ray et al. | Jan 2018 | A1 |
| Number | Date | Country |
|---|---|---|
| 106928930 | Jul 2017 | CN |
| 0194254 | Sep 1986 | EP |
| 2463350 | Jun 2012 | EP |
| 1863890 | Oct 2014 | EP |
| 2250761 | Jun 1992 | GB |
| 2334279 | Aug 1999 | GB |
| 56098482 | Aug 1981 | JP |
| 20040043935 | May 2004 | KR |
| 9821291 | May 1998 | WO |
| 03064555 | Aug 2003 | WO |
| 2004050557 | Jun 2004 | WO |
| 2009126548 | Oct 2009 | WO |
| 20015068865 | May 2015 | WO |
| 2016025137 | Feb 2016 | WO |
| 2017165754 | Sep 2017 | WO |
| Entry |
|---|
| International Search Report and Written Opinion for related PCT application PCT/US2018/057205 dated Dec. 14, 2018. |
| U.S. Appl. No. 15/468,940 Final Office Action dated Jan. 2, 2019 (10 pages). |
| International Search Report and Written Opinion for related PCT application PCT/US2018/057200 dated Dec. 14, 2018. |
| International Search Report and Written Opinion for related PCT application PCT/US2018/057202 dated Jan. 7, 2019. |
| U.S. Appl. No. 15/791,748 Non-Final Office Action dated Feb. 25, 2019 (28 pages). |
| U.S. Appl. No. 15/468,842 Final Office Action dated Apr. 25, 2019 (12 pages). |
| Kaminski, et al., “Clearly Different”, Reprinted from Oilfield Technology, Jul. 2012, 4 pgs. |
| Section B14 Solubility in Non-Aqueous Solvents, Formate Technical Manual, Mar. 2013, 1-4, Version 1, Cabot Specialty Fluids, 4 pgs. |
| Chen, et al.; Effect of Cryoprotectants on Eutectics of NaCl 2H2O/ice and KCl/ice Studied by Temperature Wave Analysis and Differential Scanning Calorimetry; Thermochimica Acta 431 (2005) 106-112; 7 pgs. |
| PCT/US2017/023995 International Search Report and Written Opinion dated May 24, 2017; 15 Pgs. |
| PCT/US2017/023996 International Search Report and Written Opinion dated May 24, 2017; 16 Pgs. |
| PCT/US2017/024008 International Search Report and Written Opinion dated May 24, 2017; 16 Pgs. |
| Telang, et al., , Effective Inhibition of Mannitol Crystallization in Frozen Solutions by Sodium Chloride, Pharmaceutical Research (Apr. 2003), vol. 20, No. 4, 660-667; 8 pgs. |
| Number | Date | Country | |
|---|---|---|---|
| 20190119557 A1 | Apr 2019 | US |
